TW201912723A - Curable composition, cured film, laminated body, near infrared cut-off filter, solid-state imaging element, image display device, and infrared sensor - Google Patents

Abstract

Provided is a curable composition which has good storage stability and with which a cured film having few aggregates originating from a near infrared absorbing pigment can be formed. Also provided are a cured film, a laminated body, a near infrared cut-off filter, a solid-state imaging element, an image display device, and an infrared sensor. The curable composition comprises a near infrared absorbing pigment, a radical polymerizable compound, and a radical polymerization initiator A, wherein the radical polymerization initiator A is a pinacol compound or a compound having a thermal decomposition temperature of 120 to 270 DEG C and a thermal decomposition rate of 33 to 60 W/DEG C.mol.

Description

Curable composition, cured film, laminated body, near-infrared cut filter, solid-state imaging device, image display device, and infrared sensor

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

A solid-state imaging device that uses a color image, such as a video camera, a digital camera, a mobile phone with a camera function, or the like, is a CCD (Charge Coupled Device) or a CMOS (Complementary Metal Oxide Semiconductor). These solid-state imaging devices use a neon diode having sensitivity to infrared rays in the light receiving portion. Therefore, the near-infrared cut filter is sometimes used to perform the visibility correction. The near-infrared cut filter is produced, for example, using a curable composition containing a near-infrared absorbing agent such as a near-infrared absorbing dye.

Further, Patent Document 1 discloses a near-infrared absorbing agent obtained by mixing and mixing a dimerized thiourea derivative and a copper compound at a molar ratio of 8:2 to 1:2 in 100 parts by mass of a polymerizable raw material. After the composition is used in an amount of 0.1 to 1.5 parts by mass, the mixture is heated and polymerized in the presence of an azo radical polymerization initiator to produce a near-infrared absorbing molded article. Further, in Patent Document 1, 2,2'-azobisisobutyronitrile is used as an azo radical polymerization initiator. [Prior Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. Hei 6-299139

When a cured film is produced using a curable composition containing a near-infrared absorbing pigment, a cured film may be produced using a curable composition immediately after preparation, and a cured film may be produced using a curable composition stored for a long period of time after preparation. However, according to the study of the present inventors, the curable composition containing the azo-based radical polymerization initiator described in Patent Document 1 has poor storage stability, and the curable composition immediately after the production is used. In the case and the use of the curable composition after storage, the spectral characteristics of the cured film obtained are likely to vary.

Further, according to the study of the present inventors, when a cured film is produced using a curable composition containing a near-infrared absorbing dye as a dye compound as a near-infrared absorbing agent, the near-infrared absorbing pigment is easily condensed at the time of film formation. tendency. In particular, when heat is applied during film formation, the near-infrared absorbing pigment tends to aggregate easily. When the size of the aggregate derived from the near-infrared absorbing pigment in the film is increased, the spectral characteristics may be deviated or the smoothness of the film surface may be lowered. Further, when the size of the aggregate becomes large, the aggregate tends to peel off from the film, and there is a possibility that pores having a size of aggregates are generated in a portion where the aggregate has existed. In addition, the composition of the near-infrared absorbing agent which is obtained by mixing the dimerized thiourea derivative and the copper compound in a molar ratio of 8:2 to 1:2 as described in Patent Document 1 is different from the dye compound. The compound is one of copper complex compounds having a dimerized thiourea derivative as a ligand.

Therefore, an object of the present invention is to provide a curable composition which is excellent in storage stability and capable of producing a cured film obtained by suppressing generation of aggregates derived from a near-infrared absorbing pigment. Further, the present invention provides a cured film, a laminate, a near-infrared cut filter, a solid-state image sensor, an image display device, and an infrared sensor.

According to the study by the present inventors, it has been found that storage stability can be formed by using a predetermined radical polymerization initiator in a curable composition containing a near-infrared absorbing dye, a radical polymerizable compound, and a radical polymerization initiator. The present invention has been completed by a cured film which is good and has few aggregates derived from a near-infrared absorbing pigment. Accordingly, the present invention provides the following. <1> A curable composition comprising a near-infrared absorbing dye, a radically polymerizable compound, and a radical polymerization initiator A, and a radical polymerization initiator A is a pinacol compound. <2> A curable composition comprising a near-infrared absorbing dye, a radically polymerizable compound, and a radical polymerization initiator A, and a radical polymerization initiator A having a thermal decomposition temperature of 120 to 270 ° C and a thermal decomposition rate It is a compound of 33 to 60 W/°C•mol. <3> The curable composition according to <2>, wherein the radical polymerization initiator A is a pinacol compound. The curable composition according to any one of the above aspects, wherein the content of the radical polymerization initiator A is from 0.1 to 20% by mass based on the total solid content of the curable composition. The curable composition according to any one of the above-mentioned <1>, wherein the radical polymerization initiator A is contained in an amount of 1 to 100 parts by mass based on 100 parts by mass of the radically polymerizable compound. . The curable composition according to any one of <1> to <5> further comprising a radical polymerization initiator B different from the radical polymerization initiator A. <7> The curable composition according to <6>, wherein the radical polymerization initiator B is at least one selected from the group consisting of an α-hydroxyacetophenone compound and a benzyldimethylketal. <8> The curable composition according to <6> or <7>, wherein the radical polymerization initiator B has a thermal decomposition temperature of from 100 to 270 °C. <9> The curable composition according to any one of <6> to <8> wherein the radical polymerization initiator B has a thermal decomposition rate of 3 to 10 W/° C. mol. The hardening composition according to any one of <6> to <9>, wherein the radical polymerization initiation is contained in an amount of 0.1 to 2000 parts by mass based on 100 parts by mass of the radical polymerization initiator A. Agent B. <11> A cured film obtained by the curable composition according to any one of <1> to <10>. <12> A laminate having the cured film of <11> on the support. <13> The laminate according to <12>, which has a film obtained by using a composition having a cyclic ether group between the support and the cured film. <14> The laminate according to <12> or <13> wherein the support system contains a glass substrate of copper. The laminate according to any one of <12> to <14> which has an inorganic film on the cured film. <16> The laminate according to <15>, which has a planarization layer between the cured film and the inorganic film. <17> A near-infrared cut filter having the cured film according to <11>. <18> A solid-state image sensor having the cured film according to <11>. <19> An image display device comprising the cured film according to <11>. <20> An infrared sensor having the cured film of <11>. [Effect of the invention]

According to the present invention, it is possible to provide a curable composition which is excellent in storage stability and which can form a cured film derived from a near-infrared absorbing pigment. Moreover, the present invention can provide a cured film, a laminate, a near-infrared cut filter, a solid-state image sensor, an image display device, and an infrared sensor.

Hereinafter, the contents of the present invention will be described in detail. In the present specification, the numerical range expressed by "~" means a range including the numerical values described before and after "~" as the lower limit and the upper limit. In the label of the group (atomic group) in the present specification, the label which is not labeled with a substituent and which is not substituted includes a group having no substituent (atomic group), and further contains a group having a substituent (atomic group). For example, "alkyl" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group). In the present specification, the "exposure" includes not only the exposure using light but also the use of particle beams such as an electron beam or an ion beam, unless otherwise specified. Further, examples of the light used for the exposure include an open line spectrum of a mercury lamp, an ultraviolet ray represented by an excimer laser, an extreme ultraviolet ray (EUV light), an X-ray, an electron beam, or the like, or radiation. In the present specification, "(meth) acrylate" means either or both of acrylate and methacrylate, and "(meth)acrylic acid" means either or both of acrylic acid and methacrylic acid, "(A) The "allyl" group means either or both of an allyl group and a methallyl group, and "(meth)acryloyl group" means either or both of an acryloyl group and a methacryl group. In the present specification, the weight average molecular weight and the number average molecular weight are defined by polystyrene-converted values measured by gel permeation chromatography (GPC). In the present specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) can be, for example, manufactured by using HLC-8220 (manufactured by OSOH CORPORATION) using TSKgel Super AWM-H (manufactured by OSOH CORPORATION, 6.0 mm ID (inner diameter) × 15.0). Cm) was determined as a column using a 10 mmol/L lithium bromide NMP (N-methylpyrrolidone) solution as a solution. In the present specification, near-infrared light refers to light having a wavelength of 700 to 2,500 nm. In the present specification, the total solid content refers to the total mass of the components after removing the solvent from all the components of the composition. In the present specification, the term "step" means not only an independent step but also a term that is not clearly distinguishable from other steps, as long as the desired effect of the step can be achieved.

<Curable composition> The first aspect of the curable composition of the present invention is characterized by comprising a near-infrared absorbing dye, a radically polymerizable compound, a radical polymerization initiator A, and a radical polymerization initiator A. Fredar alcohol compound. Further, the second aspect of the curable composition of the present invention is characterized in that it contains a near-infrared absorbing dye, a radical polymerizable compound, and a radical polymerization initiator A, and the radical polymerization initiator A has a thermal decomposition temperature of A compound having a thermal decomposition rate of from 120 to 270 ° C and a heat decomposition rate of from 33 to 60 W/° C. mol.

The curable composition of the present invention has good storage stability and can produce a cured film having less aggregates derived from a near-infrared absorbing pigment. The reason why such an effect can be obtained is presumed to be based on the following. That is, since the curable composition of the present invention contains a radically polymerizable compound and the above-mentioned radical polymerization initiator A, the polymerization of the radically polymerizable compound is polymerized by radical polymerization by heating the curable composition. The action of the radical generated by the initiator A proceeds rapidly, and the film can be rapidly hardened. Therefore, it is presumed that the near-infrared absorbing pigment rapidly enters into a crosslinked network or the like in the film. Therefore, it is estimated that the curable composition of the present invention can effectively suppress the aggregation of the near-infrared absorbing pigment at the time of heating, and can produce a cured film having less aggregates derived from the near-infrared absorbing pigment. In addition, when the stability of the radical polymerization initiator is low, the radical polymerization initiator is decomposed during storage of the curable composition to generate a radical, and radical polymerization is carried out by the radical. In the polymerization reaction of the compound, the viscosity of the curable composition increases with time, or the near-infrared absorbing pigment aggregates in the composition, or the near-infrared absorbing pigment tends to be modified by the action of a radical, but the above radical polymerization The starter A can be stably present in the curable composition. Therefore, the curable composition of the present invention can suppress an increase in viscosity during storage, aggregation of a near-infrared absorbing pigment, or modification of a near-infrared absorbing pigment by a radical, and is excellent in storage stability. Hereinafter, each component of the curable composition of the present invention will be described.

<<Near-infrared absorbing pigment>> The curable composition of the present invention contains a near-infrared absorbing dye. The near-infrared absorbing pigment 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). Further, it is also preferred to use a near infrared absorbing dye and a near infrared absorbing pigment in combination. When the near infrared absorbing dye and the near infrared absorbing pigment are used in combination, the mass ratio of the near infrared absorbing dye to the near infrared absorbing pigment is near infrared absorbing dye: near infrared absorbing pigment = 99.9: 0.1 to 0.1: 99.9 is preferable, 99.9: 0.1 ～10:90 is more preferable, and 99.9: 0.1 to 20:80 is further preferable.

In the present invention, the solubility of the near-infrared absorbing dye to 100 g of at least one solvent selected from the group consisting of cyclopentanone, cyclohexanone and dipropylene glycol monomethyl ether at 23 ° C is preferably 1 g or more, more preferably 2 g or more, and 5 g is more preferable. The above is further preferred. Further, the solubility of the near-infrared absorbing pigment for 100 g of each solvent of cyclopentanone, cyclohexanone, and dipropylene glycol monomethyl ether at 23 ° C is preferably less than 1 g, more preferably 0.1 g or less, and further preferably 0.01 g or less. .

The near-infrared absorbing dye is preferably a compound having a π-conjugated plane of an aromatic ring containing a monocyclic ring or a condensed ring. By the interaction of the aromatic rings in the π-conjugated plane of the near-infrared absorbing dye, it is easy to form a J-association of the near-infrared absorbing pigment when the cured film is produced, and it is possible to produce a cured film having excellent spectral characteristics in the near-infrared region.

The number of atoms other than hydrogen constituting the π conjugate plane of the near infrared absorbing dye is preferably 6 or more, more preferably 14 or more, still more preferably 20 or more, and still more preferably 25 or more. More than 30 are particularly good. The upper limit is preferably 80 or less, more preferably 50 or less.

The π conjugate plane of the near-infrared absorbing dye contains preferably two or more aromatic rings of a single ring or a fused ring, more preferably three or more, more preferably four or more, and more preferably five or more. It is especially good. The upper limit is preferably 100 or less, more preferably 50 or less, and still more preferably 30 or less. Examples of the aromatic ring include a benzene ring, a naphthalene ring, an anthracene ring, an anthracene ring, a heptalene ring, a terpene ring, an anthracene ring, a fused pentacene ring, a quarterene ring, and an ethane group. Anathaphthene ring, phenanthrene ring, anthracene ring, fused tetraphenyl ring, chrysene ring, extended triphenyl ring, anthracene ring, pyridine ring, quinoline ring, isoquinoline ring, imidazole ring, benzimidazole ring , pyrazole ring, thiazole ring, benzothiazole ring, triazole ring, benzotriazole ring, indazole ring, benzoxazole ring, imidazoline ring, pyrazine ring, quinoxaline ring, pyrimidine ring, quin An oxazoline ring, a pyridazine ring, a triazine ring, a pyrrole ring, an anthracene ring, an isoindole ring, an indazole ring, and a condensed ring having the rings.

The near-infrared absorbing dye is preferably a compound having a maximum absorption wavelength in the range of 700 to 1,300 nm, and more preferably a compound having a maximum absorption wavelength in the range of 700 to 1,000 nm. In the present specification, the phrase "having a maximum absorption wavelength in the range of 700 to 1,300 nm" means that the absorption spectrum in the solution of the near-infrared absorbing dye has the largest absorbance in the wavelength range of 700 to 1,300 nm. The wavelength. Examples of the measurement solvent used for the measurement of the absorption spectrum in the solution of the near-infrared absorbing dye include chloroform, methanol, dimethyl hydrazine, ethyl acetate, and tetrahydrofuran. When the near-infrared absorbing pigment is a compound dissolved in chloroform, chloroform is used as a measuring solvent. In the case of a compound which is not dissolved in chloroform, methanol is used. Further, in the case where it is not dissolved in both chloroform and methanol, dimethyl fluorene is used.

Near infrared absorbing dye having a maximum absorption wavelength and the absorbance A at 0.08 under the wavelength of 500nm ¹ and A ² in a ratio of maximum absorption at the wavelength of the absorbance A ¹ / A ² is a preferred system in the wavelength range of 700 ~ 1,000nm, 0.04 The following is better. In this way, it is easy to produce a cured film excellent in visible transparency and near-infrared shielding properties.

In the present invention, it is also preferred to use at least two kinds of compounds having different maximum absorption wavelengths as the near-infrared absorbing pigment. According to this aspect, the waveform of the absorption spectrum of the obtained cured film is expanded as compared with the case where one type of near-infrared absorbing dye is used, and it is possible to shield near-infrared rays in a wide wavelength range. When at least two kinds of compounds having different maximum absorption wavelengths are used, at least a first near-infrared absorbing dye having a maximum absorption wavelength in a wavelength range of 700 to 1,000 nm and a wavelength shorter than a maximum absorption wavelength of the first near-infrared absorbing dye are included. The second near-infrared absorbing dye having a maximum absorption wavelength in the range of 700 to 1,000 nm, and the difference between the maximum absorption wavelength of the first near-infrared absorbing dye and the maximum absorption wavelength of the second near-infrared absorbing dye is 1 to 150 nm. It is better.

In the present invention, the near-infrared absorbing pigment is selected from the group consisting of a pyrrolopyrrole compound, a cyanine compound, a squaraine compound, a phthalocyanine compound, a naphthalocyanine compound, a quartetene compound, a merocyanine compound, a ketoxime compound, At least one of an oxaphthalocyanine compound, a diimine compound, a dithiol compound, a triarylmethane compound, a pyrromethene compound, a methine azo compound, an anthraquinone compound, and a dibenzofuranone compound is preferred. At least one selected from the group consisting of a pyrrolopyrrole compound, a cyanine compound, a squaraine compound, a phthalocyanine compound, a naphthalocyanine compound, and a quartetene compound is more preferably selected from the group consisting of a pyrrolopyrrole compound, a cyanine compound, and At least one of the squaraine compounds is further preferred, and the pyrrolopyrrole compound is particularly preferred. The diimine compound is, for example, a compound described in JP-A-2008-528706, which is incorporated herein by reference. Examples of the phthalocyanine compound include a compound described in paragraph 0093 of JP-A-2012-077153, and a titanyl phthalocyanate described in JP-A-2006-343631, JP-A-2013-195480 The compound described in Paragraph Nos. 0013 to 0029 of the Japanese Patent Publication No. 6081177, and the vanadium phthalocyanine described in Japanese Patent No. 6081771 are incorporated herein by reference. The naphthylphthalocyanine compound is, for example, a compound described in Paragraph No. 0093 of JP-A-2012-077153, which is incorporated herein by reference. Further, as the cyanine compound, the phthalocyanine compound, the naphthalocyanine compound, the diimine compound, and the squaraine compound, the compound described in Paragraph No. 0010 to 0081 of JP-A-2010-111750 can be used, and the content is introduced. In this manual. Further, the cyanine compound can be referred to, for example, "Functional Pigment, Okawara Shinko / Matsuoka Kenji / Kitajima Jiro / Hiratsuka Hiroshi, Kodansha Scientific Ltd.", which is incorporated herein by reference. Further, as the near-infrared absorbing dye, a compound described in JP-A-2016-146619 can also be used, and the content is incorporated in the present specification. Further, a near-infrared absorbing dye is preferably a compound having the following structure. [Chemical Formula 1]

As the pyrrolopyrrole compound, a compound represented by the formula (PP) is preferred. [Chemical Formula 2] In the formula, R ^1a and R ^1b each independently represent an alkyl group, an aryl group or a heteroaryl group, and R ² and R ³ each independently represent a hydrogen atom or a substituent, and R ² and R ³ may be bonded to each other to form a ring. R ⁴ each 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 may be covalently bonded to at least one selected from the group consisting of R ^1a , R ^1b and R ³ . A knot or a coordination bond, and R ^4A and R ^4B each independently represent a substituent. R ^4A and R ^4B may be bonded to each other to form a ring. For the details of the formula (PP), reference is made to paragraphs 0017 to 0047 of JP-A-2009-263614, paragraphs 0011 to 0036 of JP-A-2011-068731, and paragraphs of WO01/166873. The contents of the numbers 0010 to 0024 are incorporated in the present specification.

In the formula (PP), R ^1a and R ^1b are each independently an aryl group or a heteroaryl group, and an aryl group is more preferable. Further, the alkyl group, the aryl group and the heteroaryl group represented by R ^1a and R ^1b may have a substituent or may be unsubstituted. The substituent described in Paragraph No. 0020 to 0022 of JP-A-2009-263614 or the following substituent T can be mentioned as a substituent.

