Curable composition, cured film, method for forming a pattern, near-infrared cut filter, solid-state image sensor, image display device, and infrared sensor

Abstract

A curable composition comprising an infrared absorption reagent, a polymerizable monomer, and photoinitiators, wherein the photoinitiators include a photoinitiator IA having an absorption coefficient of 1.0×103 mL / g·cm or more with respect to a wavelength of 365 nm in methanol, and a photoinitiator IB having, in methanol, an absorption coefficient of less than 1.0×103 mL / g·cm with respect to a wavelength of 365 nm and having an absorption coefficient of 1.0×103mL / g·cm or more with respect to a wavelength of 254 nm, and A1 / A2, which is the ratio of the maximum value A1 of the absorbance of the curable composition in a wavelength range of 700-2000 nm with respect to the maximum value A2 of the absorbance of the curable composition in a wavelength range of 400-600 nm, is 4.5 or more. A cured film, a pattern forming method, a near infrared cut-off filter, a solid image pickup element, an image display apparatus, and an infrared sensor, in all of which said curable composition is used.

Description

[Technical Field]

[0001] The present invention relates to a curable composition containing an infrared absorber, a polymerizable monomer, and a photopolymerization initiator. The present invention also relates to a cured film, a method for forming a pattern, a near-infrared cut filter, a solid-state image sensor, an image display device, and an infrared sensor. [Background technology]

[0002] Video cameras, digital still cameras, and mobile phones with camera functions use solid-state image sensors for color images, such as CCDs (charge-coupled devices) and CMOS (complementary metal-oxide-semiconductor) sensors. These solid-state image sensors use silicon photodiodes, which are sensitive to infrared light, in their light-receiving sections. For this reason, near-infrared cut filters are sometimes provided to correct the visual sensitivity.

[0003] Near-infrared cut filters are manufactured using curable compositions containing an infrared absorber, a polymerizable monomer, and a photopolymerization initiator (see Patent Document 1, etc.). [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2019-211764 [Overview of the project] [Problems that the invention aims to solve]

[0005] In recent years, in solid-state image sensors, non-silicon materials such as organic materials, quantum dots, and InGaAs (indium gallium arsenide) have been considered as alternatives to silicon photodiodes for photoelectric conversion, from the viewpoints of high resolution, high sensitivity, low power consumption, and miniaturization. Since these non-silicon materials are less heat-resistant than silicon-based materials, it is desirable to form the cured film using a low-temperature process, for example, below 200°C.

[0006] However, when a cured film is formed using a low-temperature process, the degree of curing of the film may be insufficient, and there was room for improvement in the solvent resistance of the cured film.

[0007] Therefore, the present invention aims to provide a curable composition capable of forming a cured film with excellent solvent resistance. Furthermore, the present invention aims to provide a cured film, a method for forming a pattern, a near-infrared cut filter, a solid-state image sensor, an image display device, and an infrared sensor. [Means for solving the problem]

[0008] The inventors provide the following: <1> A curable composition containing an infrared absorber, a polymerizable monomer, and a photopolymerization initiator, The above photopolymerization initiator has an extinction coefficient of 1.0 × 10⁻¹⁰ at a wavelength of 365 nm in methanol. 3 A photopolymerization initiator IA with a concentration of mL / g·cm or higher, and an extinction coefficient of 1.0 × 10⁻¹⁰ at a wavelength of 365 nm in methanol. 3 The concentration is less than mL / g·cm, and the extinction coefficient at a wavelength of 254 nm is 1.0 × 10⁻⁶. 3 It contains a photopolymerization initiator IB in a concentration of mL / g·cm or more. Maximum absorbance A of the above curable composition in the wavelength range of 700 to 2000 nm 1 And the maximum absorbance A in the wavelength range of 400-600 nm. 2 A is the ratio of 1 / A 2 A curable composition having a value of 4.5 or higher. <2> The above photopolymerization initiator IA is an oxime compound. <1> The curable composition described above. <3> The above photopolymerization initiator IB is a hydroxyalkylphenone compound. <1> or <2> The curable composition described above. <4> The total content of the photopolymerization initiator IA and the photopolymerization initiator IB in the total solid content of the above curable composition is 1 to 6% by mass. <1> ~ <3> A curable composition as described in any one of the following. <5> The curable composition according to any one of <1> to <4>, wherein the content of the photopolymerization initiator IB is 5 to 200 parts by mass with respect to 100 parts by mass of the photopolymerization initiator IA. <6> The curable composition according to any one of <1> to <5>, wherein the content of the infrared absorber in the total solid content of the curable composition is 10 to 40% by mass. <7> The curable composition according to any one of <1> to <6>, wherein the content of the polymerizable monomer in the total solid content of the curable composition is 10 to 50% by mass. <8> The curable composition according to any one of <1> to <7>, further comprising a resin. <9> The curable composition according to <8>, wherein the content of the resin is 10 to 500 parts by mass with respect to 100 parts by mass of the polymerizable monomer. <10> The curable composition according to any one of <1> to <9>, further comprising an ultraviolet absorber, wherein the content of the ultraviolet absorber is 10 to 500 parts by mass with respect to 100 parts by mass of the photopolymerization initiator IA. <11> The maximum absorbance A of the curable composition in a wavelength range of 700 to 2000 nm 1 and the absorbance A at a wavelength of 365 nm 3 which is a ratio of A 1 / A 3 is 1 or more and less than 9, the curable composition according to any one of <1> to <10>. <12> The curable composition according to any one of <1> to <11>, which is for a near-infrared cut filter. <13> A cured film obtained by curing the curable composition according to any one of <1> to <12>. <14> A step of forming a curable composition layer on a support using the curable composition according to any one of <1> to <12>, and a first exposure step of irradiating the curable composition layer with light having a wavelength of more than 350 nm and 380 nm or less to perform patterned exposure; a developing step of developing the curable composition layer; and A method for forming a pattern, comprising: a second exposure step of irradiating the curable composition layer with light having a wavelength of 254 nm to 350 nm after the development step described above. <15> The process includes a step of heating the curable composition layer at a temperature of less than 200°C in a low-oxygen atmosphere during at least one of the periods between the above-mentioned development step and the above-mentioned second exposure step, and after the above-mentioned second exposure step. <14> A method for forming the pattern described above. <16> <13> A near-infrared cut filter having the cured film described above. <17> <13> A solid-state image sensor having the cured film described above. <18> <13> An image display device having the cured film described above. <19> <13> An infrared sensor having the cured film described above. [Effects of the Invention]

[0009] According to the present invention, it is possible to provide a curable composition capable of forming a cured film with excellent solvent resistance. Furthermore, it is possible to provide a cured film, a method for forming a pattern, a near-infrared cut filter, a solid-state image sensor, an image display device, and an infrared sensor. [Brief explanation of the drawing]

[0010] [Figure 1] This is a schematic diagram showing one embodiment of the infrared sensor of the present invention. [Modes for carrying out the invention]

[0011] The details of the present invention will be described in detail below. In this specification, "~" is used to mean that the numbers before and after it include the lower and upper limits, respectively. In this specification, when groups (atomic groups) are not specified as substituted or unsubstituted, the notation includes both groups (atomic groups) with and without substituents. For example, "alkyl group" includes not only unsubstituted alkyl groups but also substituted alkyl groups. In this specification, "(meth)acrylate" refers to both acrylate and methacrylate, or either of them; "(meth)acrylic" refers to both acrylic and methacrylic, or either of them; and "(meth)acryloyl" refers to both acryloyl and methacryloyl, or either of them. In this specification, weight-average molecular weight and number-average molecular weight are defined as polystyrene equivalent values ​​measured by gel permeation chromatography (GPC). In this specification, near-infrared light refers to light (electromagnetic waves) with a wavelength of 700 to 2500 nm. In this specification, total solids refers to the total mass of the components of the composition excluding the solvent. In this specification, the term "process" includes not only independent processes but also any process that cannot be clearly distinguished from other processes, as long as its intended function is achieved.

[0012] <Curable composition> The curable composition of the present invention, A curable composition containing an infrared absorber, a polymerizable monomer, and a photopolymerization initiator, The above photopolymerization initiator has an extinction coefficient of 1.0 × 10⁻¹⁰ at a wavelength of 365 nm in methanol. 3 A photopolymerization initiator IA with a concentration of mL / g·cm or higher, and an extinction coefficient of 1.0 × 10⁻¹⁰ at a wavelength of 365 nm in methanol. 3 The concentration is less than mL / g·cm, and the extinction coefficient at a wavelength of 254 nm is 1.0 × 10⁻⁶. 3 It contains a photopolymerization initiator IB in a concentration of mL / g·cm or more. Maximum absorbance A of the above curable composition in the wavelength range of 700 to 2000 nm 1 And the maximum absorbance A in the wavelength range of 400-600 nm. 2 A is the ratio of 1 / A 2 It is characterized by having a value of 4.5 or higher.

[0013] The curable composition of the present invention contains the above-mentioned photopolymerization initiator IA and photopolymerization initiator IB as photopolymerization initiators, so that the cured film can be thoroughly cured to its depths by exposure. For this reason, with the curable composition of the present invention, even when the cured film is formed in a low-temperature process of less than 200°C (preferably 150°C or lower, and more preferably 120°C or lower), a cured film with excellent solvent resistance can be formed. Furthermore, since the curable composition of the present invention contains the above-mentioned photopolymerization initiator IA and photopolymerization initiator IB, the curable composition can be exposed and cured in two stages: before development and after development. That is, in the first exposure (exposure before development), the curable composition layer can be moderately cured. As a result, a pattern with good rectangularity can be formed. Then, in the next exposure (exposure after development), the entire curable composition layer can be almost cured, so a pattern with excellent solvent resistance can be formed. Therefore, when a pattern is formed by photolithography using the curable composition of the present invention, a high level of both solvent resistance and rectangularity can be achieved in the resulting cured film (pattern). Furthermore, this curable composition has a maximum absorbance A in the wavelength range of 700 to 2000 nm. 1 And the maximum absorbance A in the wavelength range of 400-600 nm. 2 A is the ratio of 1 / A 2 Since the ratio is 4.5 or higher, a cured film can be formed that has excellent visible transparency and near-infrared shielding properties, and possesses spectral characteristics suitable for near-infrared cut filters and the like.

[0014] The curable composition of the present invention has a maximum absorbance A in the wavelength range of 700 to 2000 nm. 1 And the maximum absorbance A in the wavelength range of 400-600 nm. 2 The ratio of (hereinafter referred to as absorbance ratio A) 1 / A 2 The absorbance ratio A (also known as) is 4.5 or higher, preferably 6 or higher, more preferably 8 or higher, and even more preferably 12 or higher. There is no particular upper limit, but it can be 50 or lower. 1 / A2 These conditions can be achieved by any means, but the absorbance conditions can be suitably achieved by adjusting the type and content of the infrared absorber.

[0015] The absorbance Aλ at a certain wavelength λ is defined by the following equation (Ab1). Aλ = -log(Tλ / 100) ... (Ab1) Aλ is the absorbance at wavelength λ, and Tλ is the transmittance (%) at wavelength λ.

[0016] In the present invention, the absorbance value may be the value measured in solution, or the value of a cured film formed using the curable composition. When measuring the absorbance in film form, it is preferable to apply the curable composition to a support such as a glass substrate by a method such as spin coating, heat it at 100°C for 120 seconds using a hot plate or the like, and then measure the absorbance using a cured film with a thickness of 1.0 μm that has been formed by cooling to room temperature.

[0017] The curable composition of the present invention has a maximum absorbance A in the wavelength range of 700 to 2000 nm. 1 And absorbance A at a wavelength of 365 nm 3 The ratio of (hereinafter referred to as absorbance ratio A) 1 / A 3 The absorbance ratio A (also known as ) is preferably 1 or more and less than 9, because when exposed through a mask, the unexposed portion around the mask edge can suppress exposure due to reflected or scattered light from the support, etc., and a pattern with good rectangularity can be formed. The lower limit is preferably 1.5 or more, and more preferably 2 or more. The upper limit is preferably less than 4.5, and more preferably less than 3. 1 / A 3 The above absorbance conditions can be achieved by any means, but they can be suitably achieved by methods such as including an ultraviolet absorber.

[0018] Generally, infrared absorbers have high transmittance of light such as i-rays used for exposure. Therefore, when forming patterns using photolithography with a curable composition containing an infrared absorber, a photopolymerization initiator, and a polymerizable monomer, when the curable composition is exposed through a mask, the unexposed areas around the mask are easily exposed by reflected or scattered light from the support, resulting in a pattern with poor rectangularity. However, the absorbance ratio A of the curable composition 1 / A 3 Because the range is as described above, when exposure is performed through the mask, the reflected and scattered light in the unexposed area around the mask edge can be absorbed, and a pattern with good rectangularity can be formed.

[0019] When a cured film with a thickness of 1.0 μm is formed using the curable composition of the present invention, the above-mentioned cured film has an absorbance ratio A 1 / A 2 Preferably, the value is 4.5 or higher, more preferably 6 or higher, even more preferably 8 or higher, and even more preferably 12 or higher. There is no particular upper limit, but it can be 50 or lower. Preferably, the cured film is a 1.0 μm thick cured film obtained by applying a curable composition to a support such as a glass substrate by a method such as spin coating, heating it at 100°C for 120 seconds using a hot plate or the like, and then allowing it to cool to room temperature.

[0020] Regarding the above cured film, the absorbance ratio A 1 / A 3 The value is preferably 1 or greater and less than 9. The lower limit is preferably 1.5 or greater, and more preferably 2 or greater. The upper limit is preferably less than 4.5, and more preferably less than 3.

[0021] The above cured film preferably has an average transmittance of 70% or more of light with a wavelength of 400 to 600 nm, more preferably 80% or more, even more preferably 85% or more, and particularly preferably 90% or more. Furthermore, the minimum transmittance of the above cured film with a wavelength in the 400 to 600 nm range is preferably 70% or more, more preferably 80% or more, and even more preferably 90% or more.

[0022] The curable composition of the present invention can be preferably used as a curable composition for near-infrared cut filters.

[0023] Furthermore, the curable composition of the present invention can be preferably used as a curable composition for pattern formation in photolithography. When the curable composition of the present invention is used as a composition for photolithography, it is preferable that the curable composition of the present invention further contains an ultraviolet absorber. Also, the absorbance ratio A of the curable composition 1 / A 3 It is preferable that the ratio is between 1.0 and less than 9.0. Furthermore, the curable composition preferably contains a resin, and more preferably contains a resin having an acid group.

[0024] The solid content concentration of the curable composition of the present invention is preferably 10 to 30% by mass. The lower limit is preferably 10% by mass or more, and more preferably 15% by mass or more. The upper limit is preferably 30% by mass or less, and more preferably 25% by mass or less.

[0025] The following describes each component used in the curable composition of the present invention.

[0026] <<Infrared absorber>> The curable composition of the present invention contains an infrared absorbent. The infrared absorbent used in the present invention may be a pigment (also called an infrared absorbing pigment) or a dye (also called an infrared absorbing dye). In addition, an infrared absorbing dye and an infrared absorbing pigment may be used in combination. When an infrared absorbing dye and an infrared absorbing pigment are used in combination, the mass ratio of the infrared absorbing dye to the infrared absorbing pigment is preferably 10 to 200 parts by mass of the infrared absorbing dye, more preferably 10 to 100 parts by mass of the infrared absorbing dye, and even more preferably 10 to 50 parts by mass of the infrared absorbing dye, per 100 parts by mass of the infrared absorbing pigment. When an infrared absorbent containing an infrared absorbing pigment (preferably the infrared absorbent containing only an infrared absorbing pigment) is used, the pattern formation performance in photolithography is excellent.

[0027] The infrared absorbing dye preferably has a solubility of 1 g or more, more preferably 2 g or more, and even more preferably 5 g or more in 100 g of propylene glycol methyl ether acetate at 25°C. The infrared absorbing pigment preferably has a solubility of less than 1 g, more preferably 0.1 g or less, and even more preferably 0.01 g or less in 100 g of propylene glycol methyl ether acetate at 25°C.

[0028] The infrared absorber is preferably a compound having a maximum absorption wavelength in the range of 690 to 2000 nm, more preferably a compound having a maximum absorption wavelength in the range of 700 to 1500 nm, even more preferably a compound having a maximum absorption wavelength in the range of 700 to 1300 nm, and particularly preferably a compound having a maximum absorption wavelength in the range of 700 to 1000 nm. Furthermore, the absorbance A of the infrared absorber at a wavelength of 500 nm is also specified. 500 and absorbance A at the maximum absorption wavelength max Ratio A 500 / A max It is preferably 0.08 or less, and more preferably 0.04 or less.

[0029] Examples of infrared absorbers include pyrrolopyrrole compounds, cyanine compounds, squarylium compounds, phthalocyanine compounds, naphthalocyanine compounds, quaterylene compounds, merocyanine compounds, crokonium compounds, oxonol compounds, iminium compounds, dithiol compounds, triarylmethane compounds, pyromethene compounds, azomethine compounds, anthraquinone compounds, dibenzofuranone compounds, and boradiazin compounds. It is more preferable that the infrared absorber be at least one selected from pyrrolopyrrole compounds, cyanine compounds, squarylium compounds, phthalocyanine compounds, naphthalocyanine compounds, and boradiazin compounds, and even more preferable that it be a pyrrolopyrrole compound.

[0030] The pyrrolopyrrole compound is preferably a compound represented by formula (PP-1). [ka]

[0031] In the formula, Rp 1 and Rp 2 Each of these independently represents an alkyl group, an aryl group, or a heteroaryl group. Rp 3 ~Rp 6 Each of these independently represents a hydrogen atom or a substituent. Rp 7 and Rp 8 These are, independently, a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group, and -BRp 11 Rp 12 Or it represents a metal atom, Rp 11 and Rp 12 Each of these independently represents a substituent, Rp 11 and Rp 12 They may join together to form a ring.

[0032] For details of formula (PP-1), please refer to paragraphs 0017 to 0047 of Japanese Patent Publication No. 2009-263614, paragraphs 0011 to 0036 of Japanese Patent Publication No. 2011-068731, and paragraphs 0010 to 0024 of International Publication No. 2015 / 166873, the contents of which are incorporated herein by reference.

[0033] Rp 1 and Rp 2 The number of carbon atoms in the alkyl group represented by is preferably 1 to 30, more preferably 1 to 20, and even more preferably 1 to 10. The alkyl group may be linear, branched, or cyclic, but linear or branched is preferred. Rp 1 and Rp 2 The number of carbon atoms in the aryl group represented is preferably 6 to 30, more preferably 6 to 20, and even more preferably 6 to 12. Rp 1 and Rp 2 The number of carbon atoms constituting the ring of the heteroaryl group represented by is preferably 1 to 30, and more preferably 1 to 12. Examples of heteroatoms constituting the heteroaryl group include nitrogen atoms, oxygen atoms, and sulfur atoms. The number of heteroatoms constituting the heteroaryl group is preferably 1 to 3, and more preferably 1 to 2. The heteroaryl group is preferably a monocyclic or fused ring, more preferably a monocyclic or fused ring with 2 to 8 condensation rings, and even more preferably a monocyclic or fused ring with 2 to 4 condensation rings.

[0034] Rp 1 and Rp 2 The alkyl group, aryl group, and heteroaryl group represented by may have substituents or be unsubstituted. Examples of substituents include the substituent T shown below. Also, Rp 1 and Rp 2 If the alkyl group, aryl group, and heteroaryl group represented by have two or more substituents, the substituents may be bonded together to form a ring.

[0035] In formula (PP-1), Rp 1 and Rp 2Each of these is preferably an alkyl group or an aryl group. 1 and Rp 2 A preferred embodiment of this is Rp 1 and Rp 2 One example is a configuration in which each of the elements is an alkyl group independently. Also, Rp 1 and Rp 2 Another preferred embodiment of Rp 1 and Rp 2 One example is a configuration in which each of them is an aryl group independently. Also, Rp 1 and Rp 2 Another preferred embodiment of Rp 1 and Rp 2 One embodiment is in which one of the groups is an alkyl group and the other is an aryl group.