(Substituent T) an alkyl group (preferably an alkyl group having 1 to 30 carbon atoms), an alkenyl group (preferably an alkenyl group having 2 to 30 carbon atoms), an alkynyl group (preferably an alkyne having 2 to 30 carbon atoms) An aryl group (preferably an aryl group having 6 to 30 carbon atoms), an amine group (preferably an amine group having 0 to 30 carbon atoms), an alkoxy group (preferably an alkoxy group having 1 to 30 carbon atoms) a aryloxy group (preferably an aryloxy group having 6 to 30 carbon atoms), a heteroaryloxy group, a decyl group (preferably a fluorenyl group having 1 to 30 carbon atoms), an alkoxycarbonyl group (preferably An alkoxycarbonyl group having 2 to 30 carbon atoms, an aryloxycarbonyl group (preferably an aryloxycarbonyl group having 7 to 30 carbon atoms), a decyloxy group (preferably a decyloxy group having 2 to 30 carbon atoms), Amidino group (preferably a decylamino group having 2 to 30 carbon atoms), an alkoxycarbonylamino group (preferably an alkoxycarbonylamino group having 2 to 30 carbon atoms), or an aryloxycarbonylamino group (more) Preferably, it is an aryloxycarbonylamino group having 7 to 30 carbon atoms, an aminesulfonyl group (preferably an amidoxime group having a carbon number of 0 to 30), an amine formazan group (preferably having a carbon number of 1 to 30) An amidinoyl group, 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), An arylthio group (preferably having a carbon number of 1 to 30), an alkylsulfonyl group (preferably having a carbon number of 1 to 30), an arylsulfonyl group (preferably having a carbon number of 6 to 30), and a heteroarylsulfonyl group. Sulfhydryl group (preferably having a carbon number of 1 to 30), alkylsulfinyl group (preferably having a carbon number of 1 to 30), arylsulfinyl group (preferably having a carbon number of 6 to 30), and a heteroaryl group. A sulfinyl group (preferably having a carbon number of 1 to 30), a urea group (preferably having a carbon number of 1 to 30), a hydroxyl group, a carboxyl group, a sulfonic acid group, a phosphoric acid group, a carboxylic acid sulfonium group, and a sulfonic acid sulfonium group. And an anthranilic acid group, a mercapto group, a halogen atom, a cyano group, an alkylsulfinic acid group, an arylsulfinic acid group, a fluorenyl group, an imido group, or a heteroaryl group (preferably having a carbon number of 1 to 30). When the groups are groups which can be further substituted, they may further have a substituent. The substituent described in the above substituent T can be mentioned as a substituent.

Specific examples of the group 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 a nonyloxy group as a substituent.

In the formula (PP), R ² and R ³ each independently represent a hydrogen atom or a substituent. The substituent T is mentioned as a substituent. It is preferred that at least one of R ² and R ³ is an electron withdrawing group. A substituent in which the Hammett substituent σ value (sigma value) is positive acts as an electron withdrawing group. Here, the substituent constants obtained by the Hammett equation have σp values and σm values. This value can be viewed in a large number of general publications. 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 further preferably 0.35 or more. The upper limit is not particularly limited, but is preferably 0.80 or less. Specific examples of the electron withdrawing group include a cyano group (σp value = 0.66), a carboxyl group (-COOH: σp value = 0.45), an alkoxycarbonyl group (for example, -COOMe: σp value = 0.45), and an aryloxy group. A carbonyl group (for example, -COOPh: σp value = 0.44), an amine carbenyl group (for example, -CONH ₂ : σp value = 0.36), an alkylcarbonyl group (for example, -COMe: σp value = 0.50), an arylcarbonyl group (for example, -COPh) : σp value = 0.43), alkylsulfonyl group (for example, -SO ₂ Me: σp value = 0.72), arylsulfonyl group (for example, -SO ₂ Ph: σp value = 0.68), etc., and cyano group is preferred. . Here, Me represents a methyl group, and Ph represents a phenyl group. Further, regarding the Hammett's substituent constant σ value, for example, paragraphs 0017 to 0018 of JP-A-2011-068731 can be referred to, and the contents are incorporated in the present specification.

In the formula (PP), R ² represents an electron withdrawing group (preferably a cyano group), and R ³ represents a heteroaryl group. A heteroaryl 5-membered or 6-membered ring is preferred. Further, a heteroaryl group monocyclic or fused ring is preferred, and a monocyclic ring or a condensed ring having a condensation number of 2 to 8 is preferred, and a fused ring having a single ring or a condensation number of 2 to 4 is more preferable. The number of hetero atoms constituting the heteroaryl group is preferably from 1 to 3, more preferably from 1 to 2. Examples of the hetero atom include a nitrogen atom, an oxygen atom, and a sulfur atom. It is preferred that the heteroaryl group has one or more nitrogen atoms. The two R ² in the formula (PP) may be the same or different from each other. Further, two R ³ in the formula (PP) may be the same or different.

In the formula (PP), R ⁴ is a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group or a group represented by -BR ^4A R ^4B is preferred, and a hydrogen atom, an alkyl group, an aryl group or a -BR ^4A R ^{4B group.} The group represented is more preferably, and the group represented by -BR ^4A R ^4B is further preferred. As the substituent represented by R ^4A and R ^4B , a halogen atom, an alkyl group, an alkoxy group, an aryl group or a heteroaryl group is preferred, an alkyl group, an aryl group or a heteroaryl group is more preferable, and an aryl group is particularly preferable. . These groups may further have a substituent. The two R ⁴ in the formula (PP) may be the same or different from each other. R ^4A and R ^4B may be bonded to each other to form a ring.

Specific examples of the compound represented by the formula (PP) include the following compounds. In the following structural formula, Ph represents a phenyl group. Further, examples of the pyrrolopyrrole compound include the compounds described in paragraphs 0016 to 0058 of JP-A-2009-263614, and the compounds described in paragraphs 0037 to 0052 of JP-A-2011-068731. The compounds described in paragraphs 0010 to 0033 of WO 2015/166873, the contents of which are incorporated herein by reference. [Chemical Formula 3] [Chemical Formula 4]

As the squaraine compound, a compound represented by the following formula (SQ) is preferred. [Chemical Formula 5] In the formula (SQ), A ¹ and A ² each independently represent an aryl group, a heteroaryl group or a group represented by the formula (A-1); [Chemical Formula 6] In the formula (A-1), Z ¹ represents a non-metal atomic group forming a nitrogen-containing hetero ring, R ² represents an alkyl group, an alkenyl group or an aralkyl group, d represents 0 or 1, and a wavy line represents a linking bond. For the details of the formula (SQ), reference is made to paragraphs 0020 to 0049 of JP-A-2011-208101, paragraphs 0043 to 0062 of Japanese Patent No. 6065169, and paragraph number 0024 of International Publication WO2016/181987. In the description of ～0040, the contents are incorporated in the specification.

Further, in the formula (SQ), the cations are delocalized as follows. [Chemical Formula 7]

The squaraine compound is preferably a compound represented by the following formula (SQ-1). [Chemical Formula 8] Ring A and Ring B each independently represent an aromatic ring, and X ^A and X ^B each independently represent a substituent, and G ^A and G ^B each independently represent a substituent, kA represents an integer of 0 to n _A , and kB represents 0 to An integer of n _B , n _A and n _B represent the largest integers that can be substituted on ring A or ring B, respectively, and 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. When there are a plurality of G ^A and G ^B respectively, they may be bonded to each other to form a ring structure.

The substituent represented by G ^A and G ^B may, for example, be a substituent T described in the above formula (PP).

As the substituent represented by X ^A and X ^B , a group having an active hydrogen is preferable, -OH, -SH, -COOH, -SO ₃ H, -NR ^X1 R ^X2 , -NHCOR ^X1 , -CONR ^X1 R ^X2 , -NHCONR ^X1 R ^X2 , -NHCOOR ^X1 , -NHSO ₂ R ^X1 , -B(OH) ₂ and -PO(OH) ₂ are more preferred, and -OH, -SH and -NR ^X1 R ^X2 are further preferred. . R ^X1 and R ^X1 each independently represent a hydrogen atom or a substituent. The substituent represented by X ^A and X ^B may, for example, be an alkyl group, an aryl group or a heteroaryl group, and an alkyl group is preferred.

Ring A and Ring B each independently represent an aromatic ring. The aromatic ring may be a single ring or a condensed ring. Specific examples of the aromatic ring include a benzene ring, a naphthalene ring, an anthracene ring, an anthracene ring, a heptene ring, a terpene ring, an anthracene ring, a fused pentabenzene ring, an ethane naphthalene ring, a phenanthrene ring, and an anthracene ring. Ring, fused tetraphenyl ring, anthracene ring, extended triphenyl ring, anthracene ring, biphenyl ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, indazole ring, thiazole ring, pyridine ring, pyrazine ring, pyrimidine ring , pyridazine ring, pyridazine ring, anthracene ring, benzofuran ring, benzothiophene ring, isobenzofuran ring, quinolizine ring, quinoline ring, pyridazine ring, naphthyridine ring, quinoxaline ring, a quinoxaline ring, an isoquinoline ring, an indazole ring, a phenazin ring, an acridine ring, a phenanthroline ring, a thiophene ring, a chromene ring, a mouth of a mountain ring, a thiophene ring, a phenothiazine ring, and A phenazine ring, a benzene ring or a naphthalene ring is preferred. The aromatic ring may be unsubstituted or may have a substituent. The substituent T described in the above formula (PP) is exemplified as the substituent.

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. When a plurality of G ^A and G ^B are respectively present, they may be bonded to each other to form a ring. As the ring, a 5-member ring or a 6-member ring is preferred. The ring may be a single ring or a condensed ring. 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, the groups may be directly bonded to form a ring, or may be extended via an alkyl group. -CO-, -O-, -NH-, -BR- and a divalent linking group containing such a combination are bonded to form a ring. R represents a hydrogen atom or a substituent. The substituent T, the alkyl group or the aryl group described in the above formula (PP) is preferred.

kA represents an integer of 0 to n _A , kB represents an integer of 0 to n _B , n _A represents the largest integer which can be substituted on the ring A, and n _B represents the largest integer which can be substituted on the ring B. It is preferable that kA and kB are independently 0 to 4, 0 to 2 is more preferable, and 0 to 1 is particularly preferable.

The squaraine compound is preferably a compound represented by the following formula (SQ-10), formula (SQ-11) or formula (SQ-12). Formula (SQ-10) [Chemical Formula 9] Formula (SQ-11) [Chemical Formula 10] Formula (SQ-12) [Chemical Formula 11]

In the formulae (SQ-10) to (SQ-12), X is independently a formula (1) or a formula in which one or more hydrogen atoms may be substituted by a halogen atom, an alkyl group having 1 to 12 carbon atoms or an alkoxy group ( 2) The divalent organic group represented. -(CH ₂ ) _n1 - (1) In the formula (1), n1 is 2 or 3. -(CH ₂ ) _n2 -O-(CH ₂ ) _n3 - (2) In the 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 the aryl group may have a substituent or may be unsubstituted. The substituent T described in the above formula (PP) is exemplified as the substituent. 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.

The squaraine compound may, for example, be a compound having the following structure. Further, a compound described in paragraphs 0044 to 0049 of JP-A-2011-208101, a compound described in paragraphs 0060 to 0061 of Japanese Patent No. 6065169, and WO2016/181987 The compound described in the paragraph No. 0040, the compound described in the publication of the International Publication No. WO 2013/133099, the compound described in the publication WO 2014/088063, and the compound described in JP-A-2014-126642, A compound described in JP-A-2016-146619, a compound described in JP-A-2015-176046, a compound described in JP-A-H09-025311, and WO2016/154782 The compound described in the Japanese Patent No. 5,884, 953, the compound described in Japanese Patent No. 6,036,689, the compound described in Japanese Patent No. 5,810,604, Compounds, etc., are incorporated into this specification. [Chemical Formula 12]

The compound represented by the formula (C) of the cyanine compound is preferred. Formula (C) [Chemical Formula 13] Wherein Z ¹ and Z ² are each independently a non-metal atomic group forming a nitrogen-containing heterocyclic ring of 5 or 6 members which may be condensed, and R ¹⁰¹ and R ¹⁰² each independently represent an alkyl group, an alkenyl group, an alkynyl group or An aryl group, L ¹ represents a methine chain having an odd number of methine groups, and a and b are each independently 0 or 1. When a is 0, a carbon atom and a nitrogen atom are bonded by a double bond, and when b is 0 When a carbon atom and a nitrogen atom are bonded by a single bond, when the moiety represented by Cy in the formula is a cation moiety, X ¹ represents an anion, and c represents a quantity required for taking a balance of charges, when Cy in the formula When the indicated portion is an anion portion, X ¹ represents a cation, and c represents a quantity required for taking a balance of charges. When the charge at a portion indicated by Cy in the formula is neutralized in the molecule, c is 0.

Specific examples of the cyanine compound include the compounds shown below. In addition, as the cyanine compound, the compound described in paragraphs 0044 to 0045 of JP-A-2009-108267, and the compound described in paragraphs 0026 to 0030 of JP-A-2002-194040, The compound described in JP-A-2015-172004, and the compound described in JP-A-2015-172102, and the compound described in JP-A-2008-088426, JP-A-2017-031394 The compounds described in the above, etc., are incorporated herein by reference. [Chemical Formula 14]

In the present invention, a commercially available product can also be used as the near-infrared absorbing pigment. For example, SDO-C33 (manufactured by ARIMOTO CHEMICAL CO., LTD.), EXCOLOR IR-14, EXCOLOR IR-10A, EXCOLOR TX-EX-801B, EXCOLOR TX-EX-805K (manufactured by Nippon Shokubai Co., Ltd.) ), Shigenox NIA-8041, Shigenox NIA-8042, Shigenox NIA-814, Shigenox NIA-820, Shigenox NIA-839 (manufactured by Hakkol Chemical Co., Ltd.), Epolite V-63, Epolight 3801, Epolight 3036 (manufactured by EPOLIN Inc.), PRO-JET825LDI ( Manufactured by FUJIFILM Co., Ltd., NK-3027, NK-5060 (manufactured by Hayashibara Co., Ltd.), YKR-3070 (manufactured by Mitsui Chemicals, Inc.), and the like.

The content of the near-infrared absorbing pigment is preferably from 3 to 50% by mass based on the total solid content of the curable composition. The upper limit is preferably 40% by mass or less, more preferably 35% by mass or less. The lower limit is preferably 4% by mass or more, and more preferably 5% by mass or more. The near-infrared absorbing pigment may be used alone or in combination of two or more. In the case of two or more types, the total amount of these is preferably in the above range.

<<Other near-infrared absorbing agent>> 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. Examples of other near-infrared ray absorbing agents include inorganic pigments (inorganic particles). The shape of the inorganic pigment is not particularly limited, and may be in the form of a sheet, a thread, or a tube, regardless of the spherical shape or the non-spherical shape. As the inorganic pigment, metal oxide particles or metal particles are preferred. Examples of the 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, and fluorine doping two. Tin oxide (F-doped SnO ₂ ) particles, cerium-doped titanium dioxide (Nb-doped TiO ₂ ) particles, and the like. Examples of the metal particles include silver (Ag) particles, gold (Au) particles, copper (Cu) particles, and nickel (Ni) particles. Further, as the inorganic pigment, a tungsten oxide-based compound can also be used. The tungsten oxide-based compound is preferably a tungsten oxide. For details of the tungsten oxide-based compound, paragraph number 0080 of JP-A-2016-006476 is incorporated herein by reference.

When the curable composition of the present invention contains another near-infrared ray absorbing agent, the content of the other near-infrared ray absorbing agent is preferably 0.01 to 50% by mass based on the total solid content of the curable composition. 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 ray absorbing agent among the total mass of the near-infrared absorbing dye and the other near-infrared absorbing agent is preferably from 1 to 99% by mass. The upper limit is preferably 80% by mass or less, more preferably 50% by mass or less, and still more preferably 30% by mass or less. Further, it is also preferred that the curable composition of the present invention does not substantially contain other near-infrared ray absorbing agents. The content of the other near-infrared ray absorbing agent in the total mass of the near-infrared absorbing dye and the other near-infrared absorbing agent is preferably 0.5% by mass or less, and more preferably 0.1% by mass or less. Preferably, it does not contain other near-infrared absorbing agents for further improvement.

<<Radical Polymerizable Compound>> The curable composition of the present invention contains a radically polymerizable compound. The radically polymerizable compound is preferably a compound containing one or more groups having an ethylenically unsaturated bond, and more preferably a compound containing two or more groups having an ethylenically unsaturated bond, and contains three. The above compound having a group having an ethylenically unsaturated bond is further preferred. The upper limit of the number of groups having an ethylenically unsaturated bond in the radically polymerizable compound is preferably 15 or less, and more preferably 6 or less. Examples of the group having an ethylenically unsaturated bond include a vinyl group, a (meth)allyl group, a (meth)acrylonyl group, and the like, and a (meth)acrylonyl group is preferred. The radically polymerizable compound is preferably a 3- to 15-functional (meth) acrylate compound, and more preferably a 3- to 6-functional (meth) acrylate compound.

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

The example ester of the radically polymerizable compound can be referred to in paragraphs 0033 to 0034 of JP-A-2013-253224, which is incorporated herein by reference. As a radically polymerizable compound, ethoxylated modified pentaerythritol tetraacrylate (commercially available as NK Ester ATM-35E; manufactured by Shin-Nakamura Chemical Co., Ltd.), dipentaerythritol III Acrylate (commercially available as KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (commercially available as KAYARAD D-320; manufactured by Nippon Kayaku Co., Ltd.) ), dipentaerythritol penta (meth) acrylate (commercially available as KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa(meth) acrylate (as a city) The product sold is KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., A-DPH-12E; manufactured by Shin-Nakamura Chemical Co., Ltd.) and these (meth)acrylonyl groups are via ethylene glycol residues and A compound having a structure in which a propylene glycol residue is bonded is preferred. Also, these types of oligomers can be used. Further, the description of paragraphs 0034 to 0038 of JP-A-2013-253224 is incorporated herein by reference. Further, a polymerizable monomer or the like described in Paragraph No. 0477 of the Japanese Patent Laid-Open Publication No. 2012-208494 (paragraph No. 0585 of the specification of the corresponding US Patent Application Publication No. 2012/0235099) is incorporated. In this manual. Further, diglycerin EO (ethylene oxide) modified (meth) acrylate (commercially available as M-460; manufactured by TOAGOSEI CO., LTD.), neopentyl alcohol tetraacrylate (Shin-Nakamura Chemical) Manufactured by Co., Ltd., A-TMMT), 1,6-hexanediol diacrylate (manufactured by Nippon Kayaku Co., Ltd., KAYARAD HDDA) is also preferred. These types of oligomers can also be used. For example, RP-1040 (manufactured by Nippon Kayaku Co., Ltd.) or the like can be given.