[0036] (substituent T) Examples of substituents T include the following groups: halogen atoms (e.g., fluorine atoms, chlorine atoms, bromine atoms, iodine atoms), alkyl groups (preferably alkyl groups having 1 to 30 carbon atoms), alkenyl groups (preferably alkenyl groups having 2 to 30 carbon atoms), alkynyl groups (preferably alkynyl groups having 2 to 30 carbon atoms), aryl groups (preferably aryl groups having 6 to 30 carbon atoms), heteroaryl groups (preferably heteroaryl groups having 1 to 30 carbon atoms), amino groups (preferably amino groups having 0 to 30 carbon atoms), alkoxy groups (preferably alkoxy groups having 1 to 30 carbon atoms), aryloxy groups (preferably Or, an aryloxy group having 6 to 30 carbon atoms), a heteroaryloxy group (preferably a heteroaryloxy group having 1 to 30 carbon atoms), an acyl group (preferably an acyl group having 2 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 heteroaryloxycarbonyl group (preferably a heteroaryloxycarbonyl group having 2 to 30 carbon atoms), an acyloxy group (preferably an acyloxy group having 2 to 30 carbon atoms) Group), acylamino group (preferably an acylamino group having 2 to 30 carbon atoms), aminocarbonylamino group (preferably an aminocarbonylamino group having 2 to 30 carbon atoms), alkoxycarbonylamino group (preferably an alkoxycarbonylamino group having 2 to 30 carbon atoms), aryloxycarbonylamino group (preferably an aryloxycarbonylamino group having 7 to 30 carbon atoms), sulfamoyl group (preferably a sulfamoyl group having 0 to 30 carbon atoms), sulfamoylamino group (preferably a sulfamoylamino group having 0 to 30 carbon atoms), Bamoyl group (preferably a carbamoyl group having 1 to 30 carbon atoms), alkylthio group (preferably an alkylthio group having 1 to 30 carbon atoms), arylthio group (preferably an arylthio group having 6 to 30 carbon atoms), heteroarylthio group (preferably a heteroarylthio group having 1 to 30 carbon atoms), alkylsulfonyl group (preferably an alkylsulfonyl group having 1 to 30 carbon atoms), alkylsulfonylamino group (preferably an alkylsulfonylamino group having 1 to 30 carbon atoms), arylsulfonyl group (preferably an arylsulfonyl group having 6 to 30 carbon atoms),Aryl sulfonylamino group (preferably aryl sulfonylamino group having 6 to 30 carbon atoms), heteroaryl sulfonyl group (preferably heteroaryl sulfonyl group having 1 to 30 carbon atoms), heteroaryl sulfonylamino group (preferably heteroaryl sulfonylamino group having 1 to 30 carbon atoms), alkyl sulfinyl group (preferably alkyl sulfinyl group having 1 to 30 carbon atoms), aryl sulfinyl group (preferably aryl sulfinyl group having 6 to 30 carbon atoms), heteroaryl sulf Nyl groups (preferably heteroarylsulfinyl groups having 1 to 30 carbon atoms), ureido groups (preferably ureido groups having 1 to 30 carbon atoms), hydroxyl groups, nitro groups, carboxyl groups, sulfo groups, phosphoric acid groups, carboxylic acid amide groups, sulfonic acid amide groups, imide groups, phosphino groups, mercapto groups, cyano groups, alkylsulfino groups, arylsulfino groups, arylazo groups, heteroarylazo groups, phosphinyl groups, phosphinyloxy groups, phosphinylamino groups, silyl groups, hydrazino groups, and imino groups. These groups may have further substituents if they are further substituted. Examples of substituents include those described above under substituent T.

[0037] In formula (PP-1), Rp 3 ~Rp 6 Each of these independently represents a hydrogen atom or a substituent. The substituent T mentioned above is an example of such a substituent.

[0038] R 3 and R 4 Preferably, one of the groups is a heteroaryl group and the other is an electron-withdrawing group. Also, R 5 and R 6 Preferably, one of the groups is a heteroaryl group and the other is an electron-withdrawing group.

[0039] Here, a substituent having a positive Hammett σp value (sigma para value) acts as an electron-withdrawing group. In the present specification, substituents having a Hammett σp value of 0.2 or more can be exemplified as electron-withdrawing groups. The σp value is preferably 0.25 or more, more preferably 0.3 or more, and particularly preferably 0.35 or more. The upper limit is not particularly limited, but is preferably 0.80 or less. Specific examples of the electron-withdrawing group include a cyano group (0.66), a carboxy group (-COOH: 0.45), an alkoxycarbonyl group (e.g., -COOCH3: 0.45), an aryloxycarbonyl group (e.g., -COOCH3: 0.44), a carbamoyl group (e.g., -CONH2: 0.36), an alkylcarbonyl group (e.g., -COCH3: 0.50), an arylcarbonyl group (e.g., -COPh: 0.43), an alkylsulfonyl group (e.g., -SO2CH3: 0.72), an arylsulfonyl group (e.g., -SO2Ph: 0.68), and the like. The electron-withdrawing group is preferably a cyano group, an alkylcarbonyl group, an alkylsulfonyl group or an arylsulfonyl group, and more preferably a cyano group. That is, R of formula (1) 1 and R 2 one of, and R 3 and R 4 it is preferable that one of each is a cyano group. Here, Ph represents a phenyl group. Regarding the Hammett σp value, reference can be made to paragraphs 0024 to 0025 of Japanese Patent Application Laid-Open No. 2009-263614, the content of which is incorporated herein.

[0040] R of formula (PP-1) 3 and R 4 a heteroaryl group represented by any one of, and R of formula (PP-1) 5 and R 6The number of carbon atoms constituting the ring of the heteroaryl group represented by either one is preferably 1 to 30, more preferably 1 to 12. Examples of the types of heteroatoms constituting the heteroaryl group include a nitrogen atom, an oxygen atom and a sulfur atom. The number of heteroatoms constituting the heteroaryl group is preferably 1 to 3, more preferably 1 to 2. The heteroaryl group is preferably a monocyclic ring or a fused ring, more preferably a monocyclic ring or a fused ring having 2 to 8 fused rings, and still more preferably a monocyclic ring or a fused ring having 2 to 4 fused rings. The heteroaryl group may be unsubstituted or may have a substituent. Examples of the substituent include the groups described for the aforementioned substituent T.

[0041] Rp in Formula (PP-1) 7 and Rp 8 each independently represent a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group, -BRp 11 Rp 12 or a metal atom, and is preferably -BRp 11 Rp 12 . -BRp 11 Rp 12 In the group represented by, Rp 11 and Rp 12 each represent a substituent selected from the group consisting of a halogen atom, an alkyl group, an alkenyl group, an aryl group, a heteroaryl group, an alkoxy group, an aryloxy group and a heteroaryloxy group, preferably a halogen atom, an alkyl group, an aryl group or a heteroaryl group, more preferably a halogen atom, an alkyl group or an aryl group, and still more preferably an aryl group.

[0042] Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom is preferable. The number of carbon atoms in the alkyl and alkoxy groups is preferably 1 to 20, more preferably 1 to 15, and even more preferably 1 to 8. The alkyl and alkoxy groups may be linear, branched, or cyclic, but linear or branched is preferred. The alkyl and alkoxy groups may have substituents or be unsubstituted. Examples of substituents include aryl groups, heteroaryl groups, and halogen atoms. The number of carbon atoms in the alkenyl group is preferably 2 to 20, more preferably 2 to 15, and even more preferably 2 to 8. The alkenyl group may have substituents or may be unsubstituted. Examples of substituents include alkoxy groups, aryl groups, heteroaryl groups, and halogen atoms. The number of carbon atoms in the aryl group and aryloxy group is preferably 6 to 20, and more preferably 6 to 12. The aryl group and aryloxy group may have substituents or may be unsubstituted. Examples of substituents include alkyl groups, alkoxy groups, and halogen atoms. The heteroaryl group and heteroaryloxy group may be monocyclic or fused rings. The number of heteroatoms constituting the heteroaryl ring of the heteroaryl group and heteroaryloxy group is preferably 1 to 3. The heteroatoms constituting the heteroaryl ring are preferably nitrogen, oxygen, or sulfur atoms. The number of carbon atoms constituting the heteroaryl ring is preferably 1 to 30, more preferably 1 to 18, and even more preferably 1 to 12. The heteroaryl ring is preferably a 5-membered or 6-membered ring. The heteroaryl group and heteroaryloxy group may have substituents or may be unsubstituted. Examples of substituents include alkyl groups, alkoxy groups, and halogen atoms.

[0043] -BRp 11 Rp 12 Rp in the group represented by 11 and Rp 12 These elements may bond to each other to form a ring. Examples of the rings that can be formed include the structures shown in formulas (B-1) to (B-5). In the following, Rb represents a substituent, and Rb 1 ~Rb 4Each of the following independently represents a hydrogen atom or substituent, b1 to b3 independently represents an integer from 0 to 4, b4 represents an integer from 0 to 6, and * represents a linkage. Rb and Rb 1 ~Rb 4 Examples of substituents represented by include the groups listed above for substituent T, with halogen atoms, alkyl groups, and alkoxy groups being preferred. [ka]

[0044] The pyrrolopyrrole compound is also preferably a compound represented by formula (PP-2). [ka]

[0045] In the formula, Lp 21 This represents an n-valent linking group, Rp 21 This represents an alkyl group, an aryl group, or a heteroaryl group. Rp 22 ~Rp 25 Each of these independently represents a hydrogen atom or a substituent. Rp 26 and Rp 27 These are, independently, a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group, and -BRp 31 Rp 32 Or it represents a metal atom, Rp 31 and Rp 32 Each of these independently represents a substituent, Rp 31 and Rp 32 They may be joined to each other to form a ring. n represents an integer greater than or equal to 2.

[0046] In formula (PP-2), n represents an integer greater than or equal to 2, preferably an integer between 2 and 4, and more preferably 2.

[0047] Lp of formula (PP-2) 21The n-valent linking groups represented by include aliphatic hydrocarbon groups, aromatic hydrocarbon groups, heterocyclic groups, -O-, -S-, -CO-, -COO-, -OCO-, -SO2-, and -NR. L -, -NR L CO-, -CONR L -, -NR L SO2-, -SO2NR L - and groups consisting of combinations thereof are examples. L represents a hydrogen atom, an alkyl group, or an aryl group. The number of carbon atoms in an aliphatic hydrocarbon group is preferably 1 to 20, more preferably 2 to 20, even more preferably 2 to 10, and particularly preferably 2 to 5. The aliphatic hydrocarbon group may be linear, branched, or cyclic. Furthermore, a cyclic aliphatic hydrocarbon group may be monocyclic or polycyclic. The number of carbon atoms in an aromatic hydrocarbon group is preferably 6 to 18, more preferably 6 to 14, and even more preferably 6 to 10. The aromatic hydrocarbon group is preferably a monocyclic or a fused ring with 2 to 4 condensation rings. The aromatic hydrocarbon group is preferably a benzene ring group. The heterocyclic group is preferably a monocyclic or a fused ring with 2 to 4 condensation rings. The number of heteroatoms constituting the ring of the heterocyclic group is preferably 1 to 30, more preferably 1 to 18, and even more preferably 1 to 12. Aliphatic hydrocarbon groups, aromatic hydrocarbon groups, and heterocyclic groups may have substituents. Examples of substituents include those listed as substituent T above. Also, R L The alkyl group represented by is preferably 1 to 20 carbon atoms, more preferably 1 to 15, and even more preferably 1 to 8 carbon atoms. The alkyl group may be linear, branched, or cyclic, with linear or branched being preferred, and linear being more preferred. L The alkyl group represented by may have further substituents. Examples of substituents include the substituent T mentioned above. L The number of carbon atoms in the aryl group represented by is preferably 6 to 30, more preferably 6 to 20, and even more preferably 6 to 12. L The aryl group represented by may have further substituents. Examples of substituents include the substituent T mentioned above.

[0048] Rp of formula (PP-2) 21 The number of carbon atoms in the alkyl group represented by is preferably 1 to 30, more preferably 1 to 20, and even more preferably 1 to 10. The alkyl group may be linear, branched, or cyclic, but linear or branched is preferred. Rp of formula (PP-2) 21 The number of carbon atoms in the aryl group represented is preferably 6 to 30, more preferably 6 to 20, and even more preferably 6 to 12. Rp of formula (PP-2) 21 The number of carbon atoms constituting the ring of the heteroaryl group represented by is preferably 1 to 30, and more preferably 1 to 12. Examples of heteroatoms constituting the heteroaryl group include nitrogen atoms, oxygen atoms, and sulfur atoms. The number of heteroatoms constituting the heteroaryl group is preferably 1 to 3, and more preferably 1 to 2. The heteroaryl group is preferably a monocyclic or fused ring, more preferably a monocyclic or fused ring with 2 to 8 condensation rings, and even more preferably a monocyclic or fused ring with 2 to 4 condensation rings. Rp of formula (PP-2) 21 The alkyl group, aryl group, and heteroaryl group represented by may have substituents or be unsubstituted. Examples of substituents include the substituent T mentioned above. Also, Rp 21 If the alkyl group, aryl group, and heteroaryl group represented by have two or more substituents, the substituents may be bonded together to form a ring.

[0049] Rp of formula (PP-2) 21 It is preferable that this is an alkyl group or an aryl group.

[0050] Rp of formula (PP-2) 22 ~Rp 25 Each of these independently represents a hydrogen atom or a substituent. The substituent T mentioned above is an example of such a substituent.

[0051] R 22 and R 23 Preferably, one of the groups is a heteroaryl group and the other is an electron-withdrawing group. Also, R24 and R 25 Preferably, one of the groups is a heteroaryl group and the other is an electron-withdrawing group. Examples of electron-withdrawing groups include the groups mentioned above, and it is preferable that the group is a cyano group. The heteroaryl group is R of formula (PP-1). 3 and R 4 A heteroaryl group represented by either one of the following, and the R of formula (PP-1) 5 and R 6 The heteroaryl group represented by either of the two groups is one of the groups described above, and the preferred range is also the same.

[0052] Rp of formula (PP-2) 26 and Rp 27 These are, independently, a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group, and -BRp 31 Rp 32 Alternatively, it represents a metal atom, -BRp 31 Rp 32 It is preferable that this be the case. -BRp in formula (PP-2) 31 Rp 32 Rp in the group represented by 31 and Rp 32 The substituent represented by is -BRp in formula (PP-1). 11 Rp 12 Rp in the group represented by 11 and Rp 12 The substituents represented by the group described above are examples, and the preferred range is also the same. Also, -BRp 31 Rp 32 Rp in the group represented by 31 and Rp 32 These elements may bond to each other to form a ring. Examples of the rings that can be formed include the structures shown in formulas (B-1) to (B-5) above.

[0053] Specific examples of pyrrolopyrrole compounds include compounds with the structures described in the examples below. Other examples of pyrrolopyrrole compounds include those described in paragraphs 0016 to 0058 of Japanese Patent Publication No. 2009-263614, those described in paragraphs 0037 to 0052 of Japanese Patent Publication No. 2011-068731, and those described in paragraphs 0010 to 0033 of International Publication No. 2015 / 166873. Examples of squarylium compounds include the compounds described in paragraphs 0044 to 0049 of Japanese Patent Publication No. 2011-208101, the compounds described in paragraphs 0060 to 0061 of Japanese Patent No. 6065169, the compounds described in paragraph 0040 of International Publication No. 2016 / 181987, the compounds described in Japanese Patent Publication No. 2015-176046, and the compounds described in paragraph 0072 of International Publication No. 2016 / 190162. Examples include compounds, compounds described in paragraphs 0196 to 0228 of Japanese Patent Publication No. 2016-074649, compounds described in paragraph 0124 of Japanese Patent Publication No. 2017-067963, compounds described in International Publication No. 2017 / 135359, compounds described in Japanese Patent Publication No. 2017-114956, compounds described in Japanese Patent No. 6197940, and compounds described in International Publication No. 2016 / 120166.

[0054] Specific examples of squarylium compounds include compounds with the structures described in the examples below. Furthermore, examples of squarylium compounds and crokonium compounds include the squarylium compounds described in JP 2017-197437, JP 2017-025311, JP 2016 / 154782, JP 5884953, JP 6036689, JP 5810604, JP 2017 / 213047 (paragraphs 0090-0107), JP 2018-054760 (paragraphs 0019-0075), and JP 2018-040955 (paragraph 0078). Examples include compounds described in ~0082, compounds described in paragraphs 0043 to 0069 of Japanese Patent Publication No. 2018-002773, squarylium compounds having an aromatic ring at the amide α position described in paragraphs 0024 to 0086 of Japanese Patent Publication No. 2018-041047, amide-linked squarylium compounds described in Japanese Patent Publication No. 2017-179131, compounds having a pyrrole-bis-type squarylium skeleton or crokonium skeleton described in Japanese Patent Publication No. 2017-141215, dihydrocarbazole-bis-type squarylium compounds described in Japanese Patent Publication No. 2017-082029, compounds described in paragraphs 0027 to 0114 of Japanese Patent Publication No. 2017-068120, and compounds described in Japanese Patent Publication No. 2017-067963.

[0055] Examples of boradiazine compounds include those having the structure described in the examples below. Examples of boradiazine compounds include those described in paragraphs 0103 to 0117 of Japanese Patent Publication No. 2015-040231.

[0056] Examples of cyanine compounds include those described in paragraphs 0044 to 0045 of Japanese Patent Publication No. 2009-108267, those described in paragraphs 0026 to 0030 of Japanese Patent Publication No. 2002-194040, those described in Japanese Patent Publication No. 2015-172004, those described in Japanese Patent Publication No. 2015-172102, those described in Japanese Patent Publication No. 2008-088426, those described in paragraph 0090 of International Publication No. 2016 / 190162, and those described in Japanese Patent Publication No. 2017-031394.

[0057] Examples of phthalocyanine compounds include the compound described in paragraph 0093 of Japanese Patent Publication No. 2012-077153, oxytitanium phthalocyanine described in Japanese Patent Publication No. 2006-343631, the compounds described in paragraphs 0013 to 0029 of Japanese Patent Publication No. 2013-195480, the vanadium phthalocyanine compound described in Japanese Patent No. 6081771, the vanadium phthalocyanine compound described in International Publication No. 2020 / 071486, and the phthalocyanine compound described in International Publication No. 2020 / 071470.

[0058] Examples of naphthalocyanine compounds include those described in paragraph 0093 of Japanese Patent Publication No. 2012-077153.

[0059] In this invention, commercially available infrared absorbers can also be used. For example, SDO-C33 (manufactured by Arimoto Chemical Industry Co., Ltd.), E-Excolor IR-14, E-Excolor IR-10A, E-Excolor TX-EX-801B, E-Excolor TX-EX-805K (manufactured by Nippon Shokubai Co., Ltd.), Shigenox NIA-8041, Shigenox NIA-8042, Shigenox NIA-814, Shigenox NIA-820, Shigenox NIA Examples include A-839 (manufactured by Hakko Chemical Co., Ltd.), EpoliteV-63, Epolight3801, Epolight3036 (manufactured by EPOLIN Corporation), PRO-JET825LDI (manufactured by Fujifilm Corporation), NK-3027, NK-5060 (manufactured by Hayashibara Co., Ltd.), YKR-3070 (manufactured by Mitsui Chemicals, Inc.), FDR-003, FDR-004, FDR-005 (manufactured by Yamada Chemical Industries, Ltd.).

[0060] The content of the infrared absorber in the total solid content of the curable composition is preferably 10 to 40% by mass, more preferably 10 to 30% by mass, and even more preferably 10 to 25% by mass. When the content of the infrared absorber is within the above range, a cured film can be obtained that achieves a high level of both near-infrared shielding and visible transparency. The curable composition of the present invention may contain only one infrared absorbent or two or more. When two or more infrared absorbents are included, it is preferable that their total amount falls within the above range.

[0061] <<Photopolymerization initiator>> The curable composition of the present invention contains a photopolymerization initiator. Examples of photopolymerization initiators include halogenated hydrocarbon derivatives (e.g., compounds having a triazine skeleton, compounds having an oxadiazole skeleton, etc.), acylphosphine compounds, hexaarylbiimidazole compounds, oxime compounds, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, aminoalkylphenone compounds, hydroxyalkylphenone compounds, and phenylglyoxylate compounds.

[0062] Examples of phenylglyoxylate compounds include phenylglyoxylic acid methyl ester. A commercially available example is Omnirad MBF (manufactured by IGM Resins BV).

[0063] Examples of aminoalkylphenone compounds include Omnirad 907, Omnirad 369, Omnirad 369E, and Omnirad 379EG (all manufactured by IGM Resins BV).

[0064] Examples of acylphosphine compounds include Omnirad 819 and Omnirad TPO (both manufactured by IGM Resins BV).

[0065] Examples of hydroxyalkylphenone compounds include those represented by the following formula (V). [ka] In the formula, Rv 1 represents a substituent, Rv 2 and Rv 3 Each of these independently represents a hydrogen atom or substituent, and Rv 2 and Rv 3 The elements may be joined together to form a ring, and m represents an integer from 0 to 5.

[0066] Rv 1 Examples of substituents represented by include alkyl groups (preferably alkyl groups having 1 to 10 carbon atoms) and alkoxy groups (preferably alkoxy groups having 1 to 10 carbon atoms). The alkyl and alkoxy groups are preferably linear or branched, with linear being more preferred. Rv 1 The alkyl and alkoxy groups represented by may be unsubstituted or substituted. Examples of substituents include hydroxyl groups and groups having a hydroxyalkylphenone structure. An example of a group having a hydroxyalkylphenone structure is Rv in formula (V). 1 A benzene ring or Rv to which is bonded. 1An example of a structure obtained by removing one hydrogen atom from the original is a group.

[0067] Rv 2 and Rv 3 Each of these independently represents a hydrogen atom or a substituent. Preferably, the substituent is an alkyl group (preferably an alkyl group having 1 to 10 carbon atoms). Also, Rv 2 and Rv 3 These elements 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). The alkyl group is preferably linear or branched, with linear being more preferred.

[0068] Specific examples of compounds represented by formula (V) include compounds with the following structures. [ka]

[0069] Commercially available hydroxyalkylphenone compounds include Omnirad 184, Omnirad 1173, Omnirad 2959, and Omnirad 127 (all manufactured by IGM Resins BV).

[0070] Examples of oxime compounds include the compounds described in Japanese Patent Publication No. 2001-233842, the compounds described in Japanese Patent Publication No. 2000-080068, the compounds described in Japanese Patent Publication No. 2006-342166, the compounds described in JCSPerkin II (1979, pp. 1653-1660), the compounds described in JCSPerkin II (1979, pp. 156-162), and the Journal of Photopolymer Science and Examples include compounds described in Technology (1995, pp. 202-232), compounds described in Japanese Patent Publication No. 2000-066385, compounds described in Japanese Patent Publication No. 2004-534797, compounds described in Japanese Patent Publication No. 2006-342166, compounds described in Japanese Patent Publication No. 2017-019766, compounds described in Japanese Patent Publication No. 6065596, compounds described in International Publication No. 2015 / 152153, compounds described in International Publication No. 2017 / 051680, compounds described in Japanese Patent Publication No. 2017-198865, compounds described in paragraphs 0025-0038 of International Publication No. 2017 / 164127, and compounds described in International Publication No. 2013 / 167515. Specific examples of oxime compounds include 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropane-1-one, 2-benzoyloxyimino-1-phenylpropane-1-one, 3-(4-toluenesulfonyloxy)iminobutan-2-one, 2-ethoxycarbonyloxyimino-1-phenylpropane-1-one, and 1-[4-(phenylthio)phenyl]-3-cyclohexyl-propane-1,2-dione-2-(O-acetyloxime). Examples of commercially available products include Irgacure OXE01, Irgacure OXE02, Irgacure OXE03, Irgacure OXE04 (all manufactured by BASF), TR-PBG-304, TR-PBG-327 (manufactured by Tronley), and ADEKA Optomer N-1919 (manufactured by ADEKA Corporation, photopolymerization initiator 2 described in Japanese Patent Publication No. 2012-014052).Furthermore, it is preferable to use oxime compounds that do not produce color or compounds that are highly transparent and resistant to discoloration. Examples of commercially available products include ADEKA Arclus NCI-730, NCI-831, and NCI-930 (all manufactured by ADEKA Corporation).

[0071] The oxime compound is preferably an oxime compound having a fluorine atom. Specific examples of oxime compounds having a fluorine atom include the compound described in Japanese Patent Publication No. 2010-262028, compounds 24, 36-40 described in Japanese Patent Publication No. 2014-500852, and compound (C-3) described in Japanese Patent Publication No. 2013-164471.

[0072] As the oxime compound, an oxime compound having a fluorene ring can also be used. A specific example of an oxime compound having a fluorene ring is the compound described in Japanese Patent Publication No. 2014-137466.

[0073] As oxime compounds, oxime compounds having a skeleton in which at least one benzene ring of the carbazole ring is replaced by a naphthalene ring can also be used. Specific examples of such oxime compounds include those described in International Publication No. 2013 / 083505.

[0074] As oxime compounds, oxime compounds in which a substituent having a hydroxyl group is attached to a carbazole skeleton can also be used. Examples of such photopolymerization initiators include the compounds described in International Publication No. 2019 / 088055.

[0075] As the oxime compound, an oxime compound having a nitro group can be used. The oxime compound having a nitro group is also preferably in dimer form. Specific examples of oxime compounds having a nitro group include the compounds described in paragraphs 0031 to 0047 of Japanese Patent Publication No. 2013-114249, paragraphs 0008 to 0012 and 0070 to 0079 of Japanese Patent Publication No. 2014-137466, the compounds described in paragraphs 0007 to 0025 of Japanese Patent No. 4223071, and ADEKA Arclus NCI-831 (manufactured by ADEKA Corporation).

[0076] Oxime compounds containing a benzofuran skeleton can also be used as oxime compounds. Specific examples include OE-01 to OE-75, described in International Publication No. 2015 / 036910.

[0077] As oxime compounds, oxime compounds in which a substituent having a hydroxyl group is attached to a carbazole skeleton can also be used. Examples of such photopolymerization initiators include the compounds described in International Publication No. 2019 / 088055.

[0078] Specific examples of oxime compounds are shown below, but the present invention is not limited to these.

[0079] [ka] [ka] [ka]

[0080] In this invention, as a photopolymerization initiator, The extinction coefficient at a wavelength of 365 nm in methanol is 1.0 × 10⁻⁶. 3 A photopolymerization initiator IA (hereinafter also referred to as photopolymerization initiator IA) with a concentration of mL / g·cm or higher, The extinction coefficient at a wavelength of 365 nm in methanol is 1.0 × 10⁻⁶. 3The concentration is less than mL / g·cm, and the extinction coefficient at a wavelength of 254 nm is 1.0 × 10⁻⁶. 3 Use in combination with photopolymerization initiator IB (hereinafter also referred to as photopolymerization initiator IB) which is at a concentration of mL / g·cm or higher. As photopolymerization initiators IA and IB, compounds having the above-mentioned extinction coefficient can be selected from the compounds described above and used.

[0081] In this specification, the extinction coefficient of the photopolymerization initiator at the above wavelengths is the value measured as follows. Specifically, the photopolymerization initiator was dissolved in methanol to prepare a measurement solution, and the absorbance of this measurement solution was measured to calculate the value. More precisely, the aforementioned measurement solution was placed in a 1 cm wide glass cell, and the absorbance was measured using an Agilent Technologies UV-Vis-NIR spectrometer (Cary5000). The extinction coefficients (mL / g·cm) at wavelengths of 365 nm and 254 nm were calculated by applying the results to the following formula.

number

[0082] The absorption coefficient of photopolymerization initiator IA in methanol at a wavelength of 365 nm is 1.0 × 10⁻⁶. 3 It is mL / g·cm or more, and 2.0 × 10 3 It is preferable that the concentration be mL / g·cm or higher, and 3.0 × 10 3 It is more preferable that the concentration be mL / g·cm or higher, and 5.0 × 10 3 It is even more preferable that the concentration be above mL / g·cm. The upper limit is 1.0 × 10 5 It is preferable that the concentration be mL / g·cm or less, and 1.0 × 10 4 It is more preferable that the concentration be mL / g·cm or less. Furthermore, the absorption coefficient of photopolymerization initiator IA in methanol at a wavelength of 254 nm is 1.0 × 10⁻⁶. 3 It is preferable that the concentration be mL / g·cm or higher, and 1.5 × 10 3It is more preferable that the concentration be mL / g·cm or higher, and 3.0 × 10 3 It is even more preferable that the concentration be above mL / g·cm. The upper limit is 1.0 × 10 5 It is preferable that the concentration is less than or equal to mL / g·cm. 4 It is more preferable that the concentration be mL / g·cm or less, and 8.0 × 10 4 It is even more preferable that the concentration be less than or equal to mL / g·cm.

[0083] The photopolymerization initiator IA is preferably an oxime compound, an aminoalkylphenone compound, or an acylphosphine compound, more preferably an oxime compound or an acylphosphine compound, and more preferably an oxime compound from the viewpoint of compatibility with other components contained in the composition. Specific examples of the photopolymerization initiator IA include the compounds (C-7), (C-8), (C-13), and (C-14) shown above as examples of oxime compounds. Examples of commercially available products include the oxime compounds Irgacure OXE01 and Irgacure OXE02 from BASF, and the acylphosphine compound Omnirad 819 from IGM Resins BV.

[0084] The absorption coefficient of photopolymerization initiator IB in methanol at a wavelength of 365 nm is 1.0 × 10⁻⁶. 3 Less than mL / g·cm, 3.0 × 10 2 It is preferable that the concentration be mL / g·cm or less, and 1.0 × 10 2 It is more preferable that the concentration be mL / g·cm or less. The lower limit is preferably 10 mL / g·cm or more, and more preferably 20 mL / g·cm or more. Furthermore, the difference between the absorption coefficient of photopolymerization initiator IA at a wavelength of 365 nm in methanol and the absorption coefficient of photopolymerization initiator IB at a wavelength of 365 nm in methanol is 9.0 × 10⁻⁶. 2 It is preferable that the concentration be mL / g·cm or higher, and 1.0 × 10 3 It is more preferable that the concentration be mL / g·cm or higher, and 3.0 × 10 3 It is even more preferable that the concentration is mL / g·cm or higher. Furthermore, the absorption coefficient of photopolymerization initiator IB in methanol at a wavelength of 254 nm is: 1.0 × 10 3 It is mL / g·cm or more, and 5.0 × 10 3 It is preferable that the concentration be mL / g·cm or higher. The upper limit is 1.0 × 10 6 It is preferable that the concentration be mL / g·cm or less, and 1.0 × 10 5 A concentration of mL / g·cm is more preferable.

[0085] The photopolymerization initiator IB is preferably a hydroxyalkylphenone compound, a phenylglyoxylate compound, or an acylphosphine compound, more preferably a hydroxyalkylphenone compound or a phenylglyoxylate compound, and even more preferably a hydroxyalkylphenone compound. Furthermore, the hydroxyalkylphenone compound is preferably the compound represented by formula (V) described above. Specific examples of the photopolymerization initiator IB include compounds with the structure shown as specific examples of the compound represented by formula (V) described above. Commercially available photopolymerization initiator IB include hydroxyalkylphenone compounds such as Omnirad 184 and Omnirad 2959 from IGM Resins BV.

[0086] Regarding the combination of photopolymerization initiator IA and photopolymerization initiator IB, a combination in which photopolymerization initiator IA is an oxime compound and photopolymerization initiator IB is a hydroxyalkylphenone compound is preferred because it can increase the absorption coefficient of light with wavelengths greater than 350 nm and less than or equal to 380 nm, and the absorption coefficient of light with wavelengths between 254 nm and less than or equal to 350 nm. Furthermore, it is preferable that photopolymerization initiator IB is a compound represented by the above formula (V).

[0087] The total content of photopolymerization initiator IA and photopolymerization initiator IB in the total solid content of the curable composition is preferably 1 to 12% by mass, and more preferably 1 to 6% by mass. The upper limit is preferably 5% by mass or less. The lower limit is preferably 1.5% by mass or more, and more preferably 2% by mass or more. If the total content of photopolymerization initiator IA and photopolymerization initiator IB is within the above range, a cured film with excellent solvent resistance can be formed. Furthermore, the curable composition of the present invention tends to have high transmittance of light used for exposure, and when the curable composition is exposed through a mask, the unexposed areas around the mask tend to be exposed by reflected or scattered light from the support, etc. However, if the total content of photopolymerization initiator IA and photopolymerization initiator IB is within the above range (preferably 1 to 6% by mass), the generation of active species such as radicals in the unexposed areas can be suppressed. For this reason, when pattern formation is performed by photolithography, a pattern with good rectangularity can be formed.

[0088] The content of photopolymerization initiator IB is preferably 5 to 200 parts by mass per 100 parts by mass of photopolymerization initiator IA. The upper limit is preferably 100 parts by mass or less, and more preferably 60 parts by mass or less. The lower limit is preferably 10 parts by mass or more, and more preferably 30 parts by mass or more. If the ratio of photopolymerization initiator IA to photopolymerization initiator IB is within the above range, excellent rectangularity and sufficient solvent resistance can be obtained even if the total amount of photopolymerization initiator IA and photopolymerization initiator IB is small.

[0089] The curable composition of the present invention may contain photopolymerization initiators other than photopolymerization initiator IA and photopolymerization initiator IB (hereinafter also referred to as "other photopolymerization initiators") as photopolymerization initiators, but it is preferable that it does not contain other photopolymerization initiators.

[0090] <<Polymerizable monomers>> The curable composition of the present invention contains a polymerizable monomer. Examples of polymerizable monomers include compounds having an ethylenically unsaturated bond-containing group. Examples of ethylenically unsaturated bond-containing groups include vinyl groups, (meth)allyl groups, and (meth)acryloyl groups. It is preferable that the polymerizable monomer is a compound that can be polymerized by radicals (radical polymerizable monomer).

[0091] The molecular weight of the polymerizable monomer is preferably between 100 and 2000. The upper limit is preferably 1500 or less, and more preferably 1000 or less. The lower limit is more preferably 150 or more, and even more preferably 250 or more.

[0092] The ethylenically unsaturated bond content value (hereinafter referred to as the C=C value) of polymerizable monomers is preferably 5 to 20 mmol / g. The lower limit is preferably 6 mmol / g or more, and more preferably 8 mmol / g or more. The upper limit is preferably 18 mmol / g or less, and more preferably 12 mmol / g or less. The C=C value of polymerizable monomers is calculated by dividing the number of ethylenically unsaturated bond-containing groups contained in one molecule of polymerizable monomer by the molecular weight of the polymerizable monomer.

[0093] The polymerizable monomer is preferably a compound containing two or more ethylenically unsaturated bond-containing groups, more preferably a compound containing three or more ethylenically unsaturated bond-containing groups, even more preferably a compound containing three to fifteen ethylenically unsaturated bond-containing groups, and even more preferably a compound containing three to six ethylenically unsaturated bond-containing groups. Furthermore, the compound having ethylenically unsaturated bond-containing groups is preferably a 3 to 15-functional (meth)acrylate compound, and more preferably a 3 to 6-functional (meth)acrylate compound. Specific examples of compounds having an ethylenically unsaturated bond-containing group include the compounds described in paragraphs 0095 to 0108 of Japanese Patent Publication No. 2009-288705, paragraph 0227 of Japanese Patent Publication No. 2013-029760, paragraphs 0254 to 0257 of Japanese Patent Publication No. 2008-292970, paragraphs 0034 to 0038 of Japanese Patent Publication No. 2013-253224, paragraph 0477 of Japanese Patent Publication No. 2012-208494, Japanese Patent Publication No. 2017-048367, Japanese Patent No. 6057891, Japanese Patent No. 6031807, and Japanese Patent Publication No. 2017-194662, the contents of which are incorporated herein by reference.

[0094] Preferred polymerizable monomers include dipentaerythritol tri(meth)acrylate (commercially available as KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetra(meth)acrylate (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 (commercially available as KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., NK Ester A-DPH-12E; manufactured by Shin Nakamura Chemical Industry Co., Ltd.), and compounds in which the (meth)acryloyl groups of these compounds are linked via ethylene glycol and / or propylene glycol residues (for example, SR454 and SR499, commercially available from Sartomer). In addition, polymerizable monomers such as diglycerin EO (ethylene oxide) modified (meth)acrylate (commercially available as M-460; manufactured by Toagosei), pentaerythritol tetraacrylate (manufactured by Shin-Nakamura Chemical Industry Co., Ltd., NK Ester A-TMMT), 1,6-hexanediol diacrylate (manufactured by Nippon Kayaku Co., Ltd., KAYARAD HDDA), RP-1040 (manufactured by Nippon Kayaku Co., Ltd.), Aronics TO-2349 (manufactured by Toagosei Co., Ltd.), NK Oligo UA-7200 (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), 8UH-1006, 8UH-1012 (manufactured by Taisei Fine Chemical Co., Ltd.), and light acrylate POB-A0 (manufactured by Kyoeisha Chemical Co., Ltd.) can also be used.

[0095] Furthermore, it is also preferable to use trifunctional (meth)acrylate compounds such as trimethylolpropane tri(meth)acrylate, trimethylolpropanepropylene oxide-modified tri(meth)acrylate, trimethylolpropaneethylene oxide-modified tri(meth)acrylate, isocyanurate ethylene oxide-modified tri(meth)acrylate, and pentaerythritol tri(meth)acrylate as polymerizable monomers. Commercially available trifunctional (meth)acrylate compounds include Aronics M-309, M-310, M-321, M-350, M-360, M-313, M-315, M-306, M-305, M-303, M-452, M-450 (manufactured by Toagosei Co., Ltd.), NK Ester A9300, A-GLY-9E, A-GLY-20E, A-TMM-3, A-TMM-3L, A-TMM-3LM-N, A-TMPT, TMPT (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), and KAYARAD GPO-303, TMPTA, THE-330, TPA-330, PET-30 (manufactured by Nippon Kayaku Co., Ltd.).

[0096] Polymerizable monomers having acidic groups can also be used. Examples of acidic groups include carboxyl groups, sulfol groups, and phosphate groups, with carboxyl groups being preferred. Commercially available polymerizable monomers having acidic groups include Arronix M-305, M-510, M-520, and Arronix TO-2349 (manufactured by Toagosei Co., Ltd.). The preferred acid value of polymerizable monomers having acidic groups is 0.1 to 40 mg KOH / g, and more preferably 5 to 30 mg KOH / g.

[0097] Polymerizable monomers having a caprolactone structure can also be used. Polymerizable monomers having a caprolactone structure are commercially available from Nippon Kayaku Co., Ltd. as the KAYARAD DPCA series, including DPCA-20, DPCA-30, DPCA-60, DPCA-120, and others.

[0098] Polymerizable monomers having alkylene oxy groups can also be used. The polymerizable monomer having alkylene oxy groups is preferably a polymerizable monomer having ethylene oxy groups and / or propylene oxy groups, more preferably a polymerizable monomer having ethylene oxy groups, and even more preferably a 3-6 functional (meth)acrylate compound having 4 to 20 ethylene oxy groups. Examples of commercially available polymerizable monomers having alkylene oxy groups include SR-494, a tetrafunctional (meth)acrylate having 4 ethylene oxy groups manufactured by Sartomer, and KAYARAD TPA-330, a trifunctional (meth)acrylate having 3 isobutylene oxy groups manufactured by Nippon Kayaku Co., Ltd.

[0099] Polymerizable monomers having a fluorene skeleton can also be used. Commercially available polymerizable monomers having a fluorene skeleton include Ogusol EA-0200 and EA-0300 (manufactured by Osaka Gas Chemical Co., Ltd., (meth)acrylate monomers having a fluorene skeleton).