The radically polymerizable compound may have an acid group such as a carboxyl group, a sulfonic acid group or a phosphoric acid group. For example, ARONIX M-305, M-510, M-520 (above, TOAGOSEI CO., LTD.), etc. are mentioned as a commercial item of the radical-polymerizable compound which has an acid group. The acid value of the radically polymerizable compound is preferably from 0.1 to 40 mgKOH/g. The lower limit is preferably 5 mgKOH/g or more. The upper limit is preferably 30 mgKOH/g or less.

Regarding the radical polymerizable compound, a compound having a caprolactone structure is also preferred. The radically polymerizable compound having a caprolactone structure is commercially available, for example, from Nippon Kayaku Co., Ltd. as KAYARAD DPCA series, and examples thereof include DPCA-20, DPCA-30, DPCA-60, and DPCA-120. The description of the radically polymerizable compound having a caprolactone structure can be referred to in paragraphs 004 to 0045 of JP-A-2013-253224, which is incorporated herein by reference.

As the radically polymerizable compound, a compound having an alkoxy group can also be used. The radically polymerizable compound having an alkoxy group is preferably a compound having an ethoxy group and/or a propoxy group, and a compound having an ethoxy group is more preferable, and has 4 to 20 ethoxy groups. The 3- to 6-functional (meth) acrylate compound is further preferred. As a commercial product of the radically polymerizable compound having an alkoxy group, for example, SR-494 which is a tetrafunctional (meth) acrylate having four ethylene oxide groups, which is manufactured by Sartomer Company, Inc., may be mentioned. As KAYARAD TPA-330 having three trifunctional (meth) acrylates which are isobutyloxy groups, and the like.

The radical-polymerizable compound is an amine group as described in JP-A-48-041708, JP-A-51-037193, JP-A-2-032293, and JP-A-2-016765. An acid ester acrylate or an epoxy resin described in Japanese Patent Publication No. Sho 58-049860, Japanese Patent Publication No. Sho 56-017654, Japanese Patent Publication No. Sho 62-039417, and Japanese Patent Publication No. Sho 62-039418 Alkyl skeleton amide compounds are also preferred. Further, radical polymerization having an amine group structure or a sulfide structure in a molecule described in Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. Sex compounds are also preferred. In addition, as the radically polymerizable compound, a compound described in JP-A-H08-A No. 0, 074, 807, and Japanese Patent No. 6031807 can be used. As a commercial item, UA-7200 (made by Shin-Nakamura Chemical Co., Ltd.), DPHA-40H (made by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha Chemical Co., Ltd.), and the like. Further, as the radically polymerizable compound, 8UH-1006, 8UH-1012 (above, manufactured by Taisei Fine Chemical Co., Ltd.), LIGHT ACRYLATE POB-A0 (manufactured by Kyoeisha Chemical Co., Ltd.), or the like is also used. good. In addition, as the radically polymerizable compound, a compound described in JP-A-H08-A No. 0, 074, 807, and Japanese Patent No. 6031807 can be used.

The content of the radically polymerizable compound is preferably from 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, and more preferably 1% by mass or more. The upper limit is preferably 30% by mass or less, more preferably 20% by mass or less. The content of the radically polymerizable compound is preferably from 20 to 300 parts by mass based on 100 parts by mass of the near-infrared absorbing pigment. The upper limit is preferably 200 parts by mass or less, more preferably 150 parts by mass or less, and still 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 still more preferably 60 parts by mass or more. When the ratio of the radically polymerizable compound to the near-infrared absorbing dye is within the above range, it is easy to form a cured film from which the generation of the aggregate of the near-infrared absorbing pigment is further suppressed. The curable composition of the present invention may contain only one type of radically polymerizable compound, or may contain two or more types. When two or more kinds of radically polymerizable compounds are contained, the total amount of these is preferably in the above range.

<<Radical Polymerization Initiator A>> The curable composition of the present invention contains a radical polymerization initiator A. The radical polymerization initiator A is a compound which initiates or promotes polymerization of a radically polymerizable compound by generating a radical by the action of light or heat. The radical polymerization initiator A is preferably a compound which generates a radical by at least a heat.

In the curable composition of the present invention, the pinacol compound (first aspect) is used as the radical polymerization initiator A, or the thermal decomposition temperature is 120 to 270 ° C and the thermal decomposition rate is 33 to 60 W/ °C•mol of the compound (the second aspect).

The thermal decomposition temperature of the radical polymerization initiator A used in the first aspect is preferably 270 ° C or lower, more preferably 240 ° C or lower, and further preferably 220 ° C or lower. The lower limit of the thermal decomposition temperature is preferably 100 ° C or more, more preferably 110 ° C or more, still more preferably 120 ° C or more, still more preferably 140 ° C or more, and particularly preferably 150 ° C or more. Further, the thermal decomposition rate of the radical polymerization initiator A used in the first aspect is preferably 33 W/° C. or more, more preferably 35 W/° C·mol or more, and 37 W/° C·mol or more is further. Preferably. The upper limit of the thermal decomposition rate is preferably 66 W/°C•mol or less, more preferably 65 W/° C•mol or less, and further preferably 64 W/° C•mol or less.

The radical polymerization initiator A used in the second aspect has a thermal decomposition temperature of 120 to 270 °C. The upper limit is preferably 240 ° C or less, and more preferably 220 ° C or less. The lower limit is preferably 140 ° C or more, more preferably 150 ° C or more. Further, the thermal decomposition rate of the radical polymerization initiator A used in the second aspect is 33 to 66 W/° C. mol. The lower limit is preferably 35 W/° C·mol or more, and more preferably 37 W/° C·mol or more. The upper limit is preferably 65 W/° C•mol or less, and more preferably 64 W/° C•mol or less. The radical polymerization initiator A to be used in the second aspect is not particularly limited as long as it is a compound having the above properties, and examples thereof include a pinacol compound and the like, and the effect of the present invention is more apparent. The reason is that the pinacol compound is more preferable.

Further, in the present invention, the thermal decomposition temperature of the radical polymerization initiator is a value measured by thermogravimetric differential heat (TG-DTA) measurement. More specifically, the radical polymerization initiator was heated from the state of 23 ° C at a temperature increase rate of 10 ° C /min, and the temperature at which the weight of the radical polymerization initiator started to decrease was measured. Further, the thermal decomposition rate of the radical polymerization initiator is a value measured by differential scanning calorimetry (DSC) measurement. More specifically, the radical polymerization initiator is heated from the state of 23 ° C at a temperature increase rate of 10 ° C /min, and after 100 ° C, the slope of the line connecting the rising temperature of the exothermic peak and the maximum temperature of the exothermic peak Calculate the rate of thermal decomposition.

The 1% by weight of the radical polymerization initiator A used in the first aspect and the second aspect is preferably 90 to 220 ° C. The upper limit of the weight of 1% is preferably 215 ° C or lower, more preferably 210 ° C or lower, and further preferably 200 ° C or lower. The lower limit of the 1% by weight temperature is preferably 100 ° C or more, more preferably 120 ° C or more, and further preferably 150 ° C or more. When the temperature of the radical polymerization initiator A is 1% by weight in the above range, it is easy to achieve both low-temperature curability and storage stability of the composition. Further, in the present invention, the temperature at which the radical polymerization initiator is 1% by weight refers to a temperature at which the weight of the radical polymerization initiator is reduced by 1% when the radical polymerization initiator monomer is subjected to TG-DTA measurement.

The radical polymerization initiator A used in the first aspect and the second aspect has a molar absorption coefficient of 100 L•mol ^-1 •cm ^-1 or less at a wavelength of 365 nm, preferably 50 L·mol ^-1 . cm ^-1 or less is more preferred, 10L • mol ^-1 • cm ^-1 or less is more preferred. When the radical polymerization initiator A has a Mohr absorption coefficient of 100 L•mol ^-1 •cm ^-1 or less at a wavelength of 365 nm, it is possible to effectively suppress the initiation of radical polymerization during storage of the curable composition. The agent A generates a radical, and the storage stability of the curable composition is good.

Further, in the present invention, the molar absorption coefficient of the radical polymerization initiator at a wavelength of 365 nm can prepare a 5 mol% solution of a radical polymerization initiator by dissolving a radical polymerization initiator in a solvent (determination) The solution was measured and the absorbance of the assay solution was measured. Specifically, the measurement solution was placed in a glass tank having a width of 1 cm, and the absorbance was measured using a UV-Vis-NIR spectrometer (Cary 5000) manufactured by Agilent Technologies Japan, Ltd., and substituted into the following formula to calculate the wavelength at 365 nm. The Mohr absorption coefficient (L•mol ^-1 •cm ^-1 ). [Expression 1] In the above formula, ε represents a molar absorption coefficient (L•mol ^-1 • cm ^-1 ), A represents absorbance, c represents a concentration (mol/L) of the measurement solution, and l represents an optical path length (cm).

When the molar absorption coefficient of the radical polymerization initiator A is measured, examples of the solvent used in the preparation of the measurement solution include acetonitrile and chloroform. When the radical polymerization initiator A is a compound dissolved in acetonitrile, an assay solution is prepared using acetonitrile. When the radical polymerization initiator A is a compound which is insoluble in acetonitrile but dissolved in chloroform, a measurement solution is prepared using chloroform. Further, when the radical polymerization initiator A was insoluble in acetonitrile and chloroform but dissolved in dimethyl hydrazine, a measurement solution was prepared using dimethyl hydrazine.

As the radical polymerization initiator A used in the present invention, a pinacol compound is preferred. As the pinacol compound, a benzopinacol compound is preferred. Examples of the pinacol compound include compounds represented by the following formulas (T-1) to (T-3). [Chemical Formula 15]

In the formulae (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. And, m1 one Rt ^{Rt. 1 1} 2 may be mutually bonded to each other to form a ring. When m2 is 2 to 4, m2 Rt ² may be the same or different. And, m2 Rt ² in a two Rt ² may be mutually bonded to each other to form a ring. When m3 is 2 to 4, m3 Rt ³ may be the same or different. And, m3 Rt ³ in a two Rt ³ may be mutually bonded to each other to form a ring. When m4 is 2 to 4, m4 Rt ⁴ may be the same or different. And, m4 a Rt ^{Rt. 4 4} 2 may be mutually bonded to each other to form a ring. Further, Rt ¹ and Rt ² , Rt ¹ and Rt ³ , Rt ¹ and Rt ⁴ , Rt ² and Rt ³ , Rt ² and Rt ⁴ , and Rt ³ and Rt ⁴ may be bonded to each other to form a ring. In the 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 ), and 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 the 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 represents a substituent. In the formula (T-3), M ² represents Ti(R ^M6 ), Zr(R ^M6 ), Si(R ^M6 ) or B, R ^M6 represents a substituent, and L ¹ represents a divalent linking group.

Examples of the substituent represented by Rt ¹ to Rt ⁴ and R ^M1 to R ^M6 include an alkyl group, an aryl group, a heterocyclic group, a nitro group, a cyano group, a halogen atom, -OR ^X1 , -SR ^X1 , and -COR. ^X1 , -COOR ^X1 , -OCOR ^X1 , -NR ^X1 R ^X2 , -NHCOR ^X1 , -CONR ^X1 R ^X2 , -NHCONR ^X1 R ^X2 , -NHCOOR ^X1 , -SO ₂ R ^X1 , -SO ₂ OR ^X1 , -NHSO ₂ R ^X1 and so on. R ^X1 and R ^X2 each independently represent a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. The alkyl group represented by the substituent, the alkyl group represented by R ^X1 and R ^X2 , and the alkyl group represented by Rt ⁵ and Rt ⁶ in the formula (T-1) are preferably 1 to 20 carbon atoms. The alkyl group may be any of a straight chain, a branch, and a ring, but a straight chain or a branch is preferred. The aryl group represented by the substituent, the aryl group represented by R ^X1 and R ^X2 , and the aryl group represented by Rt ⁵ and Rt ⁶ in the formula (T-1) are preferably 6 to 20, preferably 6 to 15 More preferably, 6 to 10 is further preferred. The aryl group may be a single ring or a condensed ring. The heterocyclic group as a substituent and the heterocyclic group 5-membered ring or 6-membered ring represented by R ^X1 and R ^X2 are preferred. The heterocyclic group may be a single ring or a condensed ring. The number of carbon atoms constituting the heterocyclic group is preferably from 3 to 30, more preferably from 3 to 18, still more preferably from 3 to 12. The number of hetero atoms constituting the heterocyclic group is preferably from 1 to 3. The hetero atom of the heterocyclic group is preferably a nitrogen atom, an oxygen atom or a sulfur atom. Further, a part or all of the hydrogen atom of the heterocyclic group may be substituted with the above substituent.

M1 to m4 each independently represent an integer of 0 to 4, preferably 0 to 3, more preferably 0 to 2, further preferably 0 or 1, and 0 is particularly preferable.

Examples of the divalent linking group represented by L ¹ include an alkylene group, an extended aryl group, and —NR′— (R′ represents a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent. A hydrogen atom is preferred, -SO ₂ -, -CO-, -COO-, -OCO-, -O-, -S-, and a combination thereof.

Formula (T-1) in, Rt ⁵ Rt, and at least one hydrogen atom is preferred based, Rt ⁵ and ⁶ both Rt system is more preferably a hydrogen atom in the ^6.

Specific examples of the pinacol compound include benzopinacol, 1,2-dimethoxy-1,1,2,2-tetraphenylethane, and 1,2-diethoxy- 1,1,2,2-tetraphenylethane, 1,2-diphenoxy-1,1,2,2-tetraphenylethane, 1,2-dimethoxy-1,1, 2,2-tetrakis(4-methylphenyl)ethane, 1,2-diphenoxy-1,1,2,2-tetrakis(4-methoxyphenyl)ethane, 1,2- Bis(trimethyldecyloxy)-1,1,2,2-tetraphenylethane, 1,2-bis(triethyldecyloxy)-1,1,2,2-tetraphenyl Alkane, 1,2-bis(t-butyldimethylamyloxy)-1,1,2,2-tetraphenylethane, 1-hydroxy-2-trimethylphosphonium-1,1 , 2,2-tetraphenylethane, 1-hydroxy-2-triethyl decyloxy-1,1,2,2-tetraphenylethane, 1-hydroxy-2-tert-butyl dimethyl Alkyloxy-1,1,2,2-tetraphenylethane, and the like. In addition, the content of the pinacol compound can be referred to in the specification of the Japanese Patent Publication No. 2014-521772, the Japanese Patent Publication No. 2014-523939, and the Japanese Patent Publication No. 2014-521772.

The content of the radical polymerization initiator A is preferably from 0.1 to 20% by mass based on the total solid content of the curable composition. The upper limit is preferably 15% by mass or less, more preferably 10% by mass or less. The lower limit is preferably 0.5% by mass or more, and more preferably 1% by mass or more. In addition, the curable composition contains 1 to 200 parts by mass of the radical polymerization initiator A, preferably 100 parts by mass of the radically polymerizable compound. The lower limit is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, and still more preferably 20 parts by mass or more. The upper limit is preferably 150 parts by mass or less, more preferably 120 parts by mass or less, and still more preferably 100 parts by mass or less. When the ratio of the radical polymerization initiator A to the radically polymerizable compound is within the above range, it is easy to form a cured film from which generation of aggregates derived from the near-infrared absorbing pigment is suppressed.

<<Radical Polymerization Initiator B>> In the curable composition of the present invention, as the radical polymerization initiator, a radical polymerization initiator B different from the above-mentioned radical polymerization initiator A is preferably used. . In this way, there is a tendency that the effects of the present invention can be more clearly obtained. Further, the spectral characteristics (for example, near-infrared shielding properties) of the obtained cured film can be further improved. This is because the combination of the radical polymerization initiator A and the radical polymerization initiator B can improve the association between the near-infrared absorbing pigment at the time of film formation and the like. In addition, when a compound having a thermal decomposition rate slower than the radical polymerization initiator A is used as the radical polymerization initiator B, the curability of the curable composition can be appropriately adjusted, and as a result, the source is easily formed. A cured film in which the generation of agglomerates of the near-infrared absorbing pigment is suppressed.

The radical polymerization initiator B used in the present invention may be a compound which initiates or promotes polymerization of a radically polymerizable compound by generating a radical by the action of light or heat. The radical polymerization initiator B is preferably a compound which generates a radical by at least a heat.

The thermal decomposition temperature of the radical polymerization initiator B is preferably from 100 to 270 °C. The upper limit is preferably 240 ° C or less, and more preferably 220 ° C or less. The lower limit is preferably 120 ° C or more, and more preferably 140 ° C or more. When the thermal decomposition temperature of the radical polymerization initiator B is within the above range, the storage stability of the curable composition is good. Further, the absolute value of the difference between the thermal decomposition temperature of the radical polymerization initiator A and the thermal decomposition temperature of the radical polymerization initiator B is preferably 12 ° C or more, and more preferably 13 ° C or more. The upper limit is preferably 35 ° C or lower, and more preferably 34 ° C or lower. When the difference between the two thermal decomposition temperatures is within the above range, the effect of both thermosetting property and storage stability can be obtained.

The thermal decomposition rate of the radical polymerization initiator B is preferably 3 to 30 W/° C. mol. The upper limit is preferably 20 W/° C•mol or less, more preferably 10 W/° C•mol or less, and further preferably 7 W/° C•mol or less. When the thermal decomposition rate of the radical polymerization initiator B is within the above range, the curability of the curable composition can be appropriately adjusted, and a cured film obtained by suppressing generation of aggregates derived from the near-infrared absorbing pigment can be easily formed. Further, the absolute value of the difference between the thermal decomposition rate of the radical polymerization initiator A and the thermal decomposition rate of the radical polymerization initiator B is preferably 27 W/° C·mol or more, and more preferably 30 W/° C·mol or more. . The upper limit is preferably 55 W/° C•mol or less, and more preferably 53 W/° C•mol or less. When the difference between the two thermal decomposition rates is within the above range, the curability of the curable composition can be appropriately adjusted, and the cured film obtained by suppressing the generation of the aggregate derived from the near-infrared absorbing pigment can be easily formed.

Examples of the radical polymerization initiator B include an α-hydroxyacetophenone compound, an α-aminoacetophenone compound, a benzyldimethylketal compound, an anthraquinone compound, an organic peroxide, an azo compound, and the like. In order to effectively suppress the generation of aggregates derived from the near-infrared absorbing pigment, and to easily obtain a cured film having excellent spectral characteristics, α-hydroxyacetophenone compound, α-aminoacetophenone compound, and benzyl group The dimethyl ketal compound and the hydrazine compound are preferable, and the α-hydroxyacetophenone compound and the benzyldimethylketal compound are more preferable, and the α-hydroxyacetophenone compound is further preferable.

The α-hydroxyacetophenone compound is a compound represented by the following formula (T-11). Formula (T-11) [Chemical Formula 16] In the formula, Rt ¹¹ represents a substituent, and Rt ¹² and Rt ¹³ each independently represent a hydrogen atom or a substituent, and Rt ¹² and Rt ¹³ may be bonded to each other to form a ring, and m represents an integer of 0 to 4.