[0100] As polymerizable monomers, it is also preferable to use polymerizable monomers that are substantially free of environmentally regulated substances such as toluene. Examples of commercially available polymerizable monomers include KAYARAD DPHA LT and KAYARAD DPEA-12 LT (manufactured by Nippon Kayaku Co., Ltd.).

[0101] Suitable polymerizable monomers include urethane acrylates as described in Japanese Patent Publication No. 48-041708, Japanese Unexamined Patent Publication No. 51-037193, Japanese Unexamined Patent Publication No. 02-032293, and Japanese Unexamined Patent Publication No. 02-016765, as well as urethane compounds having an ethylene oxide-based skeleton as described in Japanese Patent Publication No. 58-049860, Japanese Patent Publication No. 56-017654, Japanese Patent Publication No. 62-039417, and Japanese Patent Publication No. 62-039418. It is also preferable to use polymerizable monomers having an amino structure or sulfide structure in the molecule as described in Japanese Unexamined Patent Publication No. 63-277653, Japanese Unexamined Patent Publication No. 63-260909, and Japanese Unexamined Patent Publication No. 01-105238. In addition, commercially available polymerizable monomers such as UA-7200 (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600, and LINC-202UA (manufactured by Kyoeisha Chemical Co., Ltd.) can also be used.

[0102] The polymerizable monomer content in the total solids of the curable composition is preferably 5 to 50% by mass. The effects of the present invention are more pronounced when the polymerizable monomer content is within the above range. The lower limit is preferably 20% by mass or more, and more preferably 25% by mass or more, because exposure before development allows the curable composition layer to be moderately cured and a well rectangular pattern to be formed. The upper limit is preferably 45% by mass or less, and more preferably 40% by mass or less, because the hardness of the resulting film can be increased.

[0103] Furthermore, the curable composition of the present invention preferably contains 50 to 1500 parts by mass of polymerizable monomer per 100 parts by mass of the total of photopolymerization initiator IA and photopolymerization initiator IB. The effects of the present invention are more pronounced when the polymerizable monomer content is within the above range. The lower limit is preferably 500 parts by mass or more, and more preferably 800 parts by mass or more, because exposure before development allows the curable composition layer to be moderately cured and a pattern with good rectangularity to be formed. The upper limit is preferably 1300 parts by mass or less, and more preferably 1200 parts by mass or less, because the hardness of the resulting film can be increased.

[0104] Furthermore, the curable composition of the present invention preferably contains 100 to 2000 parts by mass of polymerizable monomer per 100 parts by mass of photopolymerization initiator IA. The lower limit is preferably 1000 parts by mass or more, and more preferably 1200 parts by mass or more. The upper limit is preferably 1800 parts by mass or less, and more preferably 1500 parts by mass or less.

[0105] Furthermore, the curable composition of the present invention preferably contains 200 to 4000 parts by mass of polymerizable monomer per 100 parts by mass of photopolymerization initiator IB. The lower limit is preferably 1500 parts by mass or more, and more preferably 2000 parts by mass or more. The upper limit is preferably 3600 parts by mass or less, and more preferably 3000 parts by mass or less.

[0106] The curable composition of the present invention may contain only one polymerizable monomer or two or more polymerizable monomers. When two or more polymerizable monomers are included, it is preferable that their total amount falls within the above range.

[0107] <<Resin>> The curable composition of the present invention may contain a resin. The resin is used, for example, to disperse particles such as pigments in the curable composition, or as a binder. A resin used primarily to disperse particles such as pigments is also called a dispersant. However, such uses of the resin are just examples, and the resin can also be used for purposes other than those described above.

[0108] The weight-average molecular weight (Mw) of the resin is preferably between 3,000 and 2,000,000. The upper limit is preferably 1,000,000 or less, and more preferably 500,000 or less. The lower limit is preferably 4,000 or more, and more preferably 5,000 or more.

[0109] Examples of resins include (meth)acrylic resins, epoxy resins, ene-thiol resins, polycarbonate resins, polyether resins, polyarylate resins, polysulfone resins, polyethersulfone resins, polyphenylene resins, polyarylene etherphosphine oxide resins, polyimide resins, polyamide resins, polyamide-imide resins, polyolefin resins, cyclic olefin resins, polyester resins, styrene resins, vinyl acetate resins, polyvinyl alcohol resins, polyvinyl acetal resins, polyurethane resins, and polyurea resins. One of these resins may be used alone, or two or more may be used in mixture form. Among cyclic olefin resins, norbornene resin is preferred from the viewpoint of improving heat resistance. Examples of commercially available norbornene resins include the ARTON series (e.g., ARTON F4520) manufactured by JSR Corporation. Furthermore, the resins include those described in the examples of International Publication No. 2016 / 088645, those described in Japanese Patent Publication No. 2017-057265, those described in Japanese Patent Publication No. 2017-032685, those described in Japanese Patent Publication No. 2017-075248, those described in Japanese Patent Publication No. 2017-066240, those described in Japanese Patent Publication No. 2017-167513, those described in Japanese Patent Publication No. 2017-173787, and those described in paragraphs 0041 to 0060 of Japanese Patent Publication No. 2017-206689. The following resins can also be used: the resin described in paragraphs 0022 to 0071 of Japanese Patent Publication No. 2018-010856, the blocked polyisocyanate resin described in Japanese Patent Publication No. 2016-222891, the resin described in Japanese Patent Publication No. 2020-122052, the resin described in Japanese Patent Publication No. 2020-111656, the resin described in Japanese Patent Publication No. 2020-139021, and the resin described in Japanese Patent Publication No. 2017-138503, which includes a structural unit having a ring structure in the main chain and a structural unit having a biphenyl group in the side chain. Furthermore, a resin having a fluorene skeleton can also be preferably used as the resin. For resins having a fluorene skeleton, the description in U.S. Patent Application Publication No. 2017 / 0102610 can be referenced, and this content is incorporated herein by reference.Furthermore, as the resin, the resin described in paragraphs 0199 to 0233 of Japanese Patent Publication No. 2020-186373, the alkali-soluble resin described in Japanese Patent Publication No. 2020-186325, and the resin represented by Formula 1 described in Korean Published Patent No. 10-2020-0078339 can also be used.

[0110] It is preferable to use a resin having acidic groups. Examples of acidic groups include carboxyl groups, phosphate groups, sulfo groups, and phenolic hydroxyl groups. Resins having acidic groups can also be used as alkali-soluble resins.

[0111] The acid value of the resin containing acid groups is preferably 30 to 500 mg KOH / g. The lower limit is more preferably 40 mg KOH / g or more, and particularly preferably 50 mg KOH / g or more. The upper limit is more preferably 400 mg KOH / g or less, even more preferably 300 mg KOH / g or less, and particularly preferably 200 mg KOH / g or less. The weight-average molecular weight (Mw) of the resin containing acid groups is preferably 5000 to 100000, and more preferably 5000 to 50000. The number-average molecular weight (Mn) of the resin containing acid groups is preferably 1000 to 20000.

[0112] Resins having acidic groups preferably contain repeating units having acidic groups in their side chains, and more preferably contain repeating units having acidic groups in their side chains in an amount of 5 to 70 mol% of the total repeating units of the resin. The upper limit of the content of repeating units having acidic groups in their side chains is preferably 50 mol% or less, and more preferably 30 mol% or less. The lower limit of the content of repeating units having acidic groups in their side chains is preferably 10 mol% or more, and more preferably 20 mol% or more.

[0113] Regarding resins having acid groups, reference can be made to paragraphs 0558-0571 of Japanese Patent Application Publication No. 2012-208494 (paragraphs 0685-0700 of the corresponding US Patent Application Publication No. 2012 / 0235099) and paragraphs 0076-0099 of Japanese Patent Application Publication No. 2012-198408, the contents of which are incorporated herein by reference. Furthermore, commercially available resins having acid groups can also be used. There are no particular restrictions on the method of introducing acid groups into the resin, but for example, the method described in Japanese Patent No. 6349629 can be cited. In addition, as a method of introducing acid groups into the resin, a method can be cited in which an acid anhydride is reacted with a hydroxyl group produced by a ring-opening reaction of an epoxy group to introduce an acid group.

[0114] The curable composition of the present invention may also preferably contain a resin having a basic group. The resin having a basic group is preferably a resin containing repeating units having a basic group in its side chain, more preferably a copolymer having repeating units having a basic group in its side chain and repeating units not having a basic group, and even more preferably a block copolymer having repeating units having a basic group in its side chain and repeating units not having a basic group. The resin having a basic group can also be used as a dispersant. The amine value of the resin having a basic group is preferably 5 to 300 mgKOH / g. The lower limit is preferably 10 mgKOH / g or more, and more preferably 20 mgKOH / g or more. The upper limit is preferably 200 mgKOH / g or less, and more preferably 100 mgKOH / g or less.

[0115] Commercially available resins containing basic groups include DISPERBYK-161, 162, 163, 164, 166, 167, 168, 174, 182, 183, 184, 185, 2000, 2001, 2050, 2150, 2163, 2164, BYK-LPN6919 (all manufactured by Bic Chemie Co., Ltd.), and Solspers 112. Examples include 00, 13240, 13650, 13940, 24000, 26000, 28000, 32000, 32500, 32550, 32600, 33000, 34750, 35100, 35200, 37500, 38500, 39000, 53095, 56000, 7100 (all manufactured by Lubrizol Japan), Efka PX 4300, 4330, 4046, 4060, 4080 (all manufactured by BASF), etc. Furthermore, the resin having basic groups may also be the block copolymer (B) described in paragraphs 0063 to 0112 of Japanese Patent Publication No. 2014-219665, the block copolymer A1 described in paragraphs 0046 to 0076 of Japanese Patent Publication No. 2018-156021, or the vinyl resin having basic groups described in paragraphs 0150 to 0153 of Japanese Patent Publication No. 2019-184763, and these details are incorporated herein by reference.

[0116] The curable composition of the present invention may also preferably contain a resin having an acidic group and a resin having a basic group. According to this embodiment, the storage stability of the curable composition can be further improved. When a resin having an acidic group and a resin having a basic group are used in combination, the content of the resin having a basic group is preferably 20 to 500 parts by mass, more preferably 30 to 300 parts by mass, and even more preferably 50 to 200 parts by mass, per 100 parts by mass of the resin having an acidic group.

[0117] As the resin, it is also preferable to use a resin that contains repeating units derived from monomer components including the compound represented by the following formula (ED1) and / or the compound represented by the following formula (ED2) (hereinafter, these compounds may also be referred to as "ether dimers").

[0118] [ka]

[0119] In formula (ED1), R 1 and R 2 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent.

Chemical Formula

[0120] As specific examples of ether dimers, for example, the description in paragraph No. 0317 of Japanese Patent Laid-Open No. 2013-029760 can be referred to, and the content thereof is incorporated into the present specification.

[0121] As the resin, it is also preferable to use a resin containing a repeating unit derived from the compound represented by formula (X).

Chemical Formula

[0122] Examples of the compound represented by formula (X) include ethylene oxide or propylene oxide modified (meth)acrylate of p-cumylphenol. Examples of commercial products include Aronix M-110 (manufactured by Toagosei Co., Ltd.).

[0123] The curable composition of the present invention may further contain a resin as a dispersant. Examples of the dispersant include acidic dispersants (acidic resins) and basic dispersants (basic resins). Here, the acidic dispersant (acidic resin) refers to a resin in which the amount of acid groups is greater than the amount of basic groups. As the acidic dispersant (acidic resin), a resin in which the amount of acid groups is 70 mol% or more when the total amount of acid groups and basic groups is 100 mol% is preferable. The acid group contained in the acidic dispersant (acidic resin) is preferably a carboxy group. The acid value of the acidic dispersant (acidic resin) is preferably 10 to 105 mgKOH / g. Further, the basic dispersant (basic resin) refers to a resin in which the amount of basic groups is greater than the amount of acid groups. As the basic dispersant (basic resin), a resin in which the amount of basic groups exceeds 50 mol% when the total amount of acid groups and basic groups is 100 mol% is preferable. The basic group contained in the basic dispersant is preferably an amino group.

[0124] The resin used as a dispersant preferably contains a repeating unit having an acid group. When the resin used as a dispersant contains a repeating unit having an acid group, residues generated on the base of a pixel can be further reduced during pattern formation by photolithography.

[0125] The resin used as a dispersant is also preferably a graft resin. For details of the graft resin, the description in paragraph numbers 0025 to 0094 of Japanese Unexamined Patent Application Publication No. 2012-255128 can be referred to, and the content thereof is incorporated herein.

[0126] The resin used as a dispersant is preferably a polyimine-based dispersant containing a nitrogen atom in at least one of its main chain and side chains. Preferably, the polyimine-based dispersant has a main chain having a substructure with functional groups having a pKa of 14 or less, and side chains with 40 to 10,000 atoms, and contains a basic nitrogen atom in at least one of its main chain and side chains. The basic nitrogen atom is not particularly limited as long as it exhibits basic properties. For polyimine-based dispersants, refer to paragraphs 0102 to 0166 of Japanese Patent Application Publication No. 2012-255128, the contents of which are incorporated herein by reference.

[0127] The resin used as a dispersant is preferably a resin with a structure in which multiple polymer chains are bonded to the core. Examples of such resins include dendrimers (including star-shaped polymers). Specific examples of dendrimers include polymer compounds C-1 to C-31 described in paragraphs 0196 to 0209 of Japanese Patent Application Publication No. 2013-043962.

[0128] The resin used as a dispersant is preferably a resin containing repeating units having ethylenically unsaturated bond-containing groups in their side chains. The content of repeating units having ethylenically unsaturated bond-containing groups in their side chains is preferably 10 mol% or more, more preferably 10 to 80 mol%, and even more preferably 20 to 70 mol% of the total repeating units of the resin.

[0129] Furthermore, as a dispersant, the resin described in Japanese Patent Publication No. 2018-087939, the block copolymers (EB-1) to (EB-9) described in paragraphs 0219 to 0221 of Japanese Patent No. 6432077, polyethyleneimine having polyester side chains described in International Publication No. 2016 / 104803, the block copolymer described in International Publication No. 2019 / 125940, the block polymer having acrylamide structural units described in Japanese Patent Publication No. 2020-066687, the block polymer having acrylamide structural units described in Japanese Patent Publication No. 2020-066688, and the dispersant described in International Publication No. 2016 / 104803 can also be used.

[0130] Dispersants are also available commercially. Specific examples include the DSIPERBYK series from BIC-Chemie (e.g., DSIPERBYK-111, 140, 161, 2001, 2026, etc.), the Solspers series from Lubrizol Nippon Co., Ltd. (e.g., Solspers 20000, 76500, etc.), and the Ajisper series from Ajinomoto Fine Techno Co., Ltd. Additionally, the products described in paragraph 0129 of Japanese Patent Publication No. 2012-137564 and paragraph 0235 of Japanese Patent Publication No. 2017-194662 can also be used as dispersants.

[0131] The resin content in the total solids of the curable composition is preferably 10 to 70% by mass. The lower limit is preferably 20% by mass or more, and more preferably 25% by mass or more. The upper limit is preferably 65% ​​by mass or less, more preferably 50% by mass or less, and even more preferably 40% by mass or less. Furthermore, the content of the resin having an acid group is preferably 1 to 70% by mass relative to the total solid content of the composition of the present invention. The lower limit is preferably 2% by mass or more, more preferably 3% by mass or more, even more preferably 5% by mass or more, even more preferably 10% by mass or more, even more preferably 20% by mass or more, and particularly preferably 25% by mass or more. The upper limit is preferably 65% ​​by mass or less, more preferably 50% by mass or less, even more preferably 40% by mass or less, and particularly preferably 30% by mass or less. The composition of the present invention may contain only one type of resin or two or more types. If two or more types are included, it is preferable that their total amount falls within the above range.

[0132] In the curable composition of the present invention, the resin content is preferably 10 to 1000 parts by mass per 100 parts by mass of polymerizable monomer. When the resin content is within the above range, a cured film with excellent solvent resistance can be formed. Furthermore, when a pattern is formed by photolithography, a pattern with good rectangularity can be formed. The upper limit of the resin content is preferably 700 parts by mass or less, and more preferably 200 parts by mass or less. The lower limit of the resin content is preferably 30 parts by mass or more, and more preferably 70 parts by mass or more.

[0133] When the curable composition of the present invention contains a resin as a dispersant, the content of the dispersant is preferably 50 to 300 parts by mass per 100 parts by mass of the infrared absorber. The lower limit is preferably 70 parts by mass or more, and more preferably 90 parts by mass or more. The upper limit is preferably 200 parts by mass or less, and more preferably 150 parts by mass or less.

[0134] The resin contained in the curable composition of the present invention preferably has an acidic group content of 50 to 100% by mass, more preferably 60 to 100% by mass, even more preferably 70 to 100% by mass, and particularly preferably 80 to 100% by mass, for the reason that it readily forms a cured film with excellent rectangularity and solvent resistance.

[0135] <<UV absorber>> The curable composition of the present invention preferably contains an ultraviolet absorber. According to this embodiment, when a pattern is formed using the curable composition of the present invention by photolithography, a pattern (cured film) with excellent solvent resistance and good rectangularity can be formed.

[0136] In this specification, an ultraviolet absorber refers to an organic compound having an ultraviolet absorption function, and is a compound different from a photopolymerization initiator that efficiently generates active species such as radicals upon irradiation with ultraviolet light. It is preferable that the ultraviolet absorber is a compound that absorbs ultraviolet light and converts it into thermal energy or other forms of energy for dissipation. Furthermore, it is preferable that the ultraviolet absorber is a compound that is stable to ultraviolet light. That is, it is preferable that the ultraviolet absorber is a compound that is not easily broken down by reactions such as decomposition, oxidation, or reduction upon irradiation with ultraviolet light.

[0137] The ultraviolet absorber is preferably a compound whose maximum absorption wavelength is in the range of 340 to 420 nm, more preferably a compound whose maximum absorption wavelength is in the range of 345 to 400 nm, and even more preferably a compound whose maximum absorption wavelength is in the range of 350 to 390 nm. Furthermore, the maximum molar extinction coefficient of the ultraviolet absorber in the wavelength range of 340 to 420 nm is 5000 L·mol. -1 ·cm -1 Preferably, it is 10,000 L·mol or more. -1 ·cm -1 It is more preferable that the amount be greater than or equal to 13,000 L·mol -1 ·cm -1 It is even more preferable that the amount be greater than or equal to the above. The upper limit is, for example, 100,000 L·mol -1 ·cm -1 The following are preferable.

[0138] Examples of UV absorbers include conjugated diene compounds, benzotriazole compounds, dibenzoyl compounds, triazine compounds, benzophenone compounds, salicylate compounds, coumarin compounds, acrylonitrile compounds, benzodithiazole compounds, cinnamic acid compounds, α-β unsaturated ketones, carbostyryl compounds, and merocyanine compounds. Conjugated diene compounds or dibenzoyl compounds are preferred, and dibenzoyl compounds are more preferred.

[0139] The conjugated diene compound is preferably a compound represented by the following formula (UV-1). [ka]

[0140] In equation (UV-1), R 1 and R 2 Each of these independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms, R 1 and R 2 These may be identical or different from each other. However, R 1 and R 2 At least one of them is an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms. 1 and R 2 R 1 and R 2 It may form a cyclic amino group with the nitrogen atom to which it is bonded. Examples of cyclic amino groups include piperidino group, morpholino group, pyrrolidino group, hexahydroazepino group, piperazino group, etc. 1 and R 2 Each of these is independently preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms, and even more preferably an alkyl group having 1 to 5 carbon atoms.

[0141] In equation (UV-1), R 3 and R 4 Each of these independently represents an electron-withdrawing group. 3 and R 4 Each of these groups is preferably an acyl group, a carbamoyl group, an alkyloxycarbonyl group, an aryloxycarbonyl group, a cyano group, a nitro group, an alkylsulfonyl group, an arylsulfonyl group, a sulfonyloxy group, or a sulfamoyl group, and more preferably an acyl group, a carbamoyl group, an alkyloxycarbonyl group, an aryloxycarbonyl group, a cyano group, an alkylsulfonyl group, an arylsulfonyl group, a sulfonyloxy group, or a sulfamoyl group. 3 and R 4 These may bond to each other to form a cyclic electron-withdrawing group. 3 and R 4Examples of the cyclic electron-withdrawing group formed by bonding to each other include a 6-membered ring containing two carbonyl groups.