The substituent represented by Rt ¹¹ may, for example, be an alkyl group or an alkoxy group. The alkyl group and the alkoxy group may be unsubstituted or may have a substituent. Examples of the substituent include a hydroxyl group and the like.

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

Specific examples of the α-hydroxyacetophenone compound include 1-hydroxy-cyclohexyl-phenyl-ketone and 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2. -Methyl-1-propan-1-one and the like. The commercially available product of the α-hydroxyacetophenone compound may, for example, be IRGACURE-184 or IRGACURE-2959 (manufactured by BASF Corporation).

The α-aminoacetophenone compound may, for example, be 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one or 2-benzyl-2-dimethyl Amino-1-(4-morpholinophenyl)-1-butanone, 2-dimethylamino-2-[(4-methylphenyl)methyl]-1-[4-( 4-morpholinyl)phenyl]-1-butanone and the like. Commercial products of the α-aminoacetophenone compound include IRGACURE-907, IRGACURE-369, and IRGACURE-379 (all manufactured by BASF Corporation).

The benzyldimethylketal compound may, for example, be 2,2-dimethoxy-2-phenylacetophenone or the like. As a commercial item, IRGACURE-651 (made by BASF Corporation) etc. are mentioned.

Examples of the azo compound include 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile) and 2,2'-azobis(2,4-dimethyl group). Valeronitrile), dimethyl-2,2'-azobis(2-methylpropionate), 2,2'-azobis(2-methylbutyronitrile), 1,1'-azo Bis(cyclohexane-1-carbonitrile), 2,2'-azobis[N-(2-propenyl)2-methylpropanamide], 1-[(1-cyano-1-methyl) Benzyl)azo]carbamamine, 2,2'-azobis(N-butyl-2-methylpropionamide), 2,2'-azobis(N-cyclohexyl-2- Methyl acrylamide) and the like. As a commercial item of an azo compound, V-70, V-65, V-60, V-59, V-40, V-30, V-501, V-601, VE-073, VA- are mentioned. 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 ( The above is manufactured by Wako Pure Chemical Industries, Ltd.) and the like. Examples of the organic peroxide include methyl ethyl ketone peroxide, cyclohexanone peroxide, 3,3,5-trimethylcyclohexanone peroxide, and methylcyclohexanone peroxide. Acetylacetone peroxide, 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(t-butylperoxy) ring Hexane, 2,2-bis(t-butylperoxy)butane, tert-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, hydrogen peroxide Oxide, 2,5-dimethylhexane-2,5-dihydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, tert-butyl cumyl peroxide Oxide, dicumyl peroxide, bis(t-butylperoxyisopropyl)benzene, 2,5-dimethyl-2,5-di(t-butylperoxy) Alkane, 2,5-hexyl decyl peroxide, peroxy succinic acid, benzammonium peroxide, 2,4-dichlorobenzamide peroxide, m-toluamyl peroxide, diisopropyl Oxydicarbonate, di-2-ethylhexylperoxydicarbonate, di-2-ethoxyethyl peroxydicarbonate, dimethoxyisopropyl peroxy Acid ester, bis(3-methyl-3-methoxybutyl)peroxy dicarbonate, tert-butylperoxyacetate, tert-butylperoxy pivalate, third Butyl peroxy neodecanoate, tert-butylperoxyoctanoate, tert-butylperoxy-3,5,5-trimethylhexanoate, tert-butylperoxylauric Acid ester, 3,3'4,4'-tetra-(t-butylperoxycarbonyl)benzophenone, 3,3'4,4'-tetra-(tripentylperoxycarbonyl) Benzophenone, 3,3'4,4'-tetrakis(t-hexylperoxycarbonyl)benzophenone, 3,3'4,4'-tetra-(t-octylperoxycarbonyl) Benzophenone, 3,3'4,4'-tetra-(isopropylphenylperoxycarbonyl)benzophenone, 3,3'4,4'-tetra-(p-isopropylisopropyl Phenylperoxycarbonyl)benzophenone, carbonyldi(t-butylperoxydihydrodicarboxylate), carbonyldi(t-hexylperoxydihydrodicaprate), and the like. Commercial products of the organic peroxide include Perbutyl O, Perbutyl Z, and Perhexa 25B (all manufactured by NOF CORPORATION).

The oxime compound is a compound described in JP-A-2001-233842, a compound described in JP-A-2000-080068, and a compound described in JP-A-2006-342166, Japan. The compound described in JP-A-2000-066385, the compound described in JP-A-2000-080068, and the compound described in JP-A-2004-534797, JP-A-2006-342166 The compound described in the Japanese Patent Publication No. 2017-019766, the compound described in Japanese Patent No. 6065596, the compound described in International Publication WO2015/152153, and the publication WO01/051680 The compound described in the above. Specific examples of the ruthenium compound include 3-benzylideneoxyimidobutan-2-one, 3-ethyloxyiminobutan-2-one, and 3-propoxyl Aminobutan-2-one, 2-ethyloxyiminopentan-3-one, 2-ethyloxyimino-1-phenylpropan-1-one, 2-benzylformamide Oxyimido-1-phenylpropan-1-one, 3-(4-toluenesulfonyloxy)iminobutan-2-one and 2-ethoxycarbonyloxyimido-1 -Phenylpropan-1-one, and the like. As a commercial item of the ruthenium compound, IRGACURE-OXE01, IRGACURE-OXE02, IRGACURE-OXE03, IRGACURE-OXE04 (above, manufactured by BASF Corporation), and TR-PBG-304 (Changzhou Tronly New Electronic Materials CO., LTD.) can be mentioned. Manufactured by ADEKA OPTOMER N-1919 (photopolymerization initiator 2 described in JP-A-2012-014052, manufactured by ADEKA CORPORATION). Further, as the ruthenium compound, a compound having no coloring property or a compound having high transparency and being difficult to discolor is preferably used. As a commercial item, ADEKA ARKLS NCI-730, NCI-831, NCI-930 (The above is manufactured by ADEKA CORPORATION), etc. are mentioned.

Further, as the ruthenium compound, a ruthenium compound having an anthracene ring can also be used. Specific examples of the ruthenium compound having an anthracene ring include the compounds described in JP-A-2014-137466. This content is incorporated in this specification. As the hydrazine compound, an anthracene compound having a benzofuran skeleton can also be used. Specific examples include the compounds OE-01 to OE-75 described in WO 2015/036910. Further, as the ruthenium compound, a ruthenium compound having a fluorine atom can also be used. Specific examples of the ruthenium compound having a fluorine atom include the compounds described in JP-A-2010-262028, and the compounds 24 and 36 to 40 described in JP-A-2014-500852. Compound (C-3) or the like described in Japanese Patent Publication No. 2013-164471. These contents are incorporated in this specification. Further, as the ruthenium compound, a ruthenium compound having a nitro group can be used. It is also preferred that the ruthenium compound having a nitro group be a dimer. Specific examples of the ruthenium compound having a nitro group include those described in paragraphs 0031 to 0047 of JP-A-2013-114249 and paragraphs 0008 to 0102 and 0070 to 0079 of JP-A-2014-137466. The compound, the compound described in paragraphs 0007 to 0025 of Japanese Patent No. 4223307, ADEKA ARKLS NCI-831 (manufactured by ADEKA CORPORATION), and the like.

Specific examples of the ruthenium compound which is preferably used in the present invention are shown below, but the present invention is not limited thereto.

[Chemical Formula 17] [Chemical Formula 18]

The content of the radical polymerization initiator B is preferably from 0.1 to 20% by mass based on the total solid content of the curable composition. The upper limit is preferably 15% by mass or less, more preferably 10% by mass or less. The lower limit is preferably 0.5% by mass or more, and more preferably 1% by mass or more. In addition, the radical polymerization initiator B is preferably contained in an amount of from 1 to 200 parts by mass per 100 parts by mass of the radically polymerizable compound. The lower limit is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, and still more preferably 20 parts by mass or more. The upper limit is preferably 150 parts by mass or less, more preferably 120 parts by mass or less, and still more preferably 100 parts by mass or less. When the ratio of the radical polymerization initiator B to the radically polymerizable compound is within the above range, it is easy to form a cured film from which generation of aggregates derived from the near-infrared absorbing pigment is suppressed. In addition, the radical polymerization initiator B is preferably contained in an amount of 0.1 to 2000 parts by mass based on 100 parts by mass of the radical polymerization initiator A. The lower limit is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, and still more preferably 10 parts by mass or more. The upper limit is preferably 1,500 parts by mass or less, more preferably 1000 parts by mass or less, and still more preferably 500 parts by mass or less. When the ratio of the radical polymerization initiator A to the radical polymerization initiator B is within the above range, it is easy to form a cured film having good spectral characteristics and suppressing generation of aggregates derived from a near-infrared absorbing pigment.

<<Compound having a cyclic ether group>> The curable composition of the present invention may contain a compound having a cyclic ether group. The cyclic ether group is preferably an epoxy group or an oxetanyl group, and an epoxy group is preferred. The compound having a cyclic ether group is preferably a compound having two or more cyclic ether groups in one molecule. The upper limit of the number of the cyclic ether groups in the compound having a cyclic ether group is preferably 100 or less, more preferably 10 or less, and still more preferably 5 or less.

The cyclic ether group equivalent of the compound having a cyclic ether group (the molecular weight of the compound having a cyclic ether group / the number of the cyclic ether group in the compound having a cyclic ether group) is preferably 50 to 400 g / equivalent. The lower limit of the cyclic ether group equivalent is preferably 100 g/eq or more, more preferably 150 g/eq or more. The upper limit is preferably 350 g/eq or less, more preferably 300 g/eq or less. Further, when the compound having a cyclic ether group is a compound having an epoxy group, the epoxy equivalent (the molecular weight of the compound having an epoxy group / the number of epoxy groups in the compound having an epoxy group) is 50 to 50 400 g / equivalent is preferred. The lower limit of the epoxy equivalent is preferably 100 g/eq or more, more preferably 150 g/eq or more. The upper limit is preferably 350 g/eq or less, more preferably 300 g/eq or less.

The compound having a cyclic ether group may be a low molecular compound (for example, having a molecular weight of less than 1,000), or may be a macromolecular compound (for example, a molecular weight of 1,000 or more, and in the case of a polymer, a weight average molecular weight of 1,000 or more) . The molecular weight of the compound having a cyclic ether group (weight average molecular weight in the case of a polymer) is preferably from 200 to 100,000, more preferably from 500 to 50,000. The upper limit of the molecular weight (weight average molecular weight in the case of a polymer) is preferably 3,000 or less, more preferably 2,000 or less, and still more preferably 1,500 or less.

A compound having a cyclic ether group is preferably a compound having a repeating unit. When the compound having a cyclic ether group is a compound having a repeating unit, it may have a cyclic ether group in the side chain of the repeating unit or a cyclic ether group at the end of the main chain. Among them, a compound having a cyclic ether group in a side chain is preferred because it is easily adsorbed on a support to easily obtain water-resistant adhesion.

The compound having a cyclic ether group is preferably a compound having an aromatic ring and/or an aliphatic ring structure, and a compound having an aromatic ring structure is further preferred. When a compound having an aromatic ring is used as a compound having a cyclic ether group, it is easy to form a cured film which is more excellent in water-resistant adhesion by interacting with a near-infrared absorbing pigment.

As the aromatic ring, an aromatic hydrocarbon ring is preferred. Further, the aromatic ring may be a single ring or a condensed ring. Specific examples of the aromatic ring include a benzene ring and a naphthalene ring. The compatibility with the near-infrared absorbing dye is improved, and it is easy to obtain excellent water-resistant adhesion. At least a naphthalene ring is preferred. When the compound having a cyclic ether group contains an aromatic ring, one or more of the number of aromatic rings is preferable, and the compatibility with the near-infrared absorbing pigment is improved, and excellent water-resistant adhesion is easily obtained. More than 2 are better. The upper limit is preferably 5 or less, and 4 or less is more preferable. Further, when the compound having a cyclic ether group is a compound having a repeating unit, the number of aromatic rings in one repeating unit is preferably from 1 to 10. The upper limit is preferably 7 or less, and the lower limit is preferably 5 or less. It is preferable that the lower limit is two or more. Further, the number of aromatic rings in the compound having a cyclic ether group is a total of the number of monocyclic aromatic rings and the number of rings constituting the condensed ring. For example, in the case of a compound having a naphthalene ring as an aromatic ring in a compound having a cyclic ether group, the number of aromatic rings of the compound having a cyclic ether group is two. In the case of a compound having a benzene ring and a naphthalene ring as an aromatic ring in a compound having a cyclic ether group, the number of aromatic rings of the compound having a cyclic ether group is three.

When the compound having a cyclic ether group is a compound having a structure of an aromatic ring and/or an aliphatic ring, it is preferred that the cyclic ether group is bonded to the aromatic ring and/or the aliphatic ring via a single bond or a linking group. . Examples of the linking group include an alkylene group, an aryl group, and -NR'- (wherein R' represents a hydrogen atom, an alkyl group which may have a substituent or an aryl group which may have a substituent, and a hydrogen atom is preferred), SO ₂ -, -CO-, -COO-, -OCO-, -O-, -S- and the groups in which these are combined.

The compound having a cyclic ether group can also be used in paragraphs 0034 to 0036 of JP-A-2013-011869, paragraphs 0147 to 0156 of JP-A-2014-043556, and JP-A-2014-089408. The compound described in No. 0085 to 0092. These contents are incorporated in this specification. For the commercially available product of the compound having a cyclic ether group, for example, EPICLON HP5000, EPICLON HP4032D (manufactured by DIC Corporation) or the like can be given as the naphthalene-modified epoxy resin. Examples of the alkyl diphenol type epoxy resin include EPICLON 820 (manufactured by DIC Corporation). Examples of the bisphenol A type epoxy resin include jER825, jER827, jER828, jER834, jER1001, jER1002, jER1003, jER1055, jER1007, jER1009, jER1010 (above, manufactured by Mitsubishi Chemical Corporation), EPICLON 860, EPICLON 1050, EPICLON 1051, and EPICLON 1055 ( The above is manufactured by DIC Corporation). Examples of the bisphenol F-type epoxy resin include jER806, jER807, jER4004, jER4005, jER4007, jER4010 (above, manufactured by Mitsubishi Chemical Corporation), EPICLON830, EPICLON835 (above, manufactured by DIC Corporation), LCE-21, RE-602S. (The above is manufactured by Nippon Kayaku Co., Ltd.) and the like. Examples of the phenol novolac type epoxy resin include jER152, jER154, jER157S70, jER157S65 (above, manufactured by Mitsubishi Chemical Corporation), EPICLON N-740, EPICLON N-770, and EPICLON N-775 (all manufactured by DIC Corporation). . Examples of the cresol novolac type epoxy resin include EPICLON N-660, EPICLON N-665, EPICLON N-670, EPICLON N-673, EPICLON N-680, EPICLON N-690, and EPICLON N-695 (above Manufactured by DIC Corporation, EOCN-1020 (manufactured by Nippon Kayaku Co., Ltd.), and the like. Examples of the aliphatic epoxy resin include ADEKA RESIN EP-4080S, ADEKA RESIN EP-4085S, ADEKA RESIN EP-4088S (above ADEKA CORPORATION), CELLOXIDE 2021P, CELLOXIDE 2081, CELLOXIDE 2083, CELLOXIDE 2085, EHPE 3150, EPOLEAD PB 3600, EPOLEAD PB 4700 (above, manufactured by Daicel Corporation), Denacol EX-212L, EX-214L, EX-216L, EX-321L, EX-850L (above, manufactured by Nagase Chemtex Corporation) and the like. Further, examples of the compound having an oxetanyl group include OXT-101, OXT-121, OXT-212, OXT-221 (above, manufactured by TOAGOSEI CO., LTD.), OXE-10, and OXE-30 ( The above is manufactured by OSAKA ORGANIC CHEMICAL INDUSTRY LTD.).

When the curable composition of the present invention contains a compound having a cyclic ether group, the content of the compound having a cyclic ether group is preferably from 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, and more preferably 3% by mass or more. The upper limit is preferably 40% by mass or less, more preferably 30% by mass or less. Further, it is also preferred that the curable composition of the present invention does not substantially contain a compound having a cyclic ether group. The content of the compound having a cyclic ether group is not particularly limited to 0.1% by mass or less based on the total solid content of the curable composition, and preferably 0.05% by mass or less, and preferably 0.01% by mass. The following is further preferred, and it is further preferred that it is not contained.

<<Resin>> The curable composition of the present invention can contain a resin. The resin is blended, for example, in a use for dispersing particles such as pigments in a composition or a use of a binder. Further, a resin mainly used for dispersing particles such as pigments is also referred to as a dispersant. However, such a use of the resin is an example, and the resin can also be used for purposes other than such use.

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.

Examples of the resin include (meth)acrylic resin, olefin-thiol resin, polycarbonate resin, polyether resin, polyarylate resin, polyfluorene resin, polyether oxime resin, polyphenylene sulfide resin, and polyarylene. An ether phosphine oxide resin, a polyimine resin, a polyamide amide resin, a polyolefin resin, a cyclic olefin resin, a polyester resin, a styrene resin, or the like. One type of these resins may be used alone or two or more types may be used in combination. As the cyclic olefin resin, a norbornene resin can be preferably used from the viewpoint of improving heat resistance. As a commercial item of a norbornene resin, the ARTON series (for example, ARTON F4520) by JSR Corporation etc. are mentioned, for example. In addition, the resin described in the examples of the publication of the Japanese Laid-Open Patent Publication No. WO-A-A-A-A-A-A No.-A-A-A No.-A-A No.-A-A-A No.-A-A The resin described in JP-A-H07-075248, and the resin described in JP-A-H09-066240, the contents of which are incorporated herein by reference.

The resin used in the present invention may have an acid group. Examples of the acid group include a carboxyl group, a phosphoric acid group, a sulfonic acid group, and a phenolic hydroxyl group, and a carboxyl group is preferred. These acid groups may be used alone or in combination of two or more. A resin having an acid group can also be used as the alkali-soluble resin.

As the resin having an acid group, a polymer having a carboxyl group in a side chain is preferred. Specific examples thereof include a methacrylic acid copolymer, an acrylic copolymer, an itaconic acid copolymer, a crotonic acid copolymer, a maleic acid copolymer, a partially esterified maleic acid copolymer, and a novolak resin. An alkali-soluble phenol resin, an acidic cellulose derivative having a carboxyl group in a side chain, and a resin obtained by adding an acid anhydride to a polymer having a hydroxyl group. In particular, a copolymer of (meth)acrylic acid and other monomers copolymerizable therewith is suitable as the alkali-soluble resin. Examples of the other monomer copolymerizable with the (meth)acrylic acid include an alkyl (meth)acrylate, an aryl (meth)acrylate, and a vinyl compound. Examples of the (meth)acrylic acid alkyl ester and the (meth)acrylic acid aryl ester include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, and (methyl). Butyl acrylate, isobutyl (meth)acrylate, amyl (meth)acrylate, hexyl (meth)acrylate, octyl (meth)acrylate, phenyl (meth)acrylate, (meth)acrylic acid Benzyl ester, toluene (meth)acrylate, naphthyl (meth)acrylate, cyclohexyl (meth)acrylate, etc., and examples of the vinyl compound include styrene, α-methylstyrene, and vinyltoluene. , glycidyl methacrylate, acrylonitrile, vinyl acetate, N-vinyl pyrrolidone, tetrahydrofurfuryl methacrylate, polystyrene macromonomer, polymethyl methacrylate macromonomer Wait. Further, the other monomer may be a maleimide monomer substituted at the N position described in JP-A-10-300922, for example, N-phenyl maleimide, N-ring. Hexyl maleimide and the like. Further, these other monomers which can be copolymerized with (meth)acrylic acid may be used alone or in combination of two or more.