[0142] At least one of R in formula (UV-1) 1 , R 2 , R 3 , and R 4 may be in the form of a polymer derived from a monomer bonded to a vinyl group via a linking group. Alternatively, it may be a copolymer with another monomer.

[0143] For the ultraviolet absorber represented by formula (UV-1), the description in paragraphs 0024 to 0033 of Japanese Unexamined Patent Publication No. 2009-265642 can be referred to, and the content thereof is incorporated herein. Specific examples of the ultraviolet absorber represented by formula (UV-1) include compounds having the following structure, and compounds described in paragraphs 0034 to 0036 of Japanese Unexamined Patent Publication No. 2009-265642. Examples of commercially available products of the ultraviolet absorber represented by formula (UV-1) include UV-503 (manufactured by Daito Chemical Industry Co., Ltd.).

Chemical Formula

[0144] The dibenzoyl compound is preferably a compound represented by the following formula (UV-2).

Chemical Formula

[0145] In formula (UV-2), R 101 and R 102 each independently represent a substituent, and m1 and m2 each independently represent an integer of 0 to 5.

[0146] R 101 and R 102The substituents represented by include halogen atoms, cyano groups, nitro groups, alkyl groups, aryl groups, heteroaryl groups, alkoxy groups, aryloxy groups, heteroaryloxy groups, alkylthio groups, arylthio groups, heteroarylthio groups, and -NR. U1 R U2 , -COR U3 ,-COOR U4 , -OCOR U5 , -NHCOR U6 ,-CONR U7 R U8 ,-NHCONR U9 R U10 , -NHCOOR U11 , -SO2R U12 , -SO2OR U13 , -NHSO2R U14 and -SO2NR U15 R U16 R is one example. U1 ~R U16 Each of these independently represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an aryl group.

[0147] R 101 and R 102 The substituents represented by are preferably, independently, alkyl groups or alkoxy groups. The number of carbon atoms in the alkyl group is preferably 1 to 20, and more preferably 1 to 10. Alkyl groups can be linear, branched, or cyclic, with linear or branched being preferred, and branched being more preferred. The number of carbon atoms in the alkoxy group is preferably 1 to 20, and more preferably 1 to 10. The alkoxy group is preferably linear or branched, and more preferably branched.

[0148] In equation (UV-2), R 101 and R 102 A combination in which one is an alkyl group and the other is an alkoxy group is preferred.

[0149] m1 and m2 each independently represent integers from 0 to 5. Preferably, m1 and m2 are integers from 0 to 4, more preferably from 0 to 2, even more preferably 0 or 1, and particularly preferably 1.

[0150] Specific examples of dibenzoyl compounds include avobenzone. Commercially available dibenzoyl compounds include Neo Heliopan 357 (manufactured by Symrise).

[0151] The triazine compound is preferably a compound represented by the following formulas (UV-3-1), (UV-3-2), or (UV-3-3). [ka]

[0152] In the formula, R d1 Each of these independently represents a hydrogen atom, a C1-C15 alkyl group, a C3-C8 alkenyl group or a C6-C18 aryl group, a C7-C18 alkylaryl group or a C7-C18 arylalkyl group. The alkyl group, alkenyl group, aryl group, alkylaryl group and arylalkyl group may have substituents. Examples of substituents include the groups described under substituent Ti below. In the formula, R d2 ~R d9 Each of these independently represents a hydrogen atom, a halogen atom, a hydroxyl group, a C1-C15 alkyl group, a C3-C8 alkenyl group or a C6-C18 aryl group, a C7-C18 alkylaryl group or a C7-C18 arylalkyl group. Alkyl groups, alkenyl groups, aryl groups, alkylaryl groups, and arylalkyl groups may have substituents. Examples of substituents include the groups described under substituent Ti below.

[0153] Substituents for Ti include halogen atoms, cyano groups, nitro groups, hydrocarbon groups, heterocyclic groups, and -ORti. 1 ,-CORti 1 ,-COORti 1 -OCORti 1 , -NRti 1 Rti 2 ,-NHCORti 1 ,-CONRti 1Rti 2 ,-NHCONRti 1 Rti 2 ,-NHCOORti 1 , -SRti 1 , -SO2Rti 1 ,-SO2ORti 1 -NHSO2Rti 1 or -SO2NRti 1 Rti 2 Rti is one example. 1 and Rti 2 Each of these independently represents a hydrogen atom, a hydrocarbon group, or a heterocyclic group. 1 and Rti 2 They may combine to form a ring.

[0154] Examples of halogen atoms include fluorine, chlorine, bromine, and iodine. Examples of hydrocarbon groups include alkyl groups, alkenyl groups, alkynyl groups, and aryl groups. The number of carbon atoms in the alkyl group is preferably 1 to 30, more preferably 1 to 15, and even more preferably 1 to 8. The alkyl group may be linear, branched, or cyclic, with linear or branched being preferred, and branched being more preferred. The number of carbon atoms in the alkenyl group is preferably 2 to 30, more preferably 2 to 12, and particularly preferably 2 to 8. The alkenyl group may be linear, branched, or cyclic, with linear or branched being preferred. The alkynyl group has 2 to 30 carbon atoms, more preferably 2 to 25. The alkynyl group may be linear, branched, or cyclic, with linear or branched being preferred. The number of carbon atoms in the aryl group is preferably 6 to 30, more preferably 6 to 20, and even more preferably 6 to 12. The heterocyclic group may be a monocyclic ring or a fused ring. A monocyclic ring or a fused ring with 2 to 4 fusions is preferred. The number of heteroatoms constituting the ring of the heterocyclic group is preferably 1 to 3. The heteroatoms constituting the ring of the heterocyclic group are preferably nitrogen atoms, oxygen atoms, or sulfur atoms. The number of carbon atoms constituting the ring of the heterocyclic group is preferably 3 to 30, more preferably 3 to 18, and even more preferably 3 to 12. The hydrocarbon group and heterocyclic group may have substituents or may be unsubstituted. Examples of substituents include those described above for substituent Ti.

[0155] Specific examples of triazine compounds include mono(hydroxyphenyl)triazine compounds such as 2-[4-[(2-hydroxy-3-dodecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[4-[(2-hydroxy-3-tridecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, and 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine; 2,4-bis(2-hydroxy-3 Examples include bis(hydroxyphenyl)triazine compounds such as -methyl-4-propyloxyphenyl)-6-(4-methylphenyl)-1,3,5-triazine and 2,4-bis(2-hydroxy-3-methyl-4-hexyloxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine; and tris(hydroxyphenyl)triazine compounds such as 2,4-bis(2-hydroxy-4-butoxyphenyl)-6-(2,4-dibutoxyphenyl)-1,3,5-triazine, 2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine and 2,4,6-tris[2-hydroxy-4-(3-butoxy-2-hydroxypropyloxy)phenyl]-1,3,5-triazine. Commercially available triazine compounds include TINUVIN 400, TINUVIN 405, TINUVIN 460, TINUVIN 477, TINUVIN 479 (all manufactured by BASF), and KEMISORB 102 (manufactured by Chemipro Chemical Co., Ltd.).

[0156] The benzotriazole compound is preferably a compound represented by the following formula (UV-4). [ka] In the formula, R e1 ~R e3 Each of these independently represents a hydrogen atom, a halogen atom, a hydroxyl group, a C1-C9 alkyl group, a C1-C9 alkoxy group, a C7-C18 alkylaryl group, or a C7-C18 arylalkyl group. The alkyl group, alkylaryl group, and arylalkyl group may have substituents. Examples of substituents include the groups described above for substituent Ti, with a C1-C9 alkoxycarbonyl group being preferred.

[0157] Specific examples of benzotriazole compounds include 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-tert-amyl-5'-isobutylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-isobutyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-isobutyl-5'-propylphenyl)-5-chlorobenzotriazole, and 2-(2'-hydroxy-3',5'-di-tert-butylphenyl Examples include benzotriazole, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-[2'-hydroxy-5'-(1,1,3,3-tetramethyl)phenyl]benzotriazole, 2-(2-hydroxy-5-tert-butylphenyl)-2H-benzotriazole, 3-(2H-benzotriazole-2-yl)-5-(1,1-dimethylethyl)-4-hydroxy, 2-(2H-benzotriazole-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol, and 2-(2H-benzotriazole-2-yl)-6-(1-methyl-1-phenylethyl)-4-(1,1,3,3-tetramethylbutyl)phenol. Commercially available products include TINUVIN P, TINUVIN PS, TINUVIN 99-2, TINUVIN 109, TINUVIN 326, TINUVIN 328, TINUVIN 384-2, TINUVIN 900, TINUVIN 928, TINUVIN 171, TINUVIN 1130 (all manufactured by BASF), Sumisorb 200, Sumisorb 250, Sumisorb 300, Sumisorb 340, Sumisorb 350 (all manufactured by Sumika Chemtex Co., Ltd.), and KEMISORB 71, KEMISORB 73, KEMISORB 74, KEMISORB 79, KEMISORB 279 (all manufactured by Chemipro Chemical Co., Ltd.). As for benzotriazole compounds, the MYUA series manufactured by Miyoshi Oil & Fat Co., Ltd. may also be used.

[0158] Examples of benzophenone compounds include 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, and 2-hydroxy-4-octoxybenzophenone. Commercially available benzophenone compounds include Uvinul A, Uvinul 049, Uvinul 3050 (all manufactured by BASF), Sumisorb 130 (manufactured by Sumika Chemtex Co., Ltd.), KEMISORB 10, KEMISORB 11, KEMISORB 11S, KEMISORB 12, and KEMISORB 111 (all manufactured by Chemipro Chemical Co., Ltd.).

[0159] Examples of salicylate compounds include phenyl salicylate, p-octylphenyl salicylate, and pt-butylphenyl salicylate.

[0160] Examples of coumarin compounds include coumarin-4, 4-hydroxycoumarin, and 7-hydroxycoumarin.

[0161] Examples of acrylonitrile compounds include ethyl 2-cyano-3,3-diphenylacrylate and 2-ethylhexyl 2-cyano-3,3-diphenylacrylate.

[0162] Furthermore, the ultraviolet absorbers may also be compounds described in paragraphs 0038 to 0052 of Japanese Patent Publication No. 2009-217221, paragraphs 0052 to 0072 of Japanese Patent Publication No. 2012-208374, paragraphs 0317 to 0334 of Japanese Patent Publication No. 2013-068814, paragraphs 0061 to 0080 of Japanese Patent Publication No. 2016-162946, paragraphs 0049 to 0059 of Japanese Patent No. 6268967, and paragraphs 0059 to 0076 of International Publication No. 2016 / 181987.

[0163] The content of the ultraviolet absorber in the total solids of the curable composition is preferably 1 to 20% by mass. The upper limit is preferably 15% by mass or less, and more preferably 10% by mass or less. The lower limit is preferably 2% by mass or more, and more preferably 4% by mass or more. Furthermore, the amount of ultraviolet absorber is preferably 10 to 500 parts by mass per 100 parts by mass of photopolymerization initiator IA. The upper limit is preferably 400 parts by mass or less, and more preferably 300 parts by mass or less. The lower limit is preferably 30 parts by mass or more, and more preferably 50 parts by mass or more. If the ratio of ultraviolet absorber to photopolymerization initiator IA is within the above range, when a pattern is formed using the curable composition of the present invention by photolithography, the resulting pattern (cured film) can achieve a high level of both solvent resistance and rectangularity. Furthermore, the amount of ultraviolet absorber is preferably 10 to 300 parts by mass per 100 parts by mass of photopolymerization initiator IA and photopolymerization initiator IB. The upper limit is preferably 250 parts by mass or less, and more preferably 200 parts by mass or less. The lower limit is preferably 30 parts by mass or more, and more preferably 50 parts by mass or more. If the ratio of ultraviolet absorber to photopolymerization initiator IA is within the above range, when a pattern is formed using the curable composition of the present invention by photolithography, the resulting pattern (cured film) can achieve a high level of both solvent resistance and rectangularity.

[0164] The curable composition of the present invention may contain only one ultraviolet absorber or two or more ultraviolet absorbers. When two or more ultraviolet absorbers are included, it is preferable that their total amount falls within the above range.

[0165] <<Solvent>> The curable composition of the present invention preferably contains a solvent. Examples of solvents include water and organic solvents, with organic solvents being preferred. Examples of organic solvents include ester solvents, ketone solvents, alcohol solvents, amide solvents, ether solvents, and hydrocarbon solvents. For further details, please refer to paragraph 0223 of International Publication No. 2015 / 166779, which is incorporated herein by reference. Ester solvents and ketone solvents substituted with cyclic alkyl groups can also be preferably used. Specific examples of organic solvents include polyethylene glycol monomethyl ether, dichloromethane, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, 2-pentanone, 3-pentanone, 4-heptanone, cyclohexanone, 2-methylcyclohexanone, 3-methylcyclohexanone, 4-methylcyclohexanone, cycloheptanone, cyclooctanone, cyclohexyl acetate, cyclopentanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether, propylene Examples include propylene glycol monomethyl ether acetate, 3-methoxy-N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropanamide, propylene glycol diacetate, 3-methoxybutanol, methyl ethyl ketone, gamma butyrolactone, sulfolane, anisole, 1,4-diacetoxybutane, diethylene glycol monoethyl ether acetate, butane-1,3-diyl diacetate, dipropylene glycol methyl ether acetate, diacetone alcohol (also known as diacetone alcohol, 4-hydroxy-4-methyl-2-pentanone), 2-methoxypropyl acetate, 2-methoxy-1-propanol, and isopropyl alcohol.However, the amount of aromatic hydrocarbons used as organic solvents (benzene, toluene, xylene, ethylbenzene, etc.) may be reduced for environmental reasons (for example, it may be possible to reduce the amount to 50 ppm (parts per million) or less, 10 ppm or less, or 1 ppm or less relative to the total amount of organic solvent).

[0166] In the present invention, it is preferable to use an organic solvent with a low metal content, and the metal content of the organic solvent is preferably, for example, 10 ppb (parts per billion) or less by mass. If necessary, an organic solvent at the ppt (parts per trillion) level by mass may be used, and such organic solvents are provided, for example, by Toyo Gosei Co., Ltd. (Chemical Daily, November 13, 2015).

[0167] Methods for removing impurities such as metals from organic solvents include, for example, distillation (molecular distillation, thin-film distillation, etc.) and filtration using filters. The pore size of the filter used for filtration is preferably 10 μm or less, more preferably 5 μm or less, and even more preferably 3 μm or less. The material of the filter is preferably polytetrafluoroethylene, polyethylene, or nylon.

[0168] Organic solvents may contain isomers (compounds with the same number of atoms but different structures). Furthermore, they may contain only one type of isomer or multiple types.

[0169] The peroxide content in the organic solvent is preferably 0.8 mmol / L or less, and more preferably substantially peroxide-free.

[0170] The solvent content in the curable composition is preferably 10 to 97% by mass. The lower limit is preferably 30% by mass or more, more preferably 40% by mass or more, even more preferably 50% by mass or more, even more preferably 60% by mass or more, and particularly preferably 70% by mass or more. The upper limit is preferably 96% by mass or less, and more preferably 95% by mass or less. The curable composition of the present invention may contain only one type of solvent, or it may contain two or more types. If two or more types of solvents are included, it is preferable that their total amount falls within the above range.

[0171] <<Pigment derivative>> The curable composition of the present invention may further contain a pigment derivative. The pigment derivative is used as a dispersion aid. A dispersion aid is a material used to improve the dispersibility of the pigment in the curable composition. If the curable composition further contains a resin such as a dispersant, a network can be formed between the pigment, the dispersion aid, and the resin to improve the dispersibility of the pigment.

[0172] Examples of pigment derivatives include compounds having a structure in which an acidic group or a basic group is bonded to the pigment skeleton.

[0173] Examples of pigment skeletons constituting the pigment derivatives include the squarylium pigment skeleton, pyrrolopyrrole pigment skeleton, diketopyrrolopyrrole pigment skeleton, quinacridone pigment skeleton, anthraquinone pigment skeleton, diantraquinone pigment skeleton, benzoisoindole pigment skeleton, thiadin indigo pigment skeleton, azo pigment skeleton, quinophthalone pigment skeleton, phthalocyanine pigment skeleton, naphthalocyanine pigment skeleton, dioxazine pigment skeleton, perylene pigment skeleton, perinone pigment skeleton, benzimidazolone pigment skeleton, benzothiazole pigment skeleton, benzimidazole pigment skeleton, and benzoxazole pigment skeleton. The squarylium pigment skeleton, pyrrolopyrrole pigment skeleton, diketopyrrolopyrrole pigment skeleton, phthalocyanine pigment skeleton, quinacridone pigment skeleton, and benzimidazolone pigment skeleton are preferred, and the squarylium pigment skeleton and pyrrolopyrrole pigment skeleton are more preferred.

[0174] Examples of acidic groups include carboxyl groups, sulfo groups, phosphate groups, boronic acid groups, carboxylic acid amide groups, sulfonic acid amide groups, imido acid groups, and salts thereof. Examples of atoms or groups of atoms constituting the salt include alkali metal ions (Li + kaNa + , K + (e.g.), alkaline earth metal ions (Ca 2+ Mg 2+ Examples include ammonium ions, imidazolium ions, pyridinium ions, and phosphonium ions. Examples of carboxylic acid amide groups include -NHCOR A1 A group represented by is preferred. As a sulfonic acid amide group, -NHSO2R A2 A group represented by is preferred. As an imido acid group, -SO2NHSO2R A3 -CONHSO2R A4 , -CONHCOR A5 or -SO2NHCOR A6 A group represented by -SO2NHSO2R is preferred. A3 R is more preferable. A1 ~R A6 Each of these independently represents an alkyl group or an aryl group. A1 ~R A6 The alkyl and aryl groups represented by may have substituents. The substituents are preferably halogen atoms, and more preferably fluorine atoms.

[0175] Basic groups include amino groups, pyridinyl groups and their salts, ammonium groups, and phthalimidomethyl groups. Atoms or groups of atoms that make up the salts include hydroxide ions, halogen ions, carboxylate ions, sulfonate ions, and phenoxide ions.

[0176] Specific examples of pigment derivatives include the compounds described in the examples below. Also, the compounds described in Japanese Patent Publication No. 56-118462, Japanese Patent Publication No. 63-264674, Japanese Patent Publication No. 01-217077, Japanese Patent Publication No. 03-009961, Japanese Patent Publication No. 03-026767, Japanese Patent Publication No. 03-153780, Japanese Patent Publication No. 03-045662, Japanese Patent Publication No. 04-285669, and Japanese Patent Publication No. 06-1455 Compounds described in Japanese Patent Publication No. 46, compounds described in Japanese Patent Publication No. 06-212088, compounds described in Japanese Patent Publication No. 06-240158, compounds described in Japanese Patent Publication No. 10-030063, compounds described in Japanese Patent Publication No. 10-195326, compounds described in paragraphs 0086-0098 of International Publication No. 2011 / 024896, compounds described in paragraphs 0063-0094 of International Publication No. 2012 / 102399, International Publication No. 2017 / 03825 The compound described in paragraph 0082 of No. 2, the compound described in paragraph 0171 of JP 2015-151530, the compound described in paragraphs 0162 to 0183 of JP 2011-252065, the compound described in JP 2003-081972, the compound described in Patent No. 5299151, the compound described in JP 2015-172732, the compound described in JP 2014-199308, and JP 2014-085562 Examples include compounds described in the publications, compounds described in Japanese Patent Publication No. 2014-035351, compounds described in Japanese Patent Publication No. 2008-081565, compounds described in Japanese Patent Publication No. 2019-109512, compounds described in Japanese Patent Publication No. 2019-133154, diketopyrrolopyrrole compounds having thiol linking groups described in International Publication No. 2020 / 002106, benzimidazolone compounds described in Japanese Patent Publication No. 2018-168244, or salts thereof.