The resin having an acid group may further have a polymerizable group. Examples of the polymerizable group include a (meth)allyl group and a (meth)acrylonitrile group. As a commercial item, a Dianal NR series (manufactured by Mitsubishi Rayon Co., Ltd.), Photomer 6173 (a carboxyl group-containing urethane acrylate oligomer, manufactured by Diamond Shamrock Co., Ltd.), VISCOAT R-264, KS can be cited. Resist 106 (all manufactured by Osaka Organic Chemical Industry Co., Ltd.), CYCLOMER P series (for example, ACA230AA), PLACCEL CF200 series (all manufactured by Daicel Corporation), Ebecryl 3800 (manufactured by Daicel UCB Co., Ltd.), Acrycure RD-F8 (manufactured by Nippon Shokubai Co., Ltd.) or the like.

The resin having an acid group can preferably be composed of a benzyl (meth) acrylate / (meth) acrylate copolymer, benzyl (meth) acrylate / (meth) acrylate / (meth) acrylate 2 - A multicomponent copolymer of a hydroxyethyl ester copolymer, benzyl (meth)acrylate/(meth)acrylic acid/other monomer. In addition, it is also possible to use 2-hydroxypropyl (meth)acrylate/poly group as described in JP-A-7-140654, which is obtained by copolymerization of 2-hydroxyethyl (meth)acrylate. Styrene macromer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxy-3-phenoxypropyl acrylate / polymethyl methacrylate macromer / benzyl methacrylate / A Acrylic acid copolymer, 2-hydroxyethyl methacrylate/polystyrene macromonomer/methyl methacrylate/methacrylic acid copolymer, 2-hydroxyethyl methacrylate/polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer and the like.

The resin having an acid group is derived from a compound represented by the following formula (ED1) and/or a compound represented by the following formula (ED2) (hereinafter, these compounds are sometimes referred to as "ether dimers" The polymer of the repeating unit of the monomer component is also preferred.

[Chemical Formula 19]

In the formula (ED1), R ¹ and R ² each independently represent a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent. [Chemical Formula 20] In the formula (ED2), R represents a hydrogen atom or an organic group having 1 to 30 carbon atoms. As a specific example of the formula (ED2), the description of JP-A-2010-168539 can be referred to.

Specific examples of the ether dimer can be referred to, for example, in paragraph 0317 of JP-A-2013-029760, which is incorporated herein by reference. The ether dimer may be used alone or in combination of two or more.

The resin having an acid group may contain a repeating unit derived from a compound represented by the following formula (X). [Chemical Formula 21] In the formula (X), R ₁ represents a hydrogen atom or a methyl group, R ₂ represents an alkylene group having 2 to 10 carbon atoms, and R ₃ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms which may include a benzene ring. n represents an integer of 1 to 15.

For the resin having an acid group, the descriptions of paragraphs 0558 to 0571 of the Japanese Patent Application Laid-Open No. 2012-208494 (paragraphs 0685 to 0700 of the specification of the corresponding US Patent Application Publication No. 2012/0235099), Japanese Patent Publication No. 2012 The description of Paragraph No. 0076 to 0099 of the Japanese Patent Publication No. 198408 is hereby incorporated by reference. Further, a commercially available product can also be used as the resin having an acid group. For example, ACRYLIC BASE FF-426 (manufactured by FUJIKURAKASEI CO., LTD.) or the like can be given.

The acid value of the acid group-containing resin is preferably from 30 to 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.

Examples of the resin having an acid group include a resin having the following structure. In the following structural formula, Me represents a methyl group. [Chemical Formula 22]

In the curable composition of the present invention, it is also preferred to use a resin having a repeating unit represented by the formulae (A3-1) to (A3-7) as the resin. [Chemical Formula 23] In the formula, R ⁵ represents a hydrogen atom or an alkyl group, and 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.

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

L ⁴ to L ⁷ each independently represent a single bond or a divalent linking group. Examples of the divalent linking group include an alkyl group, an aryl group, -O-, -S-, -CO-, -COO-, -OCO-, -SO ₂ -, -NR ¹⁰ - (R ¹⁰ A hydrogen atom or an alkyl group, preferably a hydrogen atom or a group containing the combination. The carbon number of the alkylene group is preferably from 1 to 30, more preferably from 1 to 15, and further preferably from 1 to 10. The alkylene group may have a substituent, but unsubstituted is preferred. The alkylene group may be any of a straight chain, a branch, and a ring. Further, the cyclic alkylene group may be either a single ring or a polycyclic ring. The carbon number of the aryl group is preferably from 6 to 18, more preferably from 6 to 14, and further preferably from 6 to 10.

The alkyl group represented by R ¹⁰ to R ¹³ may be any of a linear chain, a branched chain or a cyclic chain, and a cyclic group is preferred. The alkyl group may have a substituent or may be unsubstituted. The alkyl group has preferably 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and still more preferably 1 to 10 carbon atoms. 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 further preferably 6 carbon atoms. The R ¹⁰ -based cyclic alkyl or aryl group is preferred. A linear or branched alkyl group of R ¹¹ and R ¹² is preferred. R ¹³ is a linear alkyl group, a branched alkyl group or an aryl group is preferred.

The substituent represented by R ¹⁴ and R ¹⁵ may, for example, be a halogen atom, a cyano group, a nitro group, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, an alkoxy group, an aryloxy group or a heteroaryloxy group. , alkylthio, arylthio, heteroarylthio, -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. Among them, at least one of R ¹⁴ and R ¹⁵ represents a cyano group or -COOR ^a4 is preferred. R ^a4 represents a hydrogen atom, an alkyl group or an aryl group.

A commercially available product of a resin having a repeating unit represented by the formula (A3-7) is ARTON F4520 (manufactured by JSR Corporation). In addition, the details of the resin having the repeating unit represented by the formula (A3-7) can be referred to in paragraphs 0053 to 0,075 and 0127 to 0130 of JP-A-2011-100084, the contents of which are incorporated herein by reference. in.

The curable composition of the present invention can also contain a resin as a dispersing agent. In particular, in the case of using a pigment, it is preferred to include a dispersant. Examples of the dispersant include an acidic dispersant (acidic resin) and an alkaline dispersant (basic resin). Here, the acidic dispersant (acidic resin) means a resin in which the amount of the acid group is more than the amount of the basic group. The acidic dispersing agent (acidic resin) is preferably a resin having an acid group content of 70 mol% or more when the total amount of the acid group and the basic group is 100 mol%, and substantially only contains an acid. The base resin is better. The acid group-based carboxyl group which the acidic dispersing agent (acid resin) has is preferable. The acid value of the acidic dispersant (acid resin) is preferably 40 to 105 mgKOH/g, more preferably 50 to 105 mgKOH/g, and still more preferably 60 to 105 mgKOH/g. Further, the alkaline dispersant (basic resin) means a resin in which the amount of the basic group is more than the amount of the acid group. The alkaline dispersing agent (basic resin) is preferably a resin having an amount of the basic group of more than 50 mol% when the total amount of the acid group and the amount of the basic group is 100 mol%. The basic base amine group which the alkaline dispersant has is preferable.

The resin used as the dispersing agent preferably contains a repeating unit having an acid group. When the resin used as the dispersing agent contains a repeating unit having an acid group, when a pattern is formed by photolithography, the residue generated on the substrate of the pixel can be further reduced.

A resin-based graft copolymer used as a dispersant is also preferred. Since the graft copolymer has affinity with a solvent by a graft chain, it is excellent in dispersibility of a pigment and dispersion stability after a time. The details of the graft copolymer can be referred to in paragraphs 0025 to 0094 of JP-A-2012-255128, which is incorporated herein by reference. Further, specific examples of the graft copolymer include the following resins. The following resin is also a resin having an acid group (alkali-soluble resin). Further, the graft copolymer is a resin described in paragraphs 0072 to 0094 of JP-A-2012-255128, which is incorporated herein by reference. [Chemical Formula 24]

Further, in the present invention, it is also preferred that the resin (dispersant) is an oligoimide-based dispersant containing at least one of a main chain and a side chain and containing a nitrogen atom. The oligoimine-based dispersant has a structural unit including a partial structure X and a side chain containing a side chain Y having an atomic number of 40 to 10,000 and a basic nitrogen atom resin in at least one of the main chain and the side chain. Preferably, the moiety structure X has a functional group of pKa14 or less. The basic nitrogen atom is not particularly limited as long as it is a basic nitrogen atom. For the oligo-imine-based dispersant, the descriptions of paragraphs 0102 to 0166 of JP-A-2012-255128 can be referred to, and the contents are incorporated herein by reference. Specific examples of the oligomeric imide-based dispersant include the following. The following resin is also a resin having an acid group (alkali-soluble resin). Further, as the oligomeric imide-based dispersant, the resin described in paragraphs 0168 to 0174 of JP-A-2012-255128 can be used. [Chemical Formula 25]

The dispersing agent can also be obtained as a commercial product, and specific examples thereof include Disperbyk-111 (manufactured by BYK-Chemie GmbH) and Solsperse 76500 (manufactured by Lubrizol Japan Ltd.). Further, the pigment dispersant described in paragraphs 0041 to 0130 of JP-A-2014-130338 can also be used, and the content is incorporated in the present specification. Further, the above-mentioned resin having an acid group or the like can also be used as a dispersing agent.

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

Further, when a dispersant is contained as the resin, the content of the dispersant is preferably from 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, and more preferably 10% by mass or less. The lower limit is preferably 0.5% by mass or more, and more preferably 1% by mass or more. Further, the content of the dispersant is preferably from 1 to 100 parts by mass based on 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.

<<Coloring Coloring Agent>> The curable composition of the present invention can contain a coloring agent. In the present invention, the coloring agent refers to a coloring agent other than the white coloring agent and the black coloring agent. The coloring agent is preferably a coloring agent having an absorption in a wavelength range of 400 nm or more and less than 650 nm.

The colorant can be a pigment or a dye. Pigment-based organic pigments are preferred. The organic pigment can be exemplified below. Colorimetric index (CI) Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 193, 194, 199, 213, 214, etc. (the above are yellow pigments); CI Pigment Orange 2, 5, 13, 16, 17, 17, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 71, 73, etc. (above is orange pigment) ; CI Pigment Red 1, 2, 3, 4, 5, 6, 7, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48:1, 48:2, 48: 3, 48:4, 49, 49:1, 49 : 2, 52:1, 52:2, 53:1, 57:1, 60:1, 63:1, 66, 67, 81:1, 81:2, 81:3, 83, 88, 90, 105 , 112, 119, 122, 123, 144, 146, 149, 150, 155, 166, 168, 169, 170, 171, 172, 175, 176, 177, 178, 179, 184, 185, 187, 188, 190 , 200, 202, 206, 207, 208, 209, 210, 216, 220, 224, 226, 242, 246, 254, 255, 264, 270, 272, 279, etc. (above red pigment); CI Pigment Green ( Pigment Green) 7, 10, 36, 37, 58, 59, etc. (the above are green pigments); CI Pigment Violet 1, 19, 23, 27, 32, 37, 42, etc. (above purple pigment); CI Pigment Blue 1, 2, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 22, 60, 64, 66, 79, 80, etc. Blue pigment), these organic pigments can be used singly or in combination.

The dye is not particularly limited, and a known dye can be used. As the chemical structure, a pyrazole azo type, an anilino azo type, a triarylmethane type, an anthraquinone type, an anthrapyridone type, a benzylidene type, an oxaphthalocyanine type, and a pyrazolotriazole azo can be used. Dyes such as pyridine, pyridone azo, cyanine, phenothiazine, pyrrolopyrazole, azomethine, koushankou, phthalocyanine, benzopyran, indigo, pyrromethene . Further, a polymer of these dyes can also be used. Further, the dye described in JP-A-2015-0284144 and JP-A-2015-034966 can also be used.

When the curable composition of the present invention contains a coloring agent, the content of the coloring agent is preferably from 0.1 to 70% by mass based on the total solid content of the curable composition. The lower limit is preferably 0.5% by mass or more, and 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. Further, the total amount of the coloring agent and the near-infrared absorbing pigment is preferably from 1 to 80% by mass based on the total solid content of the curable composition. The lower limit is preferably 5% by mass or more, and more preferably 10% by mass or more. The upper limit is preferably 70% by mass or less, more preferably 60% by mass or less. When the curable composition of the present invention contains two or more kinds of coloring agents, the total amount of these is preferably within the above range. Further, it is also preferred that the curable composition of the present invention does not substantially contain a coloring agent. The content of the coloring agent is not particularly limited, and the content of the coloring agent is preferably 0.05% by mass or less based on the total solid content of the curable composition, more preferably 0.01% by mass or less, and further containing no coloring agent. Preferably.

<<Color material that transmits infrared light and blocks visible light>> The curable composition of the present invention can also contain a color material that transmits infrared light and blocks visible light (hereinafter also referred to as a color material that blocks visible light). In the present invention, a color material that blocks visible light is preferably a color material that absorbs light in a wavelength range from purple to red. Further, in the present invention, it is preferable that the color material that blocks visible light is a color material that blocks light in a wavelength range of 450 to 650 nm. Further, the color material that blocks visible light is preferably a color material that transmits light having a wavelength of 900 to 1300 nm. In the present invention, it is preferred that the color material that blocks visible light satisfies at least one of the following (A) and (B). (A): Two or more types of coloring agents are contained, and black is formed by the combination of two or more types of coloring agents. (B): Contains an organic black colorant.

As the coloring agent, the above may be mentioned. Examples of the organic black coloring agent include a bisbenzofuranone compound, a methine azo compound, an anthracene compound, and an azo compound, and a bisbenzofuranone compound or an anthracene compound is preferred. Examples of the bisbenzofuranone compound include JP-A-2010-534726, JP-A-2012-515233, JP-A-2012-515234, International Publication No. WO2014/208348, and Japan Special Table 2015. The compound described in the publication No. 525260 or the like can be obtained, for example, from "Irgaphor Black" manufactured by BASF Corporation. Examples of the ruthenium compound include C.I. Pigment Black 31, 32 and the like. The compound described in JP-A-1-170601, JP-A No. 2-034664, and the like, and can be produced, for example, by Dainichiseika Color & Chemicals Mfg. Co., Ltd., as a methine azo compound. The "CHROMO FINE BLACK A1103" was obtained.

The combination of the coloring agents when black is formed by a combination of two or more coloring agents is exemplified below. (1) A state containing a yellow colorant, a blue colorant, a purple colorant, and a red colorant. (2) A state containing a yellow colorant, a blue colorant, and a red colorant. (3) A state containing a yellow colorant, a purple colorant, and a red colorant. (4) A state containing a yellow coloring agent and a purple coloring agent. (5) A state containing a green colorant, a blue colorant, a purple colorant, and a red colorant. (6) A state containing a purple coloring agent and an orange coloring agent. (7) A state containing a green colorant, a purple colorant, and a red colorant. (8) A state containing a green coloring agent and a red coloring agent.

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

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

[Chemical Formula 26] In the 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, n represents an integer of 1 or more, and when m is 2 or more, plural L and X may be different from each other. When n is 2 or more, a plurality of Xs may be different from each other.

The pigment skeleton represented by P is selected from the group consisting of a pyrrolopyrrole pigment skeleton, a diketopyrrolopyrrole pigment skeleton, a quinacridone pigment skeleton, an anthraquinone skeleton, a diterpene pigment skeleton, a benzoisoindole skeleton, Thiazinium blue pigment skeleton, azo pigment skeleton, quinophthalone pigment skeleton, phthalocyanine pigment skeleton, naphthalocyanine pigment skeleton, diterpene pigment skeleton, anthraquinone skeleton, purple ring ketone pigment skeleton, benzimidazolone pigment skeleton At least one of a benzothiazole dye skeleton, a benzimidazole dye skeleton, and a benzoxazole dye skeleton is preferably selected from the group consisting of a pyrrolopyrrolone skeleton, a diketopyrrolopyrrole pigment skeleton, and a quinacridone pigment skeleton. Further, at least one of the benzimidazolone dye skeletons is further preferred, and the pyrrolopyrrole pigment skeleton is particularly preferred.

Examples of the linking group represented by L include a hydrocarbon group, a heterocyclic group, -NR-, -SO ₂ -, -S-, -O-, -CO- or a group containing a combination thereof. R represents a hydrogen atom, an alkyl group or an aryl group.

The acid group represented by X may, for example, be a carboxyl group, a sulfonic acid group, a carboxylic acid guanamine group, a sulfonate guanamine group or a ruthenium group. As the carboxylic acid amide group, a group represented by -NHCOR ^X1 is preferred. As the sulfonium sulfonate group, a group represented by -NHSO ₂ R ^X2 is preferred. As the quinone imine group, a group represented by -SO ₂ NHSO ₂ R ^X3 , -CONHSO ₂ R ^X4 , -CONHCOR ^X5 or -SO ₂ NHCOR ^X6 is preferred. R ^X1 to R ^X6 each independently represent a hydrocarbon group or a heterocyclic group. The hydrocarbon group and the heterocyclic group represented by R ^X1 to R ^X6 may further have a substituent. As a further substituent, the substituent T described in the above formula (PP) is preferred, and a halogen atom is preferred, and a fluorine atom is more preferred. The basic group represented by X may, for example, be an amine group. The salt structure represented by X may, for example, be a salt of the above acid group or basic group.

The pigment derivative may, for example, be a compound having the following structure. In addition, Japanese Laid-Open Patent Publication No. Sho 56-118462, Japanese Laid-Open Patent Publication No. SHO-63-264674, Japanese Patent Laid-Open No. Hei No. 1-217077, Japanese Patent Laid-Open No. Hei No. 3-009961, No. 3-026767 Japanese Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Japanese Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. The compound described in 0094 and the like, and the compound described in Japanese Patent No. 5299151 are incorporated herein by reference. [Chemical Formula 27]

When the curable composition of the present invention contains a pigment derivative, the content of the pigment derivative is preferably from 1 to 50 parts by mass based on 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. When the content of the pigment derivative is within the above range, the dispersibility of the pigment can be improved to efficiently suppress aggregation of the pigment. The pigment derivative may be used alone or in combination of two or more. When two or more types are used, the total amount is preferably in the above range.

<<Solvent>> The curable composition of the present invention preferably contains a solvent. As a solvent, an organic solvent is mentioned. The kind of the solvent is basically not particularly limited as long as the solubility of each component or the coating property of the composition is satisfied. Examples of the organic solvent include esters, ethers, ketones, aromatic hydrocarbons, and the like. For the details of the above, reference is made to paragraph number 0223 of International Publication WO 2015/166779, which is incorporated herein by reference. Further, a cyclic alkyl-substituted ester solvent or a cyclic alkyl-substituted ketone solvent can also be preferably used. Specific examples of the organic solvent include dichloromethane, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, and diethyl ether. Alcohol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclohexyl acetate, cyclopentanone, ethyl carbitol acetate, butyl carbene Alcohol acetate, propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate. Further, from the viewpoint of improving solubility, 3-methoxy-N,N-dimethylpropane decylamine and 3-butoxy-N,N-dimethylpropane decylamine are also preferable. In the present invention, the organic solvent may be used singly or in combination of two or more. However, it is preferable to reduce aromatic hydrocarbons (benzene, toluene, xylene, ethylbenzene, etc.) as a solvent for reasons such as environmental reasons (for example, 50 mass can be set with respect to the total amount of organic solvents) The ppm (parts per million) or less may be 10 ppm by mass or less, and may be 1 ppm by mass or less.

In the present invention, a solvent having a small metal content is preferably used. The metal content of the solvent is, for example, 10 mass ppb (parts per billion) or less. A solvent having a mass ppt (parts per trillion) level, which is supplied, for example, by Toyo Gosei Kagaku Co., Ltd. (Chemical Industry Daily, November 13, 2015), can be used as needed.

Examples of the method for removing impurities such as metals from the solvent include distillation (such as molecular distillation or thin film distillation) or 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 still more preferably 3 μm or less. The material of the filter is preferably polytetrafluoroethylene, polyethylene or nylon.

The solvent may contain isomers (compounds having the same number of atoms but different structures). Further, the isomer may be contained alone or in combination of plural kinds.

In the present invention, the content of the peroxide in the organic solvent is preferably 0.8 mmol/L or less, and it is more preferable that the peroxide is not substantially contained.

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

The content of the solvent is preferably from 10 to 97% by mass based on the total amount of the curable composition. The lower limit is preferably 30% by mass or more, more preferably 40% by mass or more, more preferably 50% by mass or more, still more preferably 60% by mass or more, and particularly preferably 70% by mass or more. The upper limit is preferably 96% by mass or less, more preferably 95% by mass or less.

<<Polymerization inhibitor>> The curable composition of the present invention can contain a polymerization inhibitor. Examples of the polymerization inhibitor include hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, t-butyl catechol, benzoquinone, 4, 4 '-Thiobis(3-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-methyl-6-tert-butylphenol), N-nitrosobenzene Hydroxylamine salt (ammonium salt, sulfonium salt, etc.). Among them, p-methoxyphenol is preferred. The content of the polymerization inhibitor is preferably 0.001 to 5% by mass based on the total solid content of the curable composition.

<<Centane coupling agent>> The curable composition of the present invention contains a decane coupling agent. In the present invention, the decane coupling agent means a decane compound having a hydrolyzable group and a functional group other than the decane. Further, the hydrolyzable group means a substituent which is directly bonded to a ruthenium atom and which can generate a siloxane chain bond by at least one of a hydrolysis reaction and a condensation reaction. The hydrolyzable group may, for example, be a halogen atom, an alkoxy group or a decyloxy group, and an alkoxy group is preferred. That is, a decane coupling agent is preferably a compound having an alkoxyfluorenyl group. Further, examples of the functional group other than the hydrolyzable group include a vinyl group, a (meth)acryl fluorenyl group, a fluorenyl group, an epoxy group, an oxetanyl group, an amine group, a urea group, a thioether group, and an isocyanate group. , phenyl, etc. Examples of the decane coupling agent include the compounds described in paragraphs 0018 to 0036 of JP-A-2009-288703, and the compounds described in paragraphs 0056 to 0066 of JP-A-2009-242604. Introduced in this manual. The decane coupling agent is preferably a ureido coupling agent having a ureido group.

The content of the decane coupling agent is preferably 0.01 to 15.0% by mass, more preferably 0.05 to 10.0% by mass, based on the total solid content of the curable composition. The decane coupling agent may be used alone or in combination of two or more. In the case of two or more types, the total amount is preferably in the above range.

<<Interfacial Active Agent>> The curable composition of the present invention can contain a surfactant. As the surfactant, various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a ruthenium-based surfactant can be used. The surfactant can be referred to in paragraphs 0238 to 0245 of International Publication WO2015/166779, which is incorporated herein by reference.

In the present invention, a surfactant-based fluorine-based surfactant is preferred. By containing a fluorine-based surfactant in the curable composition of the present invention, liquid characteristics (especially fluidity) are further improved, and liquid repellency can be further improved. Further, it is also possible to form a film having a small thickness unevenness.

The fluorine content in the fluorine-based surfactant is preferably from 3 to 40% by mass, more preferably from 5 to 30% by mass, even more preferably from 7 to 25% by mass. The fluorine-based surfactant having a fluorine content in this range is effective from the viewpoint of thickness uniformity and liquid-saving property of the coating film, and also has good solubility in the composition.

Specific examples of the fluorine-based surfactant include those described in paragraphs 0060 to 0064 of JP-A-2014-041318 (paragraph No. 0060 to 0064 of the corresponding International Publication No. 2014/017669). The surfactants described in the paragraphs 0117 to 0132 of JP-A-2011-132503, the contents of which are incorporated herein by reference. Examples of commercially available fluorine-based surfactants include MEGAFACE F171, F172, F173, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780, and EXP. MFS-330 (above manufactured by DIC Corporation), Fluorad FC430, FC431, FC171 (above 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 (above, manufactured by ASAHI GLASS CO., LTD.), PolyFox PF636, PF656, PF6320, PF6520, PF7002 (above, manufactured by OMNOVA Solutions Inc.) and the like.

Further, the fluorine-based surfactant can also preferably be an acrylic compound which has a molecular structure having a functional group containing a fluorine atom, and a functional group containing a fluorine atom is cleaved while applying heat, and a fluorine atom Volatile. As such a fluorine-based surfactant, MEGAFACE DS series (Chemical Industry Daily, February 22, 2016) manufactured by DIC Corporation (Nikkei Industry News, February 23, 2016), for example, MEGAFACE can be cited. DS-21.

A block polymer can also be used as the fluorine-based surfactant. For example, the compound described in JP-A-2011-089090 can be cited. The fluorine-based surfactant can also preferably use a fluorine-containing polymer compound containing a repeating unit derived from a (meth) acrylate compound having a fluorine atom and derived from having two or more (preferably It is a repeating unit of a (meth) acrylate compound which is an alkoxy group (preferably an ethoxy group, a propenyloxy group) of 5 or more. The following compounds can also be exemplified as the fluorine-based surfactant used in the present invention. [Chemical Formula 28] The weight average molecular weight of the above compound is preferably from 3,000 to 50,000, for example, 14,000. Among the above compounds, the % indicating the ratio of the repeating unit is mol%.

In the present invention, a compound having a fluorine atom and a curable group (hereinafter also referred to as a fluorine-containing curable compound) is preferably used as the fluorine-based surfactant. By using such a surfactant, the solvent resistance of the obtained cured film can be improved. The reason why excellent solvent resistance can be obtained by using a fluorine-containing curable compound is presumed to be based on the following. Since the surface free energy of the fluorine-containing curable compound is low, for example, in a coating film formed by coating a composition on a support such as a substrate, the fluorine-containing curable compound tends to be biased on the surface of the coating film on the side opposite to the support. nearby. When the curable composition of the present invention is cured in such a state that the fluorine-containing curable compound is so biased, a region having a large proportion of the cured product of the fluorine-containing curable compound is formed on the surface on the side away from the substrate. By the presence of such a region, even if the film is immersed in a solvent, the near-infrared absorbing pigment is hardly leached from the surface of the film, and excellent solvent resistance can be obtained.

Examples of the curable group of the fluorine-containing curable compound include a (meth)acrylonitrile group, an epoxy group, and an oxetanyl group, and a (meth)acryl fluorenyl group is preferred.

The fluorine-containing curable compound preferably has at least one selected from the group consisting of an alkyl group substituted with a fluorine atom, an alkyl group substituted with a fluorine atom, and an aryl group substituted with a fluorine atom. The alkylene group substituted by a fluorine atom is preferably a linear, branched or cyclic alkylene group in which at least one hydrogen atom is substituted by 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 alkyl group substituted by a fluorine atom and the alkyl group substituted by a fluorine atom is preferably from 1 to 20, more preferably from 1 to 10, still more preferably from 1 to 5. With respect to the aryl group substituted by a fluorine atom, it is preferred that the aryl group is directly substituted by a fluorine atom or substituted by a trifluoromethyl group. The alkyl group substituted by a fluorine atom, the alkyl group substituted by a fluorine atom, and the aryl group substituted by a fluorine atom may further have a substituent other than a fluorine atom. As a specific example of the above, for example, paragraphs 0266 to 0722 of JP-A-2011-100089 can be referred to, and the contents are incorporated herein by reference.

The fluorine-containing curable compound is preferably a compound containing a fluoroether group and a curable group. Examples of the fluoroether group include a group X (a group represented by the formula (X)) obtained by linking an alkyl group substituted with a fluorine atom and an oxygen atom. A fluoroether-based perfluoroalkylene ether group is preferred. Further, the perfluoroalkylene ether group means that L _A in the following formula (X) is a perfluoroalkylene group. The perfluoroalkylene group means a group in which all hydrogen atoms in the alkyl group are substituted by a fluorine atom. Formula (X) - (L _{A -} O) n - The above L _A represents an alkylene group substituted by a fluorine atom. The alkyl group having a fluorine atom substituted with a fluorine atom is preferably 1 to 20, more preferably 1 to 10, still more preferably 1 to 5. The alkylene group substituted by a fluorine atom may be linear or branched. n represents an integer of 1 or more, preferably 1 to 50, more preferably 1 to 20. Further, when n is 2 or more, a plurality of - (L _A -O) - in L _A may be the same, also be different.

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

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

[Chemical Formula 29]

In the formulae (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)acryl fluorenyl group, an epoxy group or an oxetanyl group, and X ² represents an alkyl group substituted with a fluorine atom or an aryl group substituted with a fluorine atom, and X ³ represents a formula represented by the formula (X). Group.

In the formulae (B1) to (B3), R ¹ to R ¹¹ each independently have a hydrogen atom or an alkyl group. When R ¹ to R ¹¹ represent an alkyl group, an alkyl group having 1 to 3 carbon atoms is preferred. When R ¹ to R ¹¹ represent a halogen atom, a fluorine atom is preferred. In the formulae (B1) to (B3), when L ¹ to L ⁴ represent a divalent linking group, the divalent linking group may be an alkyl group which may be substituted by a halogen atom and may be substituted by a halogen atom. An aryl group, -NR ¹² -, -CONR ¹² -, -CO-, -CO ₂ -, -SO ₂ NR ¹² -, -O-, -S-, -SO ₂ - or a combination thereof. Wherein, at least one selected from the group consisting of an alkylene group having 2 to 10 carbon atoms which may be substituted by a halogen atom and an alkylene group having a carbon number of 6 to 12 which may be substituted by a halogen atom, or a group containing the same And a group selected from the group consisting of -NR ¹² -, -CONR ¹² -, -CO-, -CO ₂ -, -SO ₂ NR ¹² -, -O-, -S-, and -SO ₂ - A group of a combination of groups is preferred, and an alkyl group having 2 to 10 carbon atoms which may be substituted by a halogen atom, -CO ₂ -, -O-, -CO-, -CONR ¹² - or containing the same The group of the group is better. 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 from 30 to 95 mol%, more preferably from 45 to 90 mol%, based on all the repeating units in the fluorine-containing curable compound. The total content of the repeating unit represented by the above formula (B2) and the repeating unit represented by the formula (B3) is preferably from 5 to 70 mol%, and preferably from 10 to 60, based on all the repeating units in the fluorine-containing curable compound. Molar% is better. Further, when the repeating unit represented by the formula (B2) is not contained and the repeating unit represented by the formula (B3) is contained, the content of the repeating unit represented by the formula (B2) is 0 mol% and represented by the formula (B3) The content of the repeating unit is preferably in the above range.

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

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

As a commercial item of the fluorinated curable compound, for example, MEGAFACE RS-72-K, MEGAFACE RS-75, MEGAFACE RS-76-E, MEGAFACE RS-76-NS, MEGAFACE RS-77, etc., manufactured by DIC Corporation can be used. The fluorine-containing sclerosing compound can also be used as described in paragraphs 0050 to 0090 and paragraphs 0289 to 0295 of JP-A-2010-164965, and paragraphs 0015 to 0158 of JP-A-2015-117327. The compound described. Further, as the fluorine-containing curable compound, a polymer having a repeating unit represented by (B1-1) and a repeating unit represented by the formula (B3-1) can also be used. In the formula (B3-1), X represents a fluoromethylene group or a fluorine-extended ethyl group, and r represents the number of repeating units. [Chemical Formula 30]

Examples of the nonionic surfactant include glycerol, trimethylolpropane, trimethylolethane, and the like, and ethoxylates and propoxylates (for example, glycerin C). Oxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene fluorenyl Phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester, Pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2 (manufactured by BASF Corporation) Tetronic 304, 701, 704, 901, 904, 150R1 (manufactured by BASF Corporation), Solsperse 20000 (manufactured by Japan Lubrizol Corporation), NCW-101, NCW-1001, NCW-1002 (manufactured by Wako Pure Chemical Industries, Ltd.), PIONIN D-6112, D-6112-W, D-6315 (manufactured by Takemoto Oil & Fat Co., Ltd.), OLFIN E1010, Surfynol 104, 400, 440 (manufactured by Nissin Chemical Co., Ltd.), and the like.

The content of the surfactant is preferably 0.001 to 5.0% by mass, more preferably 0.005 to 3.0% by mass, based on the total solid content of the curable composition. The surfactant may be used alone or in combination of two or more. In the case of two or more types, the total amount is preferably in the above range.

<<Ultraviolet absorber>> The curable composition of the present invention can contain an ultraviolet absorber. As the ultraviolet absorber, a conjugated diene compound, an aminobutadiene compound, a methylbenzimidyl compound, a coumarin compound, a salicylate compound, a benzophenone compound, or a benzotriazole can be used. a compound, an acrylonitrile compound, a hydroxyphenyltriazine compound, or the like. For the details of the above, the descriptions of paragraphs 0033 to 0723 of JP-A-2012-208374, and paragraphs 0317 to 0334 of JP-A-2013-068814 are incorporated herein by reference. The commercially available product of the conjugated diene compound is, for example, UV-503 (manufactured by DAITO CHEMICAL CO., LTD.). Further, as the benzotriazole compound, MYUA series (Chemical Industry Daily, February 1, 2016) manufactured by MIYOSHI OIL & FAT CO., LTD. can 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, the ultraviolet absorber may be used alone or in combination of two or more. When two or more types are used, it is preferred that the total amount of these is within the above range.

<<Other components>> The curable composition of the present invention may contain a sensitizer, a curing accelerator, a filler, a thermal polymerization inhibitor, a plasticizer, a adhesion promoter, and other auxiliary agents (for example, conductive particles) as needed. , fillers, defoamers, flame retardants, leveling agents, stripping accelerators, antioxidants, potential antioxidants, perfumes, surface tension modifiers, chain transfer agents, etc.). For the above-mentioned components, the descriptions of paragraphs 0101 to 0104 and 0107 to 0109 of JP-A-2008-250074 can be referred to, and the contents are incorporated herein by reference. Further, examples of the antioxidant include a phenol compound, a phosphite compound, and a thioether compound. 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 2 or more types. As the phenol compound, any phenol compound known as a phenolic antioxidant can be used. As a preferable phenol compound, a hindered phenol compound is mentioned. In particular, a compound having a substituent at a site adjacent to the phenolic hydroxyl group (ortho) is preferred. Further, it is also preferred that the antioxidant is a compound having a phenol group and a phosphite group in the same molecule. Further, as the antioxidant, a phosphorus-based antioxidant can also be preferably used. As the phosphorus-based antioxidant, it is exemplified to include three [2-[[2,4,8,10-tetra(1,1-dimethylethyl)dibenzo[d,f][1,3 , 2] dioxaphosphepin-6-yl]oxy]ethyl]amine, tris[2-[(4,6,9,11-tetra-t-butyldibenzo[d] , f][1,3,2]dioxaphosphinoin-2-yl)oxy]ethyl]amine and bis(2,4-di-t-butyl-6-methylphenyl) At least one compound of the group of ethyl phosphates. These can be obtained as commercial products. For example, Adekastab AO-20, Adekastab AO-30, Adekastab AO-40, Adekastab AO-50, Adekastab AO-50F, Adekastab AO-60, Adekastab AO-60G, Adekastab AO-80, Adekastab AO-330 (ADEKA) CORPORATION) and so on. Further, as the antioxidant, a polyfunctional hindered amine antioxidant described in International Publication WO2017/006600 can also be used. The content of the antioxidant is preferably from 0.01 to 20% by mass, more preferably from 0.3 to 15% by mass, based on the total solid content of the curable composition. The antioxidant may be used alone or in combination of two or more. In the case of two or more types, the total amount is preferably in the above range. The potential antioxidant is protected by a protective group, and the protective group is removed by heating at 100 to 250 ° C or in the presence of an acid/base catalyst at 80 to 200 ° C to act as an antioxidant. Functional compounds are preferred. The compound which is described in the Unexamined-Japanese-Patent No. WO2014/021023, the International Publication WO2017/030005, and the Unexamined-Japanese-Patent No. 2017-008219. As a commercial item, ADEKA ARKLS GPA-5001 (made by ADEKA CORPORATION) etc. are mentioned.

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

The container for the curable composition of the present invention is not particularly limited, and a known container can be used. Further, for the purpose of suppressing the incorporation of impurities into the material or the composition, it is preferable to use a multi-layer bottle in which the inner wall of the container is composed of six kinds of six layers of resin or a bottle having a seven-layer structure in which six kinds of resins are used. As such a container, for example, a container described in JP-A-2015-123351 can be cited.

The use of the curable composition of the present invention is not particularly limited. For example, it can be preferably used to form a near-infrared cut filter or the like. Further, when the curable composition of the present invention contains a color material that blocks visible light, an infrared transmission filter that can transmit only near-infrared rays having a specific wavelength or more can be used.

<Method for Preparing Curable Composition> The curable composition of the present invention can be prepared by mixing the above components. In the preparation of the curable composition, all of the components may be simultaneously dissolved or dispersed in a solvent to prepare a curable composition, or two or more solutions or dispersions in which each component is appropriately blended may be prepared in advance, and These were mixed at the time of application (at the time of coating) to prepare a curable composition.