[0177] The pigment derivative content is preferably 1 to 50 parts by mass per 100 parts by mass of infrared absorber. The lower limit is preferably 3 parts by mass or more, and more preferably 5 parts by mass or more. The upper limit is preferably 40 parts by mass or less, and more preferably 30 parts by mass or less. Furthermore, the pigment derivative content is preferably 1 to 50 parts by mass per 100 parts by mass of infrared absorbing pigment. The lower limit is preferably 3 parts by mass or more, and more preferably 5 parts by mass or more. The upper limit is preferably 40 parts by mass or less, and more preferably 30 parts by mass or less. The curable composition of the present invention may contain only one pigment derivative or two or more. When two or more pigment derivatives are included, it is preferable that their total amount falls within the above range.

[0178] <<Compounds containing cyclic ether groups>> The curable composition of the present invention may further contain a compound having a cyclic ether group. Examples of cyclic ether groups include epoxy groups and oxetanyl groups, with epoxy groups being preferred. Examples of compounds having a cyclic ether group include compounds having 1 to 100 cyclic ether groups in one molecule. The upper limit of the number of cyclic ether groups can be, for example, 10 or less, or 5 or less. The lower limit of the number of cyclic ether groups is preferably 2 or more.

[0179] The compound having a cyclic ether group may be a low molecular weight compound (e.g., molecular weight less than 1000) or a high molecular weight compound (macromolecule) (e.g., molecular weight 1000 or more; in the case of a polymer, weight-average molecular weight 1000 or more). The weight-average molecular weight of the cyclic ether group is preferably 200 to 100,000, more preferably 500 to 50,000. The upper limit of the weight-average molecular weight is preferably 10,000 or less, more preferably 5,000 or less, and even more preferably 3,000 or less.

[0180] As compounds having a cyclic ether group, the compounds described in paragraphs 0034 to 0036 of Japanese Patent Publication No. 2013-011869, the compounds described in paragraphs 0147 to 0156 of Japanese Patent Publication No. 2014-043556, the compounds described in paragraphs 0085 to 0092 of Japanese Patent Publication No. 2014-089408, and the compounds described in Japanese Patent Publication No. 2017-179172 can also be used.

[0181] Commercially available compounds containing cyclic ether groups include Denacol EX-212L, EX-212, EX-214L, EX-214, EX-216L, EX-216, EX-321L, EX-321, EX-850L, EX-850 (all manufactured by Nagase ChemteX Corporation), ADEKA RESIN EP-4000S, EP-4003S, EP-4010S, EP-4011S (all manufactured by ADEKA Corporation), NC-2000, NC-3000, NC-7300, XD-1000, EPPN-501, EPPN-502 (all manufactured by ADEKA Corporation), Celoxide 2021P, Celoxide 2081, Celoxide 2083, Celoxide 2085, EHPE3150, and EPOLEAD PB. 3600, PB 4700 (all manufactured by Daicel Corporation), Cyclomer P ACA 200M, ACA 230AA, ACA Z250, ACA Z251, ACA Z300, ACA Z320 (all manufactured by Daicel Corporation), jER1031S, jER157S65, jER152, jER154, jER157S70 (all manufactured by Mitsubishi Chemical Corporation), Aronoxetane OXT-121, OXT-221, OX-SQ, PNOX (all manufactured by Toagosei Co., Ltd.), Adegaglycyrrhizol Examples include ED-505 (manufactured by ADEKA Corporation, epoxy group-containing monomer), Marproof G-0150M, G-0105SA, G-0130SP, G-0250SP, G-1005S, G-1005SA, G-1010S, G-2050M, G-01100, G-01758 (manufactured by NOF Corporation, epoxy group-containing polymer), OXT-101, OXT-121, OXT-212, OXT-221 (all manufactured by Toagosei Co., Ltd., oxetanyl group-containing monomer), OXE-10, OXE-30 (all manufactured by Osaka Organic Chemical Industry Co., Ltd., oxetanyl group-containing monomer).

[0182] The content of compounds having cyclic ether groups in the total solid content of the curable composition is preferably 0.1 to 40% by mass. The lower limit is preferably 1% by mass or more, and more preferably 2% by mass or more. The upper limit is preferably 30% by mass or less, and more preferably 20% by mass or less. Furthermore, the content of compounds having cyclic ether groups is preferably 1 to 400 parts by mass, more preferably 1 to 100 parts by mass, and even more preferably 1 to 50 parts by mass, per 100 parts by mass of polymerizable monomer. The curable composition of the present invention may contain only one compound having a cyclic ether group, or it may contain two or more. When two or more compounds having cyclic ether groups are included, it is preferable that their total amount falls within the above range.

[0183] <<Hardening agent>> When the curable composition of the present invention contains a compound having a cyclic ether group, it is preferable to further contain a curing agent. Examples of curing agents include amine compounds, acid anhydride compounds, amide compounds, phenol compounds, polycarboxylic acids, and thiol compounds. Specific examples of curing agents include succinic acid, trimellitic acid, pyromellitic acid, N,N-dimethyl-4-aminopyridine, and pentaerythritol tetrakis(3-mercaptopropionate). The curing agent may also be a compound described in paragraphs 0072 to 0078 of Japanese Patent Publication No. 2016-075720 or a compound described in Japanese Patent Publication No. 2017-036379. The content of the curing agent is preferably 0.01 to 20 parts by mass, more preferably 0.01 to 10 parts by mass, and even more preferably 0.1 to 6.0 parts by mass, per 100 parts by mass of the compound having a cyclic ether group. The curable composition of the present invention may contain only one curing agent or two or more curing agents. If two or more hardening agents are included, it is preferable that their total amount falls within the above range.

[0184] <<Surfactants>> The curable composition of the present invention preferably contains a surfactant. Various surfactants can be used, such as fluorinated surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and silicone surfactants. The surfactant is preferably a silicone surfactant or a fluorinated surfactant. Examples of surfactants are those described in paragraphs 0238 to 0245 of International Publication No. 2015 / 166779, which are incorporated herein by reference.

[0185] Examples of fluorinated surfactants include those described in paragraphs 0060 to 0064 of Japanese Patent Publication No. 2014-041318 (corresponding to paragraphs 0060 to 0064 of International Publication No. 2014 / 017669), those described in paragraphs 0117 to 0132 of Japanese Patent Publication No. 2011-132503, and those described in Japanese Patent Publication No. 2020-008634, the contents of which are incorporated herein by reference. Examples of commercially available fluorine-based surfactants include Megafac F-171, F-172, F-173, F-176, F-177, F-141, F-142, F-143, F-144, F-437, F-475, F-477, F-479, F-482, F-554, F-555-A, F-556, F-557, F-558, F-559, F-560, F-561, F-563, F-565, F-568, F-575, F-780, EXP, MFS-330, and R-01. R-40, R-40-LM, R-41, R-41-LM, RS-43, TF-1956, RS-90, R-94, RS-72-K, DS-21 (all manufactured by DIC Corporation), Florard FC430, FC431, FC171 (all manufactured by Sumitomo 3M Co., Ltd.), Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, KH-40 (all manufactured by AGC Inc.), PolyFox Examples include the PF636, PF656, PF6320, PF6520, PF7002 (all manufactured by OMNOVA), the F-Tergent 208G, 215M, 245F, 601AD, 601ADH2, 602A, 610FM, 710FL, 710FM, 710FS, and the FTX-218 (all manufactured by NEOS Corporation).

[0186] Furthermore, acrylic compounds having a molecular structure with a functional group containing a fluorine atom, in which the fluorine atom-containing functional group is cleaved and the fluorine atom volatilizes when heated, can also be suitably used as fluorine-based surfactants. Examples of such fluorine-based surfactants include the Megafac DS series manufactured by DIC Corporation (Chemical Daily (February 22, 2016), Nikkei Sangyo Shimbun (February 23, 2016)), such as Megafac DS-21.

[0187] Furthermore, it is also preferable to use a polymer of a fluorine atom-containing vinyl ether compound having a fluorinated alkyl group or a fluorinated alkylene ether group and a hydrophilic vinyl ether compound as the fluorine-based surfactant. Examples of such fluorine-based surfactants include the fluorine-based surfactant described in Japanese Patent Application Publication No. 2016-216602, the details of which are incorporated herein by reference.

[0188] Block polymers can also be used as fluorine-based surfactants. Fluorine-containing polymer compounds can also be preferably used as fluorine-based surfactants, including repeating units derived from a (meth)acrylate compound having a fluorine atom and repeating units derived from a (meth)acrylate compound having two or more (preferably five or more) alkylene oxy groups (preferably ethylene oxy groups, propylene oxy groups). Furthermore, fluorine-containing surfactants described in paragraphs 0016 to 0037 of Japanese Patent Application Publication No. 2010-032698, and the following compounds are also examples of fluorine-based surfactants used in the present invention. [ka] The weight-average molecular weight of the above compounds is preferably 3,000 to 50,000, for example, 14,000. In the above compounds, the percentage indicating the proportion of repeating units is expressed as mole percent.

[0189] Furthermore, as a fluorine-based surfactant, a fluorine-containing polymer having an ethylenically unsaturated bond-containing group in its side chain can also be used. Specific examples include the compounds described in paragraphs 0050 to 0090 and 0289 to 0295 of Japanese Patent Publication No. 2010-164965, and Megafac RS-101, RS-102, RS-718K, RS-72-K, etc., manufactured by DIC Corporation. Additionally, as a fluorine-based surfactant, the compounds described in paragraphs 0015 to 0158 of Japanese Patent Publication No. 2015-117327 can also be used.

[0190] Furthermore, using the surfactant described in International Publication No. 2020 / 084854 as a substitute for surfactants having a perfluoroalkyl group with 6 or more carbon atoms is also preferable from an environmental regulatory standpoint.

[0191] Furthermore, it is also preferable to use a fluorine-containing imide salt compound represented by formula (fi-1) as a surfactant. [ka] In equation (fi-1), m represents 1 or 2, n represents an integer from 1 to 4, a represents 1 or 2, and X a+ This refers to α-valent metal ions, primary ammonium ions, secondary ammonium ions, tertiary ammonium ions, quaternary ammonium ions, or NH4. + It represents.

[0192] Nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane and their ethoxylates and propoxylates (e.g., glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, and sorbitan lipids. Examples include fatty acid esters, Pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2 (manufactured by BASF), Tetronic 304, 701, 704, 901, 904, 150R1 (manufactured by BASF), Solspers 20000 (manufactured by Lubrizol Nippon Co., Ltd.), NCW-101, NCW-1001, NCW-1002 (manufactured by Wako Pure Chemical Industries, Ltd.), Paionin D-6112, D-6112-W, D-6315 (manufactured by Takemoto Oil & Fat Co., Ltd.), Orfin E1010, Surfinol 104, 400, 440 (manufactured by Nisshin Chemical Industry Co., Ltd.).

[0193] Cationic surfactants include tetraalkylammonium salts, alkylamine salts, benzalkonium salts, alkylpyridium salts, and imidazolium salts. Specific examples include dihydroxyethylstearylamine, 2-heptadecenyl-hydroxyethylimidazoline, lauryldimethylbenzylammonium chloride, cetylpyridinium chloride, and stearamidemethylpyridium chloride.

[0194] Examples of anionic surfactants include dodecylbenzenesulfonic acid, sodium dodecylbenzenesulfonate, sodium lauryl sulfate, sodium alkyldiphenyl ether disulfonate, sodium alkylnaphthalene sulfonate, sodium dialkyl sulfosuccinate, sodium stearate, potassium oleate, sodium dioctyl sulfosuccinate, sodium polyoxyethylene alkyl ether sulfate, sodium polyoxyethylene alkyl ether sulfate, sodium polyoxyethylene alkylphenyl ether sulfate, sodium dialkyl sulfosuccinate, sodium stearate, sodium oleate, and sodium t-octylphenoxyethoxypolyethoxyethyl sulfate.

[0195] Examples of silicone-based surfactants include SH8400, SH8400 FLUID, FZ-2122, 67 Additive, 74 Additive, M Additive, SF 8419 OIL (all manufactured by Dow Toray Industries, Inc.), TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (all manufactured by Momentive Performance Materials, Inc.), KP-341, KF-6000, KF-6001, KF-6002, KF-6003 (all manufactured by Shin-Etsu Chemical Co., Ltd.), BYK-307, BYK-322, BYK-323, BYK-330, BYK-3760, BYK-UV3510 (all manufactured by BIC Chemie Inc.).

[0196] Furthermore, silicone-based surfactants can also be compounds with the following structure. [ka]

[0197] The surfactant content in the total solids of the curable composition is preferably 0.001 to 1% by mass, more preferably 0.001 to 0.5% by mass, and even more preferably 0.001 to 0.2% by mass. The curable composition of the present invention may contain only one type of surfactant, or it may contain two or more types. If two or more types of surfactants are included, it is preferable that their total amount be within the above range.

[0198] <<Silane coupling agent>> The curable composition of the present invention may contain a silane coupling agent. In this specification, a silane coupling agent means a silane compound having a hydrolyzable group and other functional groups. A hydrolyzable group is a substituent that is directly bonded to a silicon atom and can form a siloxane bond by at least one of a hydrolysis reaction and a condensation reaction. Examples of hydrolyzable groups include halogen atoms, alkoxy groups, and acyloxy groups, with alkoxy groups being preferred. That is, silane coupling agents are preferably compounds having an alkoxysilyl group. Examples of functional groups other than hydrolyzable groups include vinyl groups, (meth)acryloyl groups, mercapto groups, epoxy groups, oxetanyl groups, amino groups, ureido groups, sulfide groups, isocyanate groups, and phenyl groups, with (meth)acryloyl groups and epoxy groups being preferred. Examples of silane coupling agents include the compounds described in paragraphs 0018 to 0036 of Japanese Patent Publication No. 2009-288703 and the compounds described in paragraphs 0056 to 0066 of Japanese Patent Publication No. 2009-242604, the details of which are incorporated herein by reference. The content of the silane coupling agent in the total solid content of the curable composition is preferably 0.01 to 15.0% by mass, and more preferably 0.05 to 10.0% by mass. The curable composition of the present invention may contain only one type of silane coupling agent, or it may contain two or more types. If two or more types of silane coupling agents are included, it is preferable that their total amount be within the above range.

[0199] <<Polymerization inhibitor>> The curable composition of the present invention may contain a polymerization inhibitor. Examples of polymerization inhibitors include hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, tert-butylcatechol, benzoquinone, 4,4'-thiobis(3-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-methyl-6-t-butylphenol), and N-nitrosophenylhydroxyamine salts (ammonium salts, cerium salts, etc.), with p-methoxyphenol being preferred. The content of the polymerization inhibitor in the total solid content of the curable composition is preferably 0.0001 to 5% by mass. The curable composition of the present invention may contain only one polymerization inhibitor or two or more. If two or more polymerization inhibitors are included, it is preferable that their total amount be within the above range.

[0200] <<Antioxidant>> The curable composition of the present invention may contain an antioxidant. Examples of antioxidants include phenol compounds, phosphite ester compounds, and thioether compounds. As the phenol compound, any phenol compound known as a phenolic antioxidant can be used. A preferred phenol compound is a hindered phenol compound. Compounds having a substituent at the ortho position adjacent to the phenolic hydroxyl group are preferred. As the substituent, substituted or unsubstituted alkyl groups having 1 to 22 carbon atoms are preferred. Furthermore, compounds having both a phenol group and a phosphite ester group in the same molecule are also preferred as antioxidants. In addition, phosphorus-based antioxidants can also be suitably used as antioxidants. Examples of phosphorus-based antioxidants include tris[2-[[2,4,8,10-tetrakis(1,1-dimethylethyl)dibenzo[d,f][1,3,2]dioxaphosfepin-6-yl]oxy]ethyl]amine, tris[2-[(4,6,9,11-tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphosfepin-2-yl)oxy]ethyl]amine, and ethylbis(2,4-di-tert-butyl-6-methylphenyl) phosphate. Examples of commercially available antioxidants include ADEKA stab AO-20, ADEKA stab AO-30, ADEKA stab AO-40, ADEKA stab AO-50, ADEKA stab AO-50F, ADEKA stab AO-60, ADEKA stab AO-60G, ADEKA stab AO-80, and ADEKA stab AO-330 (all manufactured by ADEKA Corporation). Alternatively, compounds described in paragraphs 0023-0048 of Japanese Patent No. 6268967, International Publication No. 2017 / 006600, and International Publication No. 2017 / 164024 can also be used as antioxidants. The antioxidant content in the total solid content of the curable composition is preferably 0.01-20% by mass, and more preferably 0.3-15% by mass. The curable composition of the present invention may contain only one antioxidant or two or more antioxidants. When two or more antioxidants are included, it is preferable that their total amount falls within the above range.

[0201] <<Coloring agent>> The curable composition of the present invention may contain a coloring agent. Examples of coloring agents include green coloring agents, red coloring agents, yellow coloring agents, purple coloring agents, blue coloring agents, orange coloring agents, and black coloring agents. The coloring agent may be a pigment or a dye. The content of the coloring agent in the total solid content of the curable composition is preferably 5% by mass or less, and more preferably 1% by mass or less. It is preferable that the curable composition of the present invention is substantially colorant-free. When the curable composition of the present invention is substantially colorant-free, it means that the content of the coloring agent in the total solid content of the curable composition is 0.1% by mass or less, preferably 0.05% by mass or less, and more preferably colorant-free.

[0202] <<Component B>> The curable composition of the present invention may optionally contain sensitizers, curing accelerators, fillers, thermosetting accelerators, plasticizers, and other auxiliary agents (e.g., conductive particles, defoamers, flame retardants, leveling agents, peel accelerators, fragrances, surface tension modifiers, chain transfer agents, etc.). By appropriately including these components, properties such as film properties can be adjusted. These components can be described, for example, in paragraphs 0183 onwards of Japanese Patent Application Publication No. 2012-003225 (paragraph 0237 of the corresponding US Patent Application Publication No. 2013 / 0034812), paragraphs 0101-0104, 0107-0109, etc., of Japanese Patent Application Publication No. 2008-250074, and these contents are incorporated herein. Furthermore, the composition of the present invention may optionally contain latent antioxidants. Examples of latent antioxidants include compounds in which the antioxidant portion is protected by a protecting group, and which function as antioxidants when heated at 100-250°C or at 80-200°C in the presence of an acid / base catalyst, thereby removing the protecting group. Examples of latent antioxidants include compounds described in International Publication No. 2014 / 021023, International Publication No. 2017 / 030005, and Japanese Patent Publication No. 2017-008219. Examples of commercially available latent antioxidants include ADEKA Arclus GPA-5001 (manufactured by ADEKA Corporation).

[0203] <container> There are no particular limitations on the container used to house the curable composition of the present invention, and any known container can be used. Furthermore, to suppress the incorporation of impurities into the raw materials and the curable composition, it is preferable to use a multilayer bottle with an inner wall made of six types of resin in six layers, or a bottle with a seven-layer structure of six types of resin. Examples of such containers include the container described in Japanese Patent Application Publication No. 2015-123351. In addition, the inner wall of the container is preferably made of glass, stainless steel, or the like to prevent metal leaching from the inner wall, improve the long-term stability of the curable composition, and suppress component deterioration.

[0204] <Method for preparing a curable composition> The curable composition of the present invention can be prepared by mixing the aforementioned components. When preparing the curable composition, all components may be dissolved or dispersed simultaneously in a solvent to prepare the curable composition, or, if necessary, two or more solutions or dispersions containing each component in appropriate proportions may be prepared in advance and mixed at the time of use (application) to prepare the composition.

[0205] The preparation of the curable composition may include a process for dispersing the pigment. Examples of mechanical forces used in the pigment dispersion process include compression, squeezing, impact, shearing, and cavitation. Specific examples of these processes include bead mills, sand mills, roll mills, ball mills, paint shakers, microfluidizers, high-speed impellers, sand grinders, flow jet mixers, high-pressure wet atomization, and ultrasonic dispersion. Furthermore, in the grinding of pigments using a sand mill (bead mill), it is preferable to process the material under conditions that enhance grinding efficiency, such as by using small-diameter beads or increasing the bead packing density. It is also preferable to remove coarse particles after the grinding process by filtration or centrifugation. Furthermore, the processes and dispersers for dispersing the pigments can suitably be those described in "Complete Collection of Dispersion Technologies, published by Joho Kiko Co., Ltd., July 15, 2005," "Comprehensive Data Collection on Dispersion Technologies and Practical Industrial Applications, Centered on Suspensions (Solid / Liquid Dispersion Systems), published by Keiei Kaihatsu Center Publishing Department, October 10, 1978," and paragraph 0022 of Japanese Patent Publication No. 2015-157893. In addition, the pigment dispersion process may be refined by a salt milling process. For materials, equipment, and processing conditions used in the salt milling process, refer to, for example, Japanese Patent Publication No. 2015-194521 and Japanese Patent Publication No. 2012-046629. As beads used for dispersion, zirconia, agate, quartz, titania, tungsten carbide, silicon nitride, alumina, stainless steel, glass, or combinations thereof can be used. In addition, inorganic compounds with a Mohs hardness of 2 or higher can be used as beads. The curable composition may contain 1 to 10,000 ppm of the above-mentioned beads.

[0206] In preparing a curable composition, it is preferable to filter the composition with a filter for purposes such as removing foreign matter and reducing defects. Any filter that has been conventionally used for filtration purposes can be used without particular limitations. For example, filters made of materials such as fluororesins such as polytetrafluoroethylene (PTFE), polyamide resins such as nylon (e.g., nylon-6, nylon-6,6), and polyolefin resins such as polyethylene and polypropylene (PP) (including high-density and ultra-high molecular weight polyolefin resins) can be used. Among these materials, polypropylene (including high-density polypropylene) and nylon are preferred.

[0207] The pore size of the filter is preferably 0.01 to 7.0 μm, more preferably 0.01 to 3.0 μm, and even more preferably 0.05 to 0.5 μm. If the filter pore size is within the above range, fine foreign matter can be removed more reliably. The nominal value of the filter pore size can be referred to from the filter manufacturer. Various filters provided by Nippon Pall Co., Ltd. (DFA4201NXEY, DFA4201NAEY, DFA4201J006P, etc.), Advantec Toyo Co., Ltd., Nippon Integris Co., Ltd. (formerly Nippon Microlith Co., Ltd.), and KITZ Microfilter Corporation can be used.

[0208] Furthermore, it is also preferable to use fibrous filter media as a filter. Examples of fibrous filter media include polypropylene fiber, nylon fiber, and glass fiber. Commercially available products include the SBP type series (SBP008, etc.), TPR type series (TPR002, TPR005, etc.), and SHPX type series (SHPX003, etc.) from Rokitechno Co., Ltd.

[0209] When using filters, different filters (for example, a first filter and a second filter) may be combined. In this case, filtration with each filter may be performed only once or two or more times. Filters with different pore sizes within the range described above may also be combined. Furthermore, filtration with the first filter may be performed only on the dispersion, and after mixing in other components, filtration with the second filter may be performed.

[0210] <Cured film> Next, the cured film of the present invention will be described. The cured film of the present invention is obtained by curing the curable composition of the present invention described above. The cured film of the present invention can preferably be used as a near-infrared cut filter. Examples of near-infrared cut filters include near-infrared cut filters on the light-receiving side of a solid-state image sensor (for example, for a near-infrared cut filter for a wafer-level lens), infrared cut filters on the back side (opposite side from the light-receiving side) of a solid-state image sensor, and near-infrared cut filters for ambient light sensors (for example, illuminance sensors that sense the illuminance and color tone of the environment in which an information terminal device is placed and adjust the color tone of the display, and color correction sensors that adjust the color tone). In particular, it can preferably be used as a near-infrared cut filter on the light-receiving side of a solid-state image sensor.

[0211] The cured film of the present invention may have a pattern or it may be a film without a pattern (a flat film).

[0212] 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, even more preferably 5 μm or less, even more preferably 4 μm or less, and even more preferably 2.5 μm or less. The lower limit of the film thickness is preferably 0.1 μm or more, more preferably 0.2 μm or more, and even more preferably 0.5 μm or more.

[0213] The cured film of the present invention preferably has a transmittance of 20% or less at at least one point in the wavelength range of 700 to 2000 nm (preferably 700 to 1500 nm, more preferably 700 to 1300 nm, and even more preferably 700 to 1000 nm), more preferably 15% or less, and even more preferably 10% or less. Furthermore, the average transmittance of light in the wavelength range of 400 to 600 nm is preferably 70% or more, more preferably 80% or more, even more preferably 85% or more, and particularly preferably 90% or more. In addition, the minimum transmittance of light in the wavelength range of 400 to 600 nm is preferably 70% or more, more preferably 80% or more, and even more preferably 90% or more.

[0214] The cured film of the present invention has a maximum absorbance A in the wavelength range of 700 to 2000 nm. 1 And the maximum absorbance A in the wavelength range of 400-600 nm. 2 Ratio (absorbance ratio A) 1 / A 2 It is preferable that the value is 4.5 or higher, more preferably 6 or higher, even more preferably 8 or higher, and even more preferably 12 or higher. There is no particular upper limit, but it can be 50 or lower.

[0215] The cured film of the present invention has a maximum absorbance A in the wavelength range of 700 to 2000 nm. 1 And absorbance A at a wavelength of 365 nm 3 Ratio (absorbance ratio A) 1 / A 3 The value of ) is preferably 1 or greater and less than 9. The lower limit is preferably 1.5 or greater, and more preferably 2 or greater. The upper limit is preferably less than 4.5, and more preferably less than 3.

[0216] The cured film of the present invention can also be used in combination with a color filter containing a chromatic coloring agent. The color filter can be manufactured using a coloring composition containing a chromatic coloring agent. When the cured film of the present invention is used in combination with a color filter, it is preferable that the color filter is positioned on the optical path of the cured film of the present invention. For example, it is preferable to laminate the cured film of the present invention and the color filter to form a laminate. In the laminate, the cured film of the present invention and the color filter may or may not be adjacent in the thickness direction. If the cured film of the present invention and the color filter are not adjacent in the thickness direction, the cured film of the present invention may be formed on a support other than the support on which the color filter is formed, and other components constituting a solid-state image sensor (e.g., microlenses, planarization layers, etc.) may be interposed between the film of the present invention and the color filter.

[0217] The cured film of the present invention can be used in various devices such as solid-state image sensors like CCDs (charge-coupled devices) and CMOS (complementary metal-oxide-semiconductor) sensors, as well as infrared sensors and image display devices.

[0218] <Method for forming patterns> The present invention provides a method for forming a pattern, comprising the steps of: forming a curable composition layer on a support using the curable composition of the present invention; a first exposure step of irradiating the curable composition layer with light having a wavelength greater than 350 nm and less than or equal to 380 nm to expose it in a patterned manner; a developing step of developing the curable composition layer; and a second exposure step of irradiating the curable composition layer with light having a wavelength greater than or equal to 254 nm and less than or equal to 350 nm after the developing step.

[0219] In the pattern formation method of the present invention, it is preferable to perform the entire process at a temperature of less than 200°C, and more preferably at a temperature of 150°C or lower. In this specification, "performing the entire process at a temperature of less than 200°C" means that all steps of forming a patterned cured film using a curable composition are performed at a temperature of less than 200°C.

[0220] In the pattern formation method of the present invention, a heating step may be added after the second exposure step. However, in this case, the heating temperature shall be less than 200°C. The details of each step are described below.

[0221] <<Process for forming the curable composition layer>> In the step of forming a curable composition layer, the curable composition of the present invention is applied to a support to form a curable composition layer.

[0222] Examples of support materials include semiconductor substrates such as silicon substrates and transparent substrates.

[0223] A charge-coupled device (CCD), complementary metal-oxide-semiconductor (CMOS), transparent conductive film, etc., may be formed on the semiconductor substrate used as a support. Furthermore, partitions or black matrices that isolate each pixel may be formed on the semiconductor substrate. Additionally, if necessary, an undercoat layer may be provided on the semiconductor substrate to improve adhesion to the upper layer, prevent diffusion of materials, or flatten the substrate surface.

[0224] The transparent substrate used as a support is not particularly limited as long as it is made of a material that can transmit at least visible light. Examples include substrates made of glass, resin, etc. Examples of resins include polyester resins such as polyethylene terephthalate and polybutylene terephthalate, polyolefin resins such as polyethylene, polypropylene, and ethylene vinyl acetate copolymer, acrylic resins such as norbornene resin, polyacrylate, and polymethyl methacrylate, urethane resin, vinyl chloride resin, fluororesin, polycarbonate resin, polyvinyl butyral resin, and polyvinyl alcohol resin. Examples of glass include soda-lime glass, borosilicate glass, alkali-free glass, quartz glass, and copper-containing glass. Examples of copper-containing glass include copper-containing phosphate glass and copper-containing fluorophosphate glass. Commercially available copper-containing glass can also be used. An example of a commercially available copper-containing glass is NF-50 (manufactured by AGC Techno Glass Co., Ltd.).

[0225] Known methods can be used for applying the curable composition. Examples include the drop method (drop casting); slit coating method; spray method; roll coating method; spin coating method; casting method; slit and spin method; pre-wetting method (for example, the method described in Japanese Patent Application Publication No. 2009-145395); various printing methods such as inkjet (for example, on-demand, piezo, and thermal), nozzle jet printing, flexographic printing, screen printing, gravure printing, reverse offset printing, and metal mask printing; transfer methods using molds, etc.; and nanoimprint methods. The application method for inkjet printing is not particularly limited, and examples include the method shown in "Expanding and Usable Inkjet Printing - Infinite Possibilities Seen in Patents," published in February 2005 by Sumibe Techno Research (especially pages 115-133), as well as the methods described in Japanese Patent Publication Nos. 2003-262716, 2003-185831, 2003-261827, 2012-126830, and 2006-169325.

[0226] The curable composition layer formed on the support may be dried (pre-baked). When pre-baking is performed, the pre-baking temperature is preferably 80°C or lower, more preferably 70°C or lower, even more preferably 60°C or lower, and particularly preferably 50°C or lower. The lower limit can be, for example, 40°C or higher. The pre-baking time is preferably 10 to 3600 seconds. Pre-baking can be performed using a hot plate, oven, or the like.

[0227] <<First exposure process>> In the first exposure step, the curable composition layer is exposed in a pattern by irradiating it with light having a wavelength between 350 nm and 380 nm. For example, the curable composition layer can be exposed in a pattern by using an exposure device such as a stepper and exposing it through a mask having a predetermined mask pattern. This allows the exposed portion of the curable composition layer to be cured. The light that can be used for exposure is preferably light with a wavelength between 350 nm and 370 nm, and more preferably i-line (365 nm).

[0228] For example, the irradiation dose (exposure dose) is 30 to 1500 mJ / cm². 2 Preferably, 50-1000 mJ / cm² 2 This is more preferable. The oxygen concentration during exposure can be appropriately selected. In addition to exposure in the atmosphere, exposure may be carried out in a low-oxygen atmosphere with an oxygen concentration of 19 vol% or less (e.g., 15 vol%, 5 vol%, substantially oxygen-free), or in a high-oxygen atmosphere with an oxygen concentration exceeding 21 vol% (e.g., 22 vol%, 30 vol%, 50 vol%). Furthermore, the exposure intensity can be appropriately set, usually 1000 W / m². 2 ~100,000 W / m 2 (For example, 5000W / m 2 , 15000W / m 2 , 35000W / m 2 The oxygen concentration and exposure intensity can be combined as appropriate; for example, an oxygen concentration of 10% by volume and an illuminance of 10,000 W / m². 2 At an oxygen concentration of 35% by volume, the illuminance is 20,000 W / m². 2 This can be done as follows.

[0229] <<Developing process>> In the development process, the unexposed areas of the curable composition layer are developed and removed to form a pattern (pixel). The unexposed areas of the curable composition layer can be developed and removed using a developer. This causes the unexposed areas of the curable composition layer in the exposure process to dissolve in the developer, leaving only the photocured parts. Examples of developers include organic solvents and alkaline developers, with alkaline developers being preferred. The developer temperature is preferably, for example, 20 to 30°C. The development time is preferably 20 to 180 seconds. Furthermore, to improve residue removal, the developer may be emptied every 60 seconds, and the process of supplying fresh developer may be repeated several times.

[0230] The alkaline developer is preferably an alkaline aqueous solution obtained by diluting an alkaline agent with pure water. Examples of alkaline agents include organic alkaline compounds such as ammonia, ethylamine, diethylamine, dimethylethanolamine, diglycolamine, diethanolamine, hydroxyamine, ethylenediamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, ethyltrimethylammonium hydroxide, benzyltrimethylammonium hydroxide, dimethylbis(2-hydroxyethyl)ammonium hydroxide, choline, pyrrole, piperidine, and 1,8-diazabicyclo[5.4.0]-7-undecene, as well as inorganic alkaline compounds such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, sodium silicate, and sodium metasilicate. Alkaline agents with larger molecular weights are preferred from an environmental and safety perspective. The concentration of the alkaline agent in the alkaline aqueous solution is preferably 0.001 to 10% by mass, and more preferably 0.01 to 1% by mass. The developer may also further contain a surfactant. Nonionic surfactants are preferred as the surfactant. For convenience in transport and storage, the developing solution may be manufactured as a concentrated solution and then diluted to the required concentration at the time of use. The dilution ratio is not particularly limited, but can be set in the range of 1.5 to 100 times, for example.

[0231] Furthermore, it is preferable to wash (rinse) with pure water after development. It is also preferable to supply rinsing liquid to the curable composition layer after development while rotating the support on which the curable composition layer has been formed after development. It is also preferable to move the nozzle that discharges the rinsing liquid from the center of the support to the periphery of the support. In this case, the nozzle may be moved from the center to the periphery of the support while gradually decreasing the speed of the nozzle's movement. Performing rinsing in this manner can suppress in-plane variation of the rinse. A similar effect can also be obtained by gradually decreasing the rotation speed of the support while moving the nozzle from the center to the periphery of the support.

[0232] <<Second exposure process>> In the second exposure step, the curable composition layer is exposed by irradiating it with light having a wavelength of 254 nm to 350 nm. The irradiated light preferably includes light with a wavelength of 300 nm or less, and more preferably includes light with a wavelength of 254 nm. The second exposure step can be carried out, for example, using an ultraviolet photoresist curing apparatus. The ultraviolet photoresist curing apparatus may irradiate, for example, light with a wavelength of 254 nm to 350 nm, as well as other light (e.g., i-light). The difference between the wavelength of light used in the exposure before development described above and the wavelength of light used in the exposure after development (post-exposure) is preferably 200 nm or less, and more preferably 100 to 150 nm.

[0233] The irradiation dose (exposure dose) is 30-4000 mJ / cm². 2 Preferably, 50-3500 mJ / cm² 2 This is more preferable. The oxygen concentration during exposure can be appropriately selected, similar to the conditions during the first exposure step.

[0234] In this invention, by exposing the curable composition layer in two stages, before and after development, the curable composition layer can be moderately cured in the first exposure (exposure before development), and the entire curable composition layer can be almost completely cured in the second exposure (exposure after development). As a result, even under low temperature conditions of less than 200°C, the curable composition can be sufficiently cured to form a patterned cured film with excellent adhesion, as well as excellent solvent resistance, flatness, and rectangularity.

[0235] <<Post-bake>> In the pattern formation of the present invention, a step of heating the curable composition layer at a predetermined temperature (post-bake) may be performed during at least one of the periods between the development step and the second exposure step, and after the second exposure step. The heating temperature for post-bake is preferably less than 200°C, more preferably 150°C or less, and even more preferably 120°C or less. Furthermore, the heating temperature for post-bake is preferably 45°C or higher, more preferably 50°C or higher, and even more preferably 80°C or higher. In particular, when a resin substrate is used, or when the photoelectric conversion layer is composed of an organic material, the heating temperature is preferably 50 to 120°C, more preferably 80 to 100°C, and even more preferably 80 to 90°C. The heating time can be appropriately selected, for example, 1 to 10 minutes, preferably 2 to 8 minutes, and more preferably 3 to 6 minutes.

[0236] Post-baking may be performed in an atmospheric environment or in a low-oxygen atmosphere. From the viewpoint of suppressing deterioration due to oxidation of the film, post-baking is preferably performed in a low-oxygen atmosphere with an oxygen concentration of 19% by volume or less, more preferably 15% by volume or less, even more preferably 5% by volume or less, and particularly preferably 1% by volume or less (substantially oxygen-free).

[0237] Post-baking can be carried out continuously or in batches using heating means such as hot plates, convection ovens (hot air circulation dryers), or high-frequency heaters. On the other hand, post-baking may not be necessary if there are difficulties in heating the structure after exposure, or if the curable composition layer has sufficiently hardened.

[0238] The thickness of the patterned cured film after the second exposure step (or after post-baking if post-baking is performed after the second exposure step) is preferably 0.1 to 5 μm. The lower limit is preferably 0.2 μm or more, and more preferably 0.3 μm or more. The upper limit is preferably 3 μm or less, and more preferably 1.5 μm or less. The width of the pattern of the cured film is preferably 0.1 to 20 μm. The lower limit is preferably 0.3 μm or more, and more preferably 0.5 μm or more. The upper limit is preferably 15 μm or less, and more preferably 10 μm or less.

[0239] <Near-infrared cut filter> The near-infrared cut filter of the present invention has the cured film of the present invention described above. The near-infrared cut filter of the present invention preferably has an average transmittance of 70% or more for light with a wavelength of 400 to 600 nm, more preferably 80% or more, even more preferably 85% or more, and particularly preferably 90% or more. Furthermore, the minimum transmittance of light in the wavelength range of 400 to 600 nm is preferably 70% or more, more preferably 80% or more, and even more preferably 90% or more. The preferred range for near-infrared shielding of a near-infrared cut filter varies depending on the application, but it is preferable that the transmittance at at least one point in the wavelength range of 700 to 2000 nm (preferably 700 to 1500 nm, more preferably 700 to 1300 nm, and even more preferably 700 to 1000 nm) is 20% or less, more preferably 15% or less, and even more preferably 10% or less.

[0240] The near-infrared cut filter of the present invention may further include, in addition to the cured film of the present invention described above, a copper-containing layer, a dielectric multilayer film, an ultraviolet absorption layer, and the like. Examples of ultraviolet absorption layers include the absorption layers described in paragraphs 0040 to 0070 and 0119 to 0145 of International Publication No. 2015 / 099060. Examples of dielectric multilayer films include the dielectric multilayer films described in paragraphs 0255 to 0259 of Japanese Patent Application Publication No. 2014-041318. As copper-containing layers, glass substrates made of copper-containing glass (copper-containing glass substrates) or layers containing copper complexes (copper complex-containing layers) can also be used. Examples of copper-containing glass substrates include copper-containing phosphate glass and copper-containing fluorine-phosphate glass. Examples of commercially available copper-containing glass include NF-50 (manufactured by AGC Techno Glass Co., Ltd.), BG-60, BG-61 (both manufactured by Schott), and CD5000 (manufactured by HOYA Corporation).

[0241] <Solid-state image sensor> The solid-state image sensor of the present invention includes the cured film of the present invention described above. The configuration of the solid-state image sensor is not particularly limited as long as it has the cured film of the present invention and functions as a solid-state image sensor. For example, the following configurations can be given.