Further, when the curable composition of the present invention contains particles such as pigments, a process including dispersing particles is preferred. In the process of dispersing particles, as the mechanical force used for the dispersion of the particles, compression, pressing, impact, shearing, cavitation, and the like may be mentioned. Specific examples of such processes include a bead mill, a sand mill, a roll mill, a bead mill, a paint shaker, a microfluidizer, a high speed impeller, a sand mixer, and a jet stream. Flowjet mixer, high pressure wet micronization, ultrasonic dispersion, and the like. Further, when the particles in the sand mill (bead mill) are pulverized, it is preferable to carry out the treatment under the condition that the pulverization efficiency is improved by using beads having a small diameter, increasing the filling ratio of the beads, and the like. Further, it is preferred to remove coarse particles by filtration, centrifugation or the like after the pulverization treatment. Further, the process for dispersing particles and the dispersing machine can preferably be dispersed using "Dispersion Technology Encyclopedia, issued by JOHOKIKO CO., LTD., July 15, 2005" or "Dispersion (solid/liquid dispersion)" The process and disperser described in paragraph 0022 of the Japanese Patent Publication No. 2015-157893, issued on October 10, 1978. Further, in the process of dispersing the particles, the particle refining treatment may be performed by a salt milling step. The materials, the equipment, the processing conditions, and the like used in the salt milling step can be referred to, for example, in JP-A-2015-194521 and JP-A-2012-046629.

When the curable composition is prepared, it is preferred to filter the curable composition with a filter for the purpose of removing foreign matter or reducing defects. The filter can be used without any particular limitation as long as it is used for a filter or the like. For example, a fluororesin such as polytetrafluoroethylene (PTFE), a polyamide resin such as nylon (for example, nylon-6 or nylon-6,6), or a polyolefin resin such as polyethylene or polypropylene (PP) may be used. A filter comprising materials such as high density, ultra high molecular weight 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 to 7.0 μm, preferably about 0.01 to 3.0 μm, and more preferably about 0.05 to 0.5 μm. When the pore diameter of the filter is within the above range, fine foreign matter can be reliably removed. Further, it is also preferable to use a fibrous filter medium. Examples of the fibrous filter material include polypropylene fibers, nylon fibers, and glass fibers. Specifically, a filter element of the SBP type series (SBP008 or the like), the TPR type series (TPR002, TPR005, etc.), and the SHPX type series (SHPX003) manufactured by ROKI TECHNO CO., LTD. can be cited.

When a filter is used, different filters (for example, a first filter, a second filter, etc.) can be combined. In this case, the filtration by each filter may be performed only once or twice or more. Further, it is also possible to combine filters of different pore diameters within the above range. The aperture at this time can be referred to the nominal value of the filter manufacturer. As a commercially available filter, for example, it can be selected from various filters supplied by NIHON PALL LTD. (DFA4201NIEY, etc.), Advantec Toyo Kaisha, Ltd., Nihon Entegris K.K. (formerly Nippon Mykrolis Corporation) or KITZ MICROFILTER CORPORATION. The second filter can be formed using the same material as the first filter or the like. Further, the filtration by the first filter can be performed only on the dispersion, and after mixing the other components, the filtration is performed by the second filter.

<Cured film> The cured film of the present invention is obtained from the above-described curable composition of the present invention. The cured film of the present invention can be preferably used as a near-infrared cut filter. Moreover, it can also be used as a heat ray shielding filter or an infrared ray transmission filter. The cured film of the present invention may have a pattern or a film (planar film) having no pattern.

The cured film of the present invention may be used by laminating on a support, or may be used after being peeled off from the support. Examples of the support include a semiconductor substrate such as ruthenium or a transparent substrate.

The transparent substrate used as the support is not particularly limited as long as it is composed of a material capable of transmitting at least visible light. For example, a base material made of a material such as glass or resin can be given. Examples of the resin include polyester resins such as polyethylene terephthalate and polybutylene terephthalate, polyolefin resins such as polyethylene, polypropylene, and ethylene-vinyl acetate copolymer, and norbornene resins. An acrylic resin such as polyacrylate or polymethyl methacrylate, a urethane resin, a vinyl chloride resin, a fluororesin, a polycarbonate resin, a polyvinyl butyral resin, or a polyvinyl alcohol resin. Examples of the glass include soda lime glass, borosilicate glass, alkali-free glass, quartz glass, and glass containing copper. Examples of the glass containing copper include phosphate glass containing copper and fluorophosphate glass containing copper. The content of copper in the glass containing copper is preferably from 0.1 to 20% by mass, more preferably from 0.3 to 17% by mass, even more preferably from 0.5 to 15% by mass. The glass containing copper preferably has a maximum absorption wavelength in the 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 the glass containing copper include the following. (1) Containing P ₂ O ₅ 46 to 70% by mass, 0.2 to 20% of AlF ₃ , 0 to 25% of ΣRF (R = Li, Na, K), ΣR'F ₂ (R' = Mg, Ca And Sr, Ba, and Pb) are 1 to 50%, and the glass containing 0.5 to 7 parts by mass of CuO as an external percentage is contained with respect to 100 parts by mass of the base glass containing 0.5 to 32% of F and 26 to 54% of O. (2) Containing P ₂ O ₅ 25 to 60% by mass, Al ₂ O ₃ 1 to 13%, MgO 1 to 10%, CaO 1 to 16%, BaO 1 to 26%, and SrO 0 to 16%. ZnO 0 to 16%, Li ₂ O 0 to 13%, Na ₂ O 0 to 10%, K ₂ O 0 to 11%, CuO 1 to 7%, ΣRO (R = Mg, Ca, Sr, Ba) 15 to Glass of 40%, ΣR' ₂ O (R'=Li, Na, K) 3 to 18% (wherein, O ² ions of 39% molar amount are substituted by F). (3) Containing P ₂ O ₅ 5 to 45% by mass, AlF ₃ 1 to 35%, ΣRF (R=Li, Na, K) 0 to 40%, ΣR'F ₂ (R'=Mg, Ca , Sr, Ba, Pb, Zn) 10 to 75%, R"F _m (R" = La, Y, Cd, Si, B, Zr, Ta, m is the number of valences equivalent to R") 0~ 15% (wherein 70% of the total amount of fluoride can be replaced by an oxide) and glass of 0.2 to 15% of CuO. (4) P ⁵⁺ 11 to 43%, Al ³⁺ 1 in terms of cationic % ～29%, ΣR cation (R=Mg, Ca, Sr, Ba, Pb, Zn) 14～50%, ΣR′ cation (R′=Li, Na, K) 0～43%, ΣR′′ cation (R ''=La, Y, Gd, Si, B, Zr, Ta) 0 to 8% and Cu ²⁺ 0.5 to 13%, and further comprising F ^- 17 to 80% of glass in terms of anion %. (5) Included P ⁵⁺ 23 to 41%, Al ³⁺ 4 to 16%, Li ⁺ 11 to 40%, Na ⁺ 3 to 13%, ΣR cation (R = Mg, Ca, Sr, Ba, Zn) in terms of cationic % ～53% and Cu ²⁺ 2.6 to 4.7%, and further comprising F ^- 25 to 48% and O ² 52 to 75% of glass in terms of anion %. (6) P ₂ O _{5 in} terms of mass % _{70 ~ 85%, Al 2 O} 3 8 ~ 17%, B 2 O 3 1 ~ 10%, Li 2 O 0 ~ 3% _{Na 2 O 0 ~ 5%,} K 2 O 0 ~ 5%, ΣR 2 O (R = Li, Na, K) 0.1 ~ 5%, parts of SiO ₂ 0 ~ 3% of basic glass 100 mass, comprising an external percentage 0.1 to 5 parts by mass of CuO glass.

A commercially available product can also be used for the glass containing copper. As a commercial item of the copper-containing glass, NF-50 (made by AGC TECHNO GLASS Co., Ltd.) etc. are mentioned.

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 further preferably 5 μm or less. The lower limit of the film thickness is preferably 0.1 μm or more, more preferably 0.2 μm or more, and further preferably 0.3 μm or more.

When the cured film of the present invention is used as a near-infrared cut filter, the cured film of the present invention preferably has a maximum absorption wavelength in a wavelength range of 700 to 1300 nm, and has a maximum absorption wavelength in a wavelength range of 700 to 1000 nm. Preferably, it is more preferable to have a maximum absorption wavelength in the range of 720 to 980 nm, and it is particularly preferable to have a maximum absorption wavelength in the 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 satisfies at least one of the following conditions (1) to (4), and satisfies (1) to (4). All conditions are further preferred. (1) The transmittance at a wavelength of 400 nm is preferably 70% or more, more preferably 80% or more, 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, 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, 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, more preferably 90% or more, and particularly preferably 95% or more.

When the cured film of the present invention is used as a near-infrared cut filter, the cured film of the present invention has an average transmittance of 70% or more at a wavelength of 400 to 550 nm, preferably 80% or more, and more preferably 85% or more. Further preferably, more than 90% is particularly preferred. Further, the transmittance in any range of the wavelength of 400 to 550 nm is preferably 70% or more, more preferably 80% or more, and still more preferably 90% or more. Further, the transmittance at least one point in the range of the wavelength of 700 to 1300 nm is preferably 20% or less, more preferably 15% or less, and still more preferably 10% or less.

The cured film of the present invention can also be used in combination with a color filter containing a coloring agent. The color filter can be manufactured using a colored composition containing a coloring agent. As the coloring agent, a coloring agent which can be included in the curable composition of the present invention can be mentioned. Further, the cured film of the present invention may contain a coloring agent to form a filter having a function as a near-infrared cut filter and a color filter.

When the cured film of the present invention is used as a near-infrared cut filter and the cured film of the present invention is used in combination with a color filter, a color filter is preferably disposed on the optical path of the cured film of the present invention. For example, the cured film of the present invention and a color filter can be laminated to be used as a laminate. In the laminate, both the cured film of the present invention and the color filter may be adjacent to each other in the thickness direction or may not be adjacent. 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 another support different from the support on which the color filter is formed, or may be in the present invention. Other components (for example, microlenses, planarization layers, etc.) constituting the solid-state imaging device are interposed between the cured film and the color filter.

Further, in the present invention, the near-infrared cut filter refers to a filter that transmits light (visible light) of a wavelength in a visible region and blocks at least a part of light (near infrared rays) of a wavelength in a near-infrared region. The near-infrared cut filter may transmit all of the light of the wavelength of the visible region, or may transmit light of a specific wavelength region of the light of the visible region to block the light of the specific wavelength region. Further, in the present invention, the color filter refers to a filter that transmits light of a specific wavelength region of light of a wavelength in a visible region and blocks light of a specific wavelength region. Further, in the present invention, the near-infrared transmission filter refers to a filter that blocks visible light and transmits at least a part of near-infrared rays.

<Laminated body> The laminated body of the present invention has the cured film of the present invention on the support. As the support, a transparent substrate is preferred, a glass substrate is preferred, and a glass substrate containing copper is more preferred. In particular, when the cured film of the present invention is used as a near-infrared cut filter, the cured film of the present invention is laminated on a glass substrate containing copper to form a laminate, and a wide range of near-infrared rays can be blocked.

In the laminate of the present invention, the cured film of the present invention may be directly laminated on the surface of the support, but a composition containing a compound having a cyclic ether group is used between the support and the cured film of the present invention (below A film obtained also as a composition A) is preferred. Further, when the laminate of the present invention has a film obtained by using the above-described composition A (hereinafter also referred to as film A) between the cured film of the present invention and the support, one side of the film A is in contact with the support and the other side Contact with the cured film of the present invention is preferred. In this way, the cured film of the present invention has good adhesion to the support. In particular, when a glass substrate containing copper is used as a support, the adhesion can be remarkably improved.

The cyclic ether group which the compound which has a cyclic ether group has an epoxy group and an oxetanyl group, and an epoxy group is preferable. The details of the compound having a cyclic ether group include the materials described in the compound of the above-mentioned curable composition having a cyclic ether group.

In the composition A, the content of the compound having a cyclic ether group is not particularly limited, and is preferably 1% by mass or more, more preferably 2% by mass or more, and more preferably 3 parts by mass based on the total solid content of the composition A. More preferably, % or more is further more preferable, and 5% by mass or more is further more preferable. The upper limit can be set to 100% by mass. Further, the composition A may further contain a radical polymerizable compound, a radical polymerization initiator, a solvent, a surfactant, and the like in addition to the compound having a cyclic ether group. The above materials can be mentioned as the details of these.

The thickness of the above film A is not particularly limited. For example, it is preferably 1 μm or less, more preferably 0.5 μm or less, and further preferably 0.2 μm or less. The lower limit of the film thickness is preferably 0.01 μm or more, more preferably 0.03 μm or more, and further preferably 0.05 μm or more. Further, the ratio of the thickness t1 of the cured film of the present invention to the thickness t2 of the film A is preferably t1: t2 = 1: 0.002 to 0.2, more preferably 1: 0.006 to 0.1, and further 1: 0.01 to 0.04. good.

The layered body of the present invention preferably has an inorganic film on the cured film of the present invention. Examples of the inorganic film include a dielectric multilayer film and the like.

The dielectric multilayer film shields the infrared film by the interference effect of light. Specifically, a film obtained by alternately laminating two or more layers of a dielectric layer (a high refractive index material layer and a low refractive index material layer) having different refractive indices is used. As the material constituting the high refractive index material layer, a material having a refractive index of 1.7 or more (preferably 1.7 to 2.5) is preferably used. For example, titanium oxide, zirconium oxide, antimony pentoxide, antimony pentoxide, antimony oxide, antimony oxide, zinc oxide, zinc sulfide or indium oxide as a main component and containing a small amount of titanium oxide, tin oxide and/or antimony oxide may be mentioned. And so on. As the material constituting the low refractive index material layer, a material having a refractive index of 1.6 or less (preferably 1.2 to 1.6) is preferably used. For example, cerium oxide, aluminum oxide, cerium fluoride, magnesium fluoride, and sodium aluminum hexafluoride can be mentioned. The thickness of each layer of the high refractive index material layer and the low refractive index material layer is preferably a thickness of 0.1 λ to 0.5 λ of the wavelength λ (nm) of the infrared ray to be blocked. Further, the total number of laminated layers of the high refractive index material layer and the low refractive index material layer in the dielectric multilayer film is preferably 2 to 100 layers, more preferably 2 to 60 layers, and still more preferably 2 to 40 layers. For the details of the dielectric multilayer film, the descriptions of paragraphs 0255 to 0259 of JP-A-2014-041318 can be referred to, and the contents are incorporated herein by reference.

When the laminate of the present invention has an inorganic film on the cured film of the present invention, an inorganic film can be directly laminated on the surface of the cured film of the present invention, but from the viewpoint of film formability of the inorganic film or adhesion of the inorganic film Further, it is preferable to further have a planarization layer between the cured film of the present invention and the inorganic film. The planarization layer can be formed using a resin composition or the like. The above materials are mentioned as a resin. Further, the resin composition may further contain a radical polymerizable compound, a radical polymerization initiator, a solvent, a surfactant, and the like. The above materials can be mentioned as the details of these.

The thickness of the planarization layer is not particularly limited. For example, it is preferably 5 μm or less, more preferably 3 μm or less, and still more preferably 1 μm or less. The lower limit of the film thickness is preferably 0.1 μm or more, more preferably 0.3 μm or more, and further preferably 0.5 μm or more.

The laminate of the present invention can be used for various devices such as a near-infrared cut filter, a solid-state imaging device such as a CCD (Charge Coupled Device) or a CMOS (Complementary Metal Oxide Semiconductor), an infrared sensor, and an image display device.

<Method for Producing Cured Film> Next, a method for producing the cured film of the present invention will be described. The method for producing a cured film of the present invention comprises the steps of applying the curable composition of the present invention to form a curable composition layer, and the step of heat-hardening the curable composition layer.

In the method for producing a cured film, it is preferred to apply a curable composition to a support. The support may be mentioned as a support. As a method of applying a curable composition to a support, a well-known method can be used. For example, a dropping method (drop casting); a slit coating method; a spray method; a roll coating method; a spin coating method (spin coating method); a casting coating method; a slit spin coating method; and a pre-wetting method ( For example, the method described in Japanese Laid-Open Patent Publication No. 2009-145395); inkjet (for example, on-demand method, piezoelectric method, thermal method), nozzle ejection, and the like, discharge printing, flexographic printing, screen printing, and gravure printing. Various printing methods such as reverse offset printing and metal mask printing; a transfer method such as a mold; a nano imprint method, and the like. The method of applying the inkjet is not particularly limited, and for example, "Inkjet that can be promoted and used - the infinite possibility seen in the patent - issued in February 2005, SB RESEARCH CO., LTD." The method of the present invention (in particular, from page 115 to page 133), or JP-A-2003-262716, JP-A-2003-185831, JP-A-2003-261827, JP-A-2012-126830 The method described in JP-A-2006-169325 or the like. Moreover, the method of applying the curable composition can be referred to the description of International Publication No. WO2017/030174 and International Publication No. WO2017/018419, the contents of which are incorporated herein by reference.

The hardenable composition suitable for the support can be dried (prebaked). When prebaking is carried out, the prebaking temperature is preferably 150 ° C or lower, more preferably 120 ° C or lower, and further preferably 110 ° C or lower. The lower limit can be, for example, 50 ° C or higher, and can be 80 ° C or higher. The prebaking time is preferably from 10 seconds to 3,000 seconds, more preferably from 40 to 2,500 seconds, and further preferably from 80 to 220 seconds. Drying can be carried out using a hot plate, an oven, or the like.

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

The step of forming a pattern may be further included in the method of producing the cured film of the present invention. As the pattern forming method, a pattern forming method using a photolithography method or a pattern forming method using a dry etching method can be given. When the pattern is formed by photolithography, it is preferred to perform heat curing of the curable composition layer after patterning. Further, when the pattern is formed by the dry etching method, it is preferable to form a pattern after performing heat curing of the curable composition layer. Further, when the cured film of the present invention is used as a flat film, the step of forming a pattern may not be performed. Hereinafter, the steps of forming a pattern will be described in detail.

(When Forming Pattern by Photolithography) The pattern forming method by photolithography includes the following steps: exposing the curable composition layer formed by applying the curable composition of the present invention in a pattern a step (exposure step); and a step of developing and patterning by removing the hardenable composition layer of the unexposed portion (developing step). A step of baking the developed pattern (post-baking step) may be provided as needed.

(When the pattern is formed by the dry etching method) Pattern formation by the dry etching method can be performed by heat-hardening the curable composition layer to form a cured layer, and then forming on the cured layer. The patterned resist layer is then subjected to dry etching of the cured layer using an etching gas using the patterned resist layer as a mask. For the pattern formation by the dry etching method, the description of paragraphs 0010 to 0067 of JP-A-2013-064993 is incorporated herein by reference.

<Near-infrared cut filter> Next, the near-infrared cut filter of the present invention will be described. The near-infrared cut filter of the present invention includes the cured film of the present invention. The near-infrared cut filter of the present invention preferably has the cured film of the present invention on the support. As the support, the support may be mentioned, a transparent substrate is preferable, a glass substrate is more preferable, and a glass substrate containing copper is more preferable. In this way, a wide range of near infrared rays can be blocked.