[0242] The imaging device has a support on which a plurality of photodiodes constituting the light-receiving area of ​​a solid-state image sensor and a transfer electrode made of polysilicon or the like are provided. The photodiodes and transfer electrode have a light-shielding film made of tungsten or the like with an opening only for the light-receiving portion of the photodiode. The light-shielding film has a device protection film made of silicon nitride or the like formed on the light-shielding film so as to cover the entire surface of the light-shielding film and the light-receiving portion of the photodiode. The device protection film has the cured film of the present invention. Furthermore, the device protection film may have a configuration in which a light-gathering means (e.g., a microlens; the same applies hereinafter) is provided below the cured film of the present invention (on the side closer to the support), or a configuration in which the light-gathering means is provided on the cured film of the present invention. The color filter may also have a structure in which a film forming each pixel is embedded in a space partitioned, for example, in a grid pattern by partitions. In this case, it is preferable that the partitions have a lower refractive index than each pixel. Examples of imaging devices having such a structure include the devices described in Japanese Patent Application Publication No. 2012-227478 and Japanese Patent Application Publication No. 2014-179577.

[0243] <Image display device> The image display device of the present invention includes the cured film of the present invention. Examples of image display devices include liquid crystal displays and organic electroluminescent (organic EL) displays. Definitions and details of image display devices are described, for example, in "Electronic Display Devices" (by Akio Sasaki, Kogyo Chosakai Co., Ltd., published in 1990) and "Display Devices" (by Yoshiaki Ibuki, Sangyo Tosho Co., Ltd., published in 1989). Liquid crystal displays are described, for example, in "Next-Generation Liquid Crystal Display Technology" (edited by Tatsuo Uchida, Kogyo Chosakai Co., Ltd., published in 1994). There are no particular restrictions on the liquid crystal display devices to which the present invention can be applied; for example, it can be applied to various types of liquid crystal display devices described in the above-mentioned "Next-Generation Liquid Crystal Display Technology". The image display device may also have a white organic EL element. The white organic EL element is preferably in a tandem structure. The tandem structure of organic EL elements is described in Japanese Patent Publication No. 2003-045676, supervised by Akiyoshi Mikami, "The Cutting Edge of Organic EL Technology Development - High Brightness, High Precision, Long Lifespan, and Know-how Collection," Technical Information Association, pp. 326-328, 2008, etc. The spectrum of white light emitted by the organic EL element preferably has strong maximum emission peaks in the blue region (430-485 nm), the green region (530-580 nm), and the yellow region (580-620 nm). In addition to these emission peaks, it is even more preferable to have a maximum emission peak in the red region (650-700 nm).

[0244] <Infrared sensor> The infrared sensor of the present invention includes the cured film of the present invention described above. The configuration of the infrared sensor is not particularly limited as long as it functions as an infrared sensor. Hereinafter, one embodiment of the infrared sensor of the present invention will be described with reference to the drawings.

[0245] In Figure 1, reference numeral 110 denotes a solid-state image sensor. A near-infrared cut filter 111 and an infrared transmission filter 114 are arranged on the imaging area of ​​the solid-state image sensor 110. A color filter 112 is also arranged on the near-infrared cut filter 111. Microlenses 115 are arranged on the incident light hν side of the color filter 112 and the infrared transmission filter 114. A planarization layer 116 is formed to cover the microlenses 115.

[0246] The near-infrared cut filter 111 can be formed using the curable composition of the present invention. The color filter 112 is a color filter in which pixels that transmit and absorb light of specific wavelengths in the visible region are formed, and is not particularly limited; conventionally known color filters for pixel formation can be used. For example, a color filter in which red (R), green (G), and blue (B) pixels are formed can be used. For example, the description in paragraphs 0214 to 0263 of Japanese Patent Application Publication No. 2014-043556 can be referenced, and this content is incorporated herein. The characteristics of the infrared transmission filter 114 are selected according to the emission wavelength of the infrared LED used.

[0247] In the infrared sensor shown in Figure 1, a near-infrared cut filter (another near-infrared cut filter) separate from the near-infrared cut filter 111 may be further arranged on the planarization layer 116. Examples of other near-infrared cut filters include those having a copper-containing layer and / or a dielectric multilayer film. Details of these are described above. A dual bandpass filter may also be used as the other near-infrared cut filter. [Examples]

[0248] The present invention will be specifically described below with reference to examples. The materials, amounts used, proportions, processing content, and processing procedures shown in the following examples can be modified as appropriate, as long as they do not depart from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below.

[0249] <Manufacturing of curable compositions> A curable composition was prepared by mixing the materials listed in the table below. For the dispersion, the materials of the types listed in the "Dispersion" column of the table below were mixed in the amounts indicated by parts by mass in the "Dispersion" column of the table below. Then, 230 parts by mass of 0.3 mm diameter zirconia beads were added, and the mixture was dispersed using a paint shaker for 5 hours. The beads were then separated by filtration to prepare the dispersion. The values ​​listed in the "Amount" column for infrared absorber, dispersion aid, dispersant, polymerizable monomer, photopolymerization initiator, ultraviolet absorber, additive, resin, surfactant, and polymerization inhibitor are based on solid content.

[0250] [Table 1] [Table 2] [Table 3]

[0251] [Table 4] [Table 5] [Table 6]

[0252] [Table 7] [Table 8] [Table 9]

[0253] [Table 10] [Table 11] [Table 12]

[0254] The details of the materials listed in the table above are as follows:

[0255] (Infrared filtration agent) A1-A15: Compounds with the following structure [ka] [ka] [ka] A16: FDR-003 (Yamada Chemical Industry Co., Ltd.) A17: FDR-004 (Yamada Chemical Industry Co., Ltd.) A18: FDR-005 (Yamada Chemical Industry Co., Ltd.)

[0256] (Dispersing agent) S1~S9: Compounds with the following structure [ka] [ka] [ka]

[0257] (Dispersant) C1: Resin with the following structure (the values ​​attached to the main chain are molar ratios, and the values ​​attached to the side chains are the number of repeating units. Weight-average molecular weight: 20000) [ka] C2: Resin with the following structure (the values ​​attached to the main chain are molar ratios, and the values ​​attached to the side chains are the number of repeating units. Weight-average molecular weight: 10000) [ka] C3: DSIPERBYK-140 (manufactured by Big Chemie Co., Ltd.) C4: DSIPERBYK-2026 (manufactured by Big Chemie)

[0258] (solvent) J1: Propylene glycol monomethyl ether acetate (PGMEA)

[0259] (polymerizable monomer) D1: Arronix M-305 (manufactured by Toagosei Co., Ltd.) D2: NK ester A-TMMT (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) D3: KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.)

[0260] (Photopolymerization initiator) [Photopolymerization initiator IA] I-A1: Compound with the following structure (oxime compound, extinction coefficient of 7.0 × 10⁻¹⁰ at a wavelength of 365 nm in methanol) 3 mL / g·cm) I-A2: Compound with the following structure (oxime compound, extinction coefficient at a wavelength of 365 nm in methanol: 7.7 × 10⁻¹⁰) 3 mL / g·cm) [ka] [Photopolymerization initiator IB] I-B1: Compound with the following structure (hydroxyalkylphenone compound, with an extinction coefficient of 48.9 mL / g·cm at a wavelength of 365 nm in methanol and an extinction coefficient of 3.0 × 10 at a wavelength of 254 nm) 4 mL / g·cm) I-B2: Compound with the following structure (hydroxyalkylphenone compound, with an extinction coefficient of 48.9 mL / g·cm at a wavelength of 365 nm in methanol and an extinction coefficient of 5.0 × 10 at a wavelength of 254 nm) 4 mL / g·cm) [ka]

[0261] (UV absorber) U1: Avobenzone (a compound with the structure shown below, a dibenzoyl compound) [ka] U2: Compound with the following structure (conjugated diene compound) [ka]

[0262] (Additives) E1: ADEKA Stab AO-80 (manufactured by ADEKA Corporation, antioxidant)

[0263] (resin) P1: Resin with the following structure (the values ​​appended to the main chain are molar ratios. Weight-average molecular weight: 30,000) P2: Resin with the following structure (the values ​​appended to the main chain are molar ratios. Weight-average molecular weight: 30,000) P3: Resin with the following structure (the values ​​appended to the main chain are molar ratios. Weight-average molecular weight: 10000) P4: Resin with the following structure (weight-average molecular weight 20,000) P5: Resin with the following structure (the values ​​appended to the main chain are molar ratios. Weight-average molecular weight: 15000) P6: Resin with the following structure (the values ​​appended to the main chain are molar ratios. Weight-average molecular weight: 15000) P7: Resin with the following structure (the values ​​appended to the main chain are molar ratios. Weight-average molecular weight: 15000) [ka] [ka]

[0264] (Surfactants) F1: Compound with the following structure (silicone-based surfactant) [ka] F2: Megafac RS-72-K (manufactured by DIC Corporation, 30% solid content propylene glycol monomethyl ether acetate solution, fluorine-based surfactant)

[0265] (Polymerization inhibitor) G1: p-Methoxyphenol

[0266] For each curable composition, the total content of photopolymerization initiator IA and photopolymerization initiator IB in the total solids content of the curable composition shall be indicated in the "Content of Photopolymerization Initiator" column, the content of photopolymerization initiator IB per 100 parts by mass of photopolymerization initiator IA shall be indicated in the "Content of Photopolymerization Initiator IB" column, the content of infrared absorber in the total solids content of the curable composition shall be indicated in the "Content of Infrared Absorber" column, the content of polymerizable monomer in the total solids content of the curable composition shall be indicated in the "Content of Polymerizable Monomer" column, the content of resin per 100 parts by mass of polymerizable monomer shall be indicated in the "Content of Resin" column, and the content of ultraviolet absorber per 100 parts by mass of photopolymerization initiator IA shall be indicated in the "Content of Ultraviolet Absorber" column.

[0267] [Table 13] [Table 14] [Table 15]

[0268] [Table 16] <Evaluation of Spectroscopic Characteristics> Each curable composition was applied to a glass substrate using a spin coater to form a coating film. Then, the coating film was pre-baked using a 100°C hot plate for 120 seconds to achieve a dry film thickness of 1.0 μm. Next, using an i-line stepper exposure system FPA-i5+ (manufactured by Canon Inc.), the coating film was exposed to 365 nm wavelength light at a rate of 1000 mJ / cm². 2 The first exposure was performed by irradiating with the specified exposure dose. Next, the entire glass substrate was treated with 10,000 mJ / cm² using an ultraviolet photoresist curing device (MMA-802-HC-552, manufactured by Ushio Electric Co., Ltd.). 2 The film was irradiated with the specified exposure dose, and a second exposure was performed to obtain a cured film. For the spectroscopy of the obtained cured film, the absorption spectrum in the wavelength range of 300 to 2000 nm was measured using a spectrophotometer (U-4100, manufactured by Hitachi High-Tech Corporation), and the maximum absorbance A in the wavelength range of 700 to 2000 nm was determined. 1 And the maximum absorbance A in the wavelength range of 400-600 nm. 2 Ratio (absorbance ratio A) 1 / A 2 ), and the maximum absorbance A in the wavelength range of 700-2000 nm. 1 And absorbance A at a wavelength of 365 nm 3 Ratio (absorbance ratio A) 1 / A 3 The following values ​​were measured:

[0269] -A 1 / A 2 Evaluation criteria - 5:A 1 / A 2 The value is 8 or greater. 4:A 1 / A 2 The value is 6 or greater and less than 8. 3:A 1 / A 2 The value is 4.5 or greater and less than 6. 2:A 1 / A 2 The value is 2 or greater and less than 4.5. 1:A 1 / A 2 The value is less than 2.

[0270] -A 1 / A 3 Evaluation criteria - 5:A 1 / A 3 The value is 2 or greater and less than 3. 4:A 1 / A 3 The value is 1.5 or greater but less than 2, or 3 or greater but less than 4.5. 3:A 1 / A 3 The value is 1 or greater and less than 1.5, or 4.5 or greater and less than 9. 2:A 1 / A 3 The value is 0.5 or greater and less than 1, or 9 or greater and less than 12. 1:A 1 / A 3 The value is less than 0.5 or 12 or greater.

[0271] <Evaluation of solvent resistance> Each curable composition was applied to a glass substrate using a spin coater to form a coating film. Then, the coating film was pre-baked using a 100°C hot plate for 120 seconds to achieve a dry film thickness of 1.0 μm. Next, using an i-line stepper exposure system FPA-i5+ (manufactured by Canon Inc.), the coating film was exposed to 365 nm wavelength light at a rate of 1000 mJ / cm². 2 The first exposure was performed by irradiating with the specified exposure dose. Next, the entire glass substrate was treated with 10,000 mJ / cm² using an ultraviolet photoresist curing device (MMA-802-HC-552, manufactured by Ushio Electric Co., Ltd.). 2 The film was irradiated with the specified exposure dose, and a second exposure was performed to obtain a cured film. The spectrum of the obtained cured film was measured using an ultraviolet-visible-near-infrared spectrophotometer. The obtained cured film was then immersed in acetone for 600 seconds and spray-dried (solvent resistance test). The spectrum of the cured film after the solvent resistance test was measured using an ultraviolet-visible-near-infrared spectrophotometer, and the solvent resistance was evaluated according to the following criteria. -Evaluation criteria for solvent resistance- C1 is defined as the minimum transmittance in the wavelength range of 700 to 2000 nm before the solvent resistance test, and D1 is defined as the minimum transmittance in the wavelength range of 700 to 2000 nm after the solvent resistance test. 5: The value of D1-C1 is less than 0.1%. 4: The value of D1-C1 is between 0.1% and less than 0.5%. 3: The value of D1-C1 is between 0.5% and less than 1.0%. 2: The value of D1-C1 is between 1.0% and 5.0%. 1: The value of D1-C1 is 5.0% or higher.

[0272] <Evaluation of Rectangularity> Each curable composition was applied to a silicon wafer using a spin coater (Mikasa Corporation) to form a coating film with a film thickness of 1.0 μm after pre-baking. Next, the wafers were heated on a hot plate at 100°C for 2 minutes (pre-baking). Then, an i-line stepper exposure system FPA-3000i5+ (Canon Corporation) was used to expose the wafers at 1000 mJ / cm². 2 The wafer was exposed to a 1 μm square Bayer pattern mask at the specified exposure level. Next, paddle development was performed at 23°C for 60 seconds using a 0.3 mass% aqueous solution of tetramethylammonium hydroxide (TMAH). After that, rinsing was performed with a spin shower and then washed with pure water to form the pattern. The silicon wafer on which the above pattern was formed was divided, platinum deposition was performed, and cross-sectional scanning electron microscope (SEM) images of the pattern were obtained using a scanning electron microscope (Hitachi High-Tech Corporation). Five patterns were extracted from the obtained cross-sectional SEM images, and the average slope of the cross-sections of the five patterns was calculated and evaluated according to the following criteria. The inclination of the pattern's cross-section was measured by determining the inclination in the thickness direction of the cured film on the silicon wafer in the area where the pattern was formed. Specifically, the angle of the portion formed by the silicon wafer and the edge of the cured film in the thickness direction was measured. If the inclination of the pattern is less than 90 degrees with respect to the silicon wafer, it means that the cured film tapers from the silicon wafer side towards the surface side of the cured film. 5: The average slope of the 5 patterns is between 80 and 100 degrees relative to the silicon wafer. 4: The average slope of the 5 patterns is between 70 and 80 degrees relative to the silicon wafer. 3: The average slope of the 5 patterns is between 60 and 70 degrees relative to the silicon wafer. 2: The average slope of the 5 patterns is between 50 and 60 degrees relative to the silicon wafer. 1: The average slope of the 5 patterns is less than 50 degrees or greater than 100 degrees relative to the silicon wafer.

[0273] [Table 17] [Table 18] [Table 19] [Table 20]

[0274] As shown in the table above, the curable compositions of the examples were able to form cured films with excellent solvent resistance. In contrast, Comparative Examples 1 and 2, which contained only one of either photopolymerization initiator IA or photopolymerization initiator IB, showed inferior solvent resistance compared to the examples.

[0275] Even if a curable composition is manufactured in the same manner as in Example 9, except that infrared absorber A9 is replaced with infrared absorbers A19 to A32 shown below, and each property is evaluated in the same manner as above, the same performance (spectral characteristics, solvent resistance) as in Example 9 can be obtained. In particular, infrared absorbers A19 to A32 have high visible light transmittance, and the curable composition using these infrared absorbers has a maximum absorbance A in the wavelength range of 700 to 2000 nm. 1 And the maximum absorbance A in the wavelength range of 400-600 nm. 2 Ratio (absorbance ratio A) 1 / A 2 ) can form a larger cured film.

[0276] Infrared absorbers A19-A32: Compounds with the following structure [ka] [ka] [ka] [Explanation of symbols]

[0277] 110: Solid-state image sensor, 111: Near-infrared cut filter, 112: Color filter, 114: Infrared transmission filter, 115: Microlens, 116: Planarization layer

Claims

1. A curable composition containing an infrared absorber, a polymerizable monomer, and a photopolymerization initiator, The content of the infrared absorber in the total solid content of the curable composition is 10 to 25% by mass. The aforementioned photopolymerization initiator has an absorption coefficient of 1.0 × 10⁻¹⁰ at a wavelength of 365 nm in methanol. ３ A photopolymerization initiator IA with a concentration of mL / g·cm or higher, and an extinction coefficient of 1.0 × 10⁻¹⁰ at a wavelength of 365 nm in methanol. ３ The concentration is less than mL / g·cm, and the extinction coefficient at a wavelength of 254 nm is 1.0 × 10⁻⁶. ３ It contains a photopolymerization initiator IB in a concentration of mL / g·cm or more, Maximum absorbance A of the curable composition in the wavelength range of 700 to 2000 nm １ And the maximum absorbance A in the wavelength range of 400-600 nm. ２ A is the ratio of １ / A ２ A curable composition having a value of 4.5 or higher.

2. The curable composition according to claim 1, wherein the photopolymerization initiator IA is an oxime compound.

3. The curable composition according to claim 1 or 2, wherein the photopolymerization initiator IB is a hydroxyalkylphenone compound.

4. The curable composition according to claim 1 or 2, wherein the total content of the photopolymerization initiator IA and the photopolymerization initiator IB in the total solid content of the curable composition is 1 to 6% by mass.

5. The curable composition according to claim 1 or 2, wherein the content of the photopolymerization initiator IB is 5 to 200 parts by mass per 100 parts by mass of the photopolymerization initiator IA.

6. The curable composition according to claim 1 or 2, wherein the content of the colorant in the total solid content of the curable composition is 0.1% by mass or less.

7. The curable composition according to claim 1 or 2, wherein the content of the polymerizable monomer in the total solid content of the curable composition is 10 to 50% by mass.

8. Furthermore, the curable composition according to claim 1 or 2, further comprising a resin.

9. The curable composition according to claim 8, wherein the content of the resin is 10 to 500 parts by mass per 100 parts by mass of the polymerizable monomer.

10. Furthermore, the curable composition according to claim 1 or 2, comprising an ultraviolet absorber, wherein the amount of the ultraviolet absorber is 10 to 500 parts by mass per 100 parts by mass of the photopolymerization initiator IA.

11. The maximum absorbance value A of the curable composition in the wavelength range of 700 to 2000 nm １ and the absorbance A at a wavelength of 365 nm ３ , which is the ratio of A １ / A ３ is 1 or more and less than 9. The curable composition according to claim 1 or 2.

12. A curable composition according to claim 1 or 2, for use in near-infrared cut filters.

13. A cured film obtained by curing the curable composition according to claim 1 or 2.

14. A step of forming a curable composition layer on a support using the curable composition according to claim 1 or 2, A first exposure step involves irradiating the curable composition layer with light having a wavelength greater than 350 nm and less than or equal to 380 nm to expose it in a patterned manner. A developing step for developing the curable composition layer, A method for forming a pattern, comprising: a second exposure step of irradiating the curable composition layer with light having a wavelength of 254 nm to 350 nm after the development step.

15. The method for forming a pattern according to claim 14, further comprising the step of heating the curable composition layer at a temperature of less than 200°C in a low-oxygen atmosphere during at least one of the periods between the developing step and the second exposure step, and after the second exposure step.

16. A near-infrared cut filter having a cured film as described in claim 13.

17. A solid-state image sensor having the cured film described in claim 13.

18. An image display device having a cured film according to claim 13.

19. An infrared sensor having a cured film according to claim 13.

Images