In addition to the cured film of the present invention, the near-infrared cut filter of the present invention may further include an inorganic film such as a dielectric multilayer film or an ultraviolet absorbing layer. Further, the near-infrared cut filter further has a dielectric multilayer film, and it is easy to obtain a near-infrared cut filter having a wide viewing angle and excellent near-infrared shielding properties. Further, the near-infrared cut filter further has an ultraviolet absorbing layer, and a near-infrared cut filter excellent in ultraviolet shielding properties can be obtained. As the ultraviolet absorbing layer, for example, the absorbent layer described in paragraphs 0040 to 0070 and 0119 to 0145 of International Publication WO2015/099060 can be referred to, and the contents are incorporated in the present specification. As a dielectric multilayer film, the description of paragraphs 0255 to 0259 of JP-A-2014-041318 can be referred to, and the contents are incorporated herein by reference.

In addition, when the near-infrared cut filter of the present invention further has an inorganic film such as a dielectric multilayer film in addition to the cured film of the present invention, an inorganic film may be provided on the surface layer of the cured film of the present invention. A planarization layer is provided between the cured film of the invention and the inorganic film. From the viewpoint of the film forming property of the inorganic film or the adhesion of the inorganic film, it is preferred to provide a planarizing layer between the cured film of the present invention and the inorganic film.

The near-infrared cut filter of the present invention can be used for various devices such as a solid-state imaging device such as a CCD (Charge Coupled Device) or a CMOS (Complementary Metal Oxide Semiconductor), or an infrared sensor or an image display device.

<Solid-State Imaging Device> 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 a configuration in which it functions as a solid-state imaging device. For example, the following configuration can be mentioned.

The photoreceptor has a plurality of photodiodes constituting a light receiving region of the solid-state imaging device and a transmission electrode including a polysilicon or the like, and the photodiode and the transmission electrode have a light-receiving portion opening only of the photodiode including tungsten. The light-shielding film has a device protective film which is formed to cover the entire light-shielding film and the photodiode light-receiving portion and includes tantalum nitride or the like on the light-shielding film, and has the cured film of the present invention on the device protective film. Further, it may be a configuration of a light collecting means (for example, a microlens or the like, the same applies hereinafter) on the device protective film and on the lower side (the side close to the support) of the cured film of the present invention, or hardening in the present invention. The film has a configuration of a light collecting mechanism and the like. Further, the color filter may have a structure in which a film for forming each pixel is buried in a space partitioned by, for example, a lattice wall. In this case, the refractive index of the wall wall is preferably lower than the refractive index of each pixel. Examples of the image pickup apparatus having such a configuration include those described in Japanese Laid-Open Patent Publication No. Hei. No. Hei.

<Image Display Device> The image display device of the present invention includes the cured film of the present invention. Examples of the image display device include a liquid crystal display device, an organic electroluminescence (organic EL) display device, and the like. The definition or details of the image display device are described, for example, in "Electronic Display Devices (Kozoo Chosakai Publishing Co., Ltd., 1990)", "Display Devices (Ibuki Shun, Sangyo Tosho Publishing Co) .,Ltd., issued in the first year of Heisei) and so on. Further, the liquid crystal display device is described, for example, in "Next Generation Liquid Crystal Display Technology (Edited by Kogyo Chosakai Publishing Co., Ltd., 1994)". The liquid crystal display device to which the present invention can be applied is not particularly limited, and can be applied to, for example, various types of liquid crystal display devices described in the "Next Generation Liquid Crystal Display Technology". The image display device may be a person having a white organic EL element. As the white organic EL element, a tandem structure is preferable. The series structure of the organic EL device is described in Japanese Patent Laid-Open Publication No. 2003-045676, Sansei Mingyi, "The forefront of organic EL technology development - high brightness, high precision, long life, skill set", and Technical Information. Institute Co., Ltd., p. 326 - page 328, 2008, etc. The spectrum of the white light emitted from the organic EL element is preferably a blue region (430 nm to 485 nm), a green region (530 nm to 580 nm), and a yellow region (580 nm to 620 nm) having a strong maximum luminescence peak. In addition to these luminescence peaks, it is more preferable to further have a large luminescence peak in the red region (650 nm to 700 nm).

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

In Fig. 1, reference numeral 110 is a solid-state imaging element. The imaging region provided on the solid-state imaging device 110 has a near-infrared cut filter 111 and an infrared transmission filter 114. Further, a color filter 112 is laminated on the near-infrared cut filter 111. The microlens 115 is disposed on the side of the incident light hν of the color filter 112 and the infrared ray transmitting 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 in accordance with the light-emitting wavelength of the infrared light-emitting diode (infrared LED) to be used.

The color filter 112 is formed of a color filter that transmits and absorbs pixels of light of a specific wavelength in a visible region, and is not particularly limited, and a conventionally known color filter for pixel formation can be used. For example, a color filter in which pixels of red (R), green (G), and blue (B) are formed can be used. For example, the descriptions of paragraphs 0214 to 0263 of JP-A-2014-043556 can be referred to, and the contents are incorporated herein by reference.

The infrared transmission filter 114 selects its characteristics in accordance with the wavelength of the light emitted from the infrared LED.

In the infrared sensor shown in FIG. 1, another near-infrared cut filter (other near-infrared cut filter) different from the near-infrared cut filter 111 may be further disposed on the planarization layer 116. Examples of the other near-infrared cut filter include a layer containing copper and/or a multilayer film of a dielectric. The details of these are mentioned above. Further, as another near-infrared cut filter, a dual band pass filter can be used. Further, in the infrared sensor shown in Fig. 1, the near-infrared cut filter 111 and the color filter 112 can also be switched positions. Further, another layer may be disposed 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. The other layer may, for example, be an organic layer formed using a composition containing a polymerizable compound, a resin, and a photopolymerization initiator. Further, a planarization layer may be formed on the color filter 112. [Examples]

Hereinafter, the present invention will be further specifically described by way of examples. The materials, the amounts used, the ratios, the processing contents, the processing steps, and the like shown in the following examples can be appropriately changed without departing from the gist of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. In addition, "parts" and "%" are quality standards unless otherwise specified. Further, in the structural formula, Me represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, and Ph represents a phenyl group.

<Method for Measuring Thermal Decomposition Temperature of Radical Polymerization Starter> The thermal decomposition temperature of the radical polymerization initiator was measured by differential thermal (TG-DTA) measurement. Specifically, the radical polymerization initiator was heated from the state of 23 ° C at a temperature increase rate of 10 ° C /min, and the temperature at which the weight of the radical polymerization initiator started to decrease was measured.

<Method for Measuring Thermal Decomposition Rate of Radical Polymerization Starter> The thermal decomposition rate of the radical polymerization initiator was measured by differential scanning calorimetry (DSC) measurement. Specifically, the radical polymerization initiator is heated from the state of 23 ° C at a temperature increase rate of 10 ° C /min, and after 100 ° C, the slope of the line connecting the rising temperature of the exothermic peak and the maximum temperature of the exothermic peak is used. Calculate the rate of thermal decomposition.

<Preparation of the curable composition> The raw materials shown in the following table were mixed and stirred in the ratio (parts by mass) shown in the following table, and then filtered using a nylon filter (manufactured by NIHON PALL LTD.) having a pore size of 0.45 μm. A hardenable composition was prepared. [Table 1] [Table 2] [table 3] [Table 4] [table 5] [Table 6]

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

(Near-infrared absorbing dye) A1 to A18, A20 to A22: a compound having the following structure. A19: NK-5060 (manufactured by Hayashibara Co., Ltd., cyanine compound) [Chemical Formula 31] [Chemical Formula 32]

(Resin) • Resin 1: A cyclopentanone 30% by mass solution of a resin having a structure of the following structure (weight average molecular weight: 41,400, the number of moles in the repeating unit is a molar number). [Chemical Formula 33] • Resin 2: a cyclopentanone 30% by mass solution of a resin having a structure of the following structure (weight average molecular weight: 33,100, the number of moles in the repeating unit is a molar number). [Chemical Formula 34]

(Organic solvent) • Organic solvent 1: Cyclopentanone • Organic solvent 2: 3-methoxy-N,N-dimethylpropanamide • Organic solvent 3:3-butoxy-N,N-dimethyl Propylamine

(radical polymerizable compound) • Radical polymerizable compound 1: a mixture of the following compounds (a mixture of the left side compound and the right side compound having a molar ratio of 7:3) [Chemical Formula 35]

• Radical polymerizable compound 2: a mixture of the following compounds (height ratio measured by high performance liquid chromatography: 46.15:49.39:4.46) [Chemical Formula 36] • Radical polymerizable compound 3: the following compound [Chemical Formula 37] • Radical polymerizable compound 4: the following compound [Chemical Formula 38]

(Free radical polymerization initiator A) • Radical polymerization initiator A1: a compound of the following structure (pinacol compound, thermal decomposition temperature 182 ° C, thermal decomposition rate 56 W / ° C • mol) [Chemical Formula 39] • Radical polymerization initiator A2: a compound of the following structure (pinacol compound, thermal decomposition temperature: 178 ° C, thermal decomposition rate: 54 W/° C. mol. In the following structural formula, Ph represents a phenyl group, and Bu represents a butyl group. ) [Chemical Formula 40] • Radical polymerization initiator A3: a compound of the following structure (pinacol compound, thermal decomposition temperature: 178 ° C, thermal decomposition rate: 54 W / ° C • mol. In the following structural formula, Ph represents a phenyl group, and iPr represents an isopropyl group. .) [Chemical Formula 41] • Radical polymerization initiator A4: a compound of the following structure (pinacol compound, thermal decomposition temperature: 172 ° C, thermal decomposition rate: 50 W/° C. mol. In the following structural formula, Ph represents a phenyl group.) [Chemical Formula 42]

(Free radical polymerization initiator B) • Radical polymerization initiator B1: IRGACURE-184 (manufactured by BASF, α-hydroxyacetophenone compound, thermal decomposition temperature 151 ° C, thermal decomposition rate 4 W / ° C • mol) • Free radical polymerization initiator B2: IRGACURE-2959 (manufactured by BASF, α-hydroxyacetophenone compound, thermal decomposition temperature 165 ° C, thermal decomposition rate 8 W / ° C • mol) • Free radical polymerization initiator B3: IRGACURE- 651 (Manufactured by BASF, benzyl dimethyl ketal compound, thermal decomposition temperature 170 ° C, thermal decomposition rate 5 W / ° C · mol) • Free radical polymerization initiator B4: IRGACURE-OXE01 (manufactured by BASF Corporation, bismuth compound, Thermal decomposition temperature 170 ° C, thermal decomposition rate 30 W / ° C • mol)

• decane coupling agent: urea propyl trimethoxy decane

• 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, B1-1: B3-1) = 92.5: 7.5 (mole ratio) of a propylene glycol monomethyl ether acetate (PGMEA) 30 mass% solution. In the following formula (B3-1), X represents a perfluoromethylene group or a perfluoroethyl group, and r represents the number of repeating units. On _{X, -CF 2 -CF 2 -,} - CF 2 - and -CH ₂ -CF ₂ - the ratio of the number of _{-CF 2 -CF 2 -: - CF} 2 -: - CH 2 -CF 2 - = 4.2: 1.9: 1.0. [Chemical Formula 43]

• UV (ultraviolet) absorber: a compound of the following structure [Chemical Formula 44]

• Polymerization inhibitor: p-methoxyphenol

(Dispersion 1) Using a zirconia bead of 0.3 mm diameter, a bead mill (a high-pressure disperser NANO-3000-10 (manufactured by Nippon BEE Co., Ltd.) equipped with a pressure reducing mechanism) was used as a raw material of the following composition. Dispersion 1 was prepared by dispersion over 2 hours. - Composition of Dispersion 1 - - Near-infrared absorbing pigment of the following structure (average primary particle diameter: 200 nm) ... 11.6 parts by mass [Chemical Formula 45] • A pigment derivative of the following structure... 3.5 parts by mass [Chemical Formula 46] • Dispersant (resin of 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 value recorded in the repeating unit of the side chain indicates the number of repeating units.) 7.2 parts by mass [Chemical Formula 47] • cyclohexanone... 77.77 parts by mass

(Dispersion 2) 60 parts by mass of CI Pigment Black 32, 20 parts by mass of Pig Pigment Blue 15:6, 20 parts by mass of CI Pigment Yellow 139, 80 parts by mass Solsperse 76500 (manufactured by Lubrizol Japan Ltd., solid content concentration: 50% by mass) and 700 parts by mass of propylene glycol monomethyl ether acetate were mixed and dispersed for 8 hours using a paint shaker to obtain a dispersion 2.

<Evaluation of Near Infrared Shielding Property> Each of the curable compositions was spin-coated on a glass substrate (EAGLE XG, manufactured by Corning Incorporated, alkaline earth aluminoborosilicate) by a MIKASA coater to form a film after film formation. The thickness was 2.5 μm, and it was dried at 100 ° C for 120 seconds using a hot plate, followed by heating at 220 ° C for 5 minutes to produce a cured film. Using a UV-visible near-infrared spectrophotometer U-4100 (manufactured by Hitachi High-Technologies Corp.), the obtained cured film was measured for a transmittance in a wavelength range of 700 to 1300 nm, and the transmittance of the cured film at a maximum absorption wavelength was used. (T), the near-infrared shielding property was evaluated on the basis of the following criteria. 5: T≤1% 4:1%<T≤3% 3:3%<T≤5% 2:5%<T≤10% 1:10%<T

<Evaluation of Coacervation Size> Each of the curable compositions was spin-coated on a glass substrate by a MIKASA coater so that the film thickness after film formation was 2.5 μm, and dried at 100 ° C for 120 seconds using a hot plate. Then, it was heated at 220 ° C for 5 minutes to produce a cured film. The glass substrate on which the cured film was formed was immersed in acetone at 23 ° C for 5 minutes, and then an ultrahigh decomposition energy scanning electron microscope (manufactured by Hitachi High-Technologies Corp.) was used to observe the film at an acceleration voltage of 2.0 kV and an observation magnification of 50,000 times. The image of the section. In the image, the length in the long axis direction of any three pore portions (the portion in which the pores were formed in the film when observed) was measured, and the average value was calculated as the aggregation size.

<Evaluation of storage stability> Immediately after preparation of each curable composition, Act8 (manufactured by Tokyo Electron Limited) was spin-coated on a glass substrate so that the thickness of the film after film formation was 1.0 μm, and then heating was used. The plate was heated at 220 ° C for 5 minutes to produce a cured film. The light transmittance in the range of 400 to 1,300 nm was measured for the obtained cured film using an ultraviolet-visible near-infrared spectrophotometer U-4100 (manufactured by Hitachi High-Technologies Corp.). The spectroscopic light of the cured film produced using the curable composition immediately after preparation was used as the spectroscopic light 1. Then, each of the curable compositions immediately after preparation was stored in a clean room at a temperature of 23° C. for 2 months, and then each of the curable compositions after storage was used to produce a cured film in the same manner as described above, and the measurement was performed. Light transmittance in the range of wavelength 400 to 1,300 nm. The spectroscopic light of the cured film produced using the curable composition after storage is used as the spectroscopic light 2. Using the above-described spectroscopic light 1 and spectroscopic light 2, the difference in transmittance between the cured film produced by using the curable composition immediately after preparation at each wavelength and the cured film produced by using the curable composition after storage is calculated, and the wavelength is determined. The maximum value (ΔT%) of the difference in the above-described transmittance in the range of 400 to 1,300 nm, and the storage stability was evaluated on the basis of the following criteria. 3: ΔT% < 1 2: 1 ≤ ΔT% < 5 1: 5 ≤ ΔT%

[Table 7] [Table 8] [Table 9] [Table 10] [Table 11] [Table 12]

As shown in the above table, the storage stability of the examples was good and both of them were able to produce a cured film having a small aggregate size. The curable composition of Example 1 was changed from a glass substrate to a fluorophosphate glass substrate (product name: NF-50, manufactured by AGC TECHNO GLASS Co., Ltd., size 50 mm × 50 mm, thickness 0.05 mm, The glass substrate containing copper was evaluated, and the near-infrared shielding property was evaluated, and as a result, the same result was obtained.

110‧‧‧Solid camera components

111‧‧‧Infrared cut filter

112‧‧‧ color filter

114‧‧‧Infrared transmission filter

115‧‧‧Microlens

116‧‧‧flattening layer

Hν‧‧‧ incident light

Fig. 1 is a schematic view showing an embodiment of an infrared sensor.

Claims (20)

A curable composition comprising a near-infrared absorbing dye, a radically polymerizable compound, and a radical polymerization initiator A, wherein the radical polymerization initiator A is a pinacol compound. A curable composition comprising a near-infrared absorbing dye, a radical polymerizable compound, and a radical polymerization initiator A, the radical polymerization initiator A having a thermal decomposition temperature of 120 to 270 ° C and a thermal decomposition rate of 33 ~60W / ° C · mol of the compound. The sclerosing composition according to claim 2, wherein the radical polymerization initiator A is a pinacol compound. The curable composition according to any one of claims 1 to 3, wherein the content of the radical polymerization initiator A is 0.1 to 20 by mass based on the total solid content of the curable composition. %. The curable composition according to any one of claims 1 to 3, wherein the radical polymerization initiation is contained in an amount of from 1 to 100 parts by mass based on 100 parts by mass of the radically polymerizable compound. Agent A. The curable composition according to any one of claims 1 to 3, further comprising a radical polymerization initiator B different from the radical polymerization initiator A. The curable composition according to claim 6, wherein the radical polymerization initiator B is at least one selected from the group consisting of an α-hydroxyacetophenone compound and a benzyldimethylketal. The sclerosing composition according to claim 6, wherein the radical polymerization initiator B has a thermal decomposition temperature of from 100 to 270 °C. The curable composition according to any one of claims 6 to 6, wherein the radical polymerization initiator B has a thermal decomposition rate of 3 to 10 W/° C. mol. The curable composition according to any one of claims 6, wherein the radical polymerization initiator B is contained in an amount of 0.1 to 2000 parts by mass based on 100 parts by mass of the radical polymerization initiator A. . A cured film obtained by the curable composition according to any one of claims 1 to 10. A laminate having a cured film according to claim 11 on a support. The laminate according to claim 12, wherein a film obtained by using the following composition between the support and the cured film, the composition comprising a compound having a cyclic ether group. The laminate according to claim 12, wherein the support system comprises a glass substrate of copper. The laminate according to claim 12, wherein the cured film has an inorganic film. The laminate according to claim 15, wherein a planarization layer is provided between the cured film and the inorganic film. A near-infrared cut filter having the cured film described in claim 11 of the patent application. A solid-state imaging device having the cured film described in claim 11 of the patent application. An image display device having the cured film described in claim 11 of the patent application. An infrared sensor having the cured film described in claim 11 of the patent application.