Curable composition, cured product, color filter, method for producing color filter, solid imaging element, and image display device

Abstract

To provide a curable composition having superior depth curability.SOLUTION: Provided are a curable composition including a pigment, a resin having a structural unit represented by Formula 1, and a photopolymerization initiator; as well as a cured product obtained by curing the curable composition, a color filter including the cured product, a method for producing the color filter, or a solid-state imaging element or an image display device, each of which includes the color filter. R1 to R3 each independently represent a hydrogen atom or an alkyl group, X1 represents -COO-, -CONR-, or an arylene group, R4 represents a divalent linking group, L1 represents a group resulting from a reaction between an isocyanate or epoxy group and a hydroxy group, R5 represents a (n+1)-valent linking group, X2 represents an oxygen atom or -NRA-, RA represents a hydrogen atom, an alkyl group, or an aryl group, and n represents an integer of 1 or more.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present disclosure relates to a curable composition, a cured product, a color filter, a method for producing a color filter, a solid-state imaging device, and an image display device. [Background technology]

[0002] Components such as color filters are produced by adding a polyfunctional monomer, a photopolymerization initiator, an alkali-soluble resin and other components to a pigment dispersion composition in which an organic pigment or an inorganic pigment is dispersed, to form a colored photosensitive composition, and using this composition by a photolithography method or the like.

[0003] Examples of compositions used in the formation of conventional color filters include those described in Patent Documents 1 to 4.

[0004] Patent Document 1 describes a photosensitive composition comprising (A) a photopolymerization initiator and (B) a binder resin having a structure in which an epoxy moiety of a compound having an ethylenically unsaturated group and an epoxy group is added to a carboxylic acid moiety of a resin having a carboxylic acid, wherein the compound having an ethylenically unsaturated group and an epoxy group is represented by the following structural formula I.

[0005] [ka] (In structural formula I, R1 represents a divalent linking group, and R2 represents hydrogen or a methyl group.)

[0006] Patent Document 2 discloses a photopolymerizable composition containing a binder resin having a carboxyl group and / or a hydroxyl group, a photopolymerizable monomer, and a photopolymerization initiator, in which the binder resin is represented by the following formula (I):

[0007] [ka]

[0008] (R1 represents hydrogen or an alkyl group having 1 to 6 carbon atoms, and R2 represents a divalent linking group), and (1) the carbonyl group contained in the binder resin is a copolymer having a repeating unit represented by the formula: (2) a part of the carboxyl groups of the binder resin forms a -COO-Y1-R6 structure (wherein Y1 is a divalent linking group and R6 is a group having an ethylenically unsaturated group), or (3) at least a part of the hydroxyl groups of the binder resin forms a -O-Y2-R6 structure. 13 (wherein Y2 is a divalent linking group, R 13 represents a group having an ethylenically unsaturated group.) structure is formed.

[0009] Patent Document 3 describes a colored photosensitive resin composition containing a binder resin (A), a photopolymerizable monomer (B), a photopolymerization initiator (C), a coloring material (D) and a solvent (E), characterized in that the binder resin (A) is an unsaturated group-containing binder resin obtained by reacting a polymer containing a structural unit derived from an unsaturated carboxylic acid with a compound of formula (1), and the photopolymerization initiator (C) contains at least one compound selected from the group consisting of triazine compounds, acetophenone compounds and biimidazole compounds.

[0010] [ka] (In the formula, R 1 represents a hydrogen atom or a methyl group, and R 2 represents an aliphatic hydrocarbon residue having 1 to 6 carbon atoms.

[0011] Patent Document 4 describes a photosensitive composition containing a photosensitive resin obtained by reacting 0.2 to 0.9 mol of epoxy groups in an epoxy group-containing ethylenically unsaturated monomer (c) with 1 mol of carboxyl groups in a copolymer (I) obtained by radical polymerization of an ethylenically unsaturated monomer (M) containing 10 to 90% by weight of an ethylenically unsaturated monomer (a) having no carboxyl group and a formula weight of 70 to 120 and 10 to 70% by weight of a carboxyl group-containing ethylenically unsaturated monomer (b).

[0012] Patent Document 1: Japanese Patent Application Laid-Open No. 2003-233179 Patent Document 2: Japanese Patent Application Laid-Open No. 2000-227655 Patent Document 3: JP 2004-138950 A Patent Document 4: JP 2014-81639 A Summary of the Invention [Problem to be solved by the invention]

[0013] An object of the present invention is to provide a curable composition that is excellent in deep section curing ability. Another problem to be solved by another embodiment of the present invention is to provide a cured product obtained by curing the curable composition, a color filter including the cured product, a method for producing the color filter, or a solid-state imaging element or an image display device including the color filter. [Means for solving the problem]

[0014] Means for solving the above problems include the following aspects. <1> A hardener comprising a pigment, a resin having a constitutional unit represented by the following formula 1, and a photopolymerization initiator. chemical composition.

[0015] [ka]

[0016] In formula 1, R 1 ~R3 each independently represents a hydrogen atom or an alkyl group; X 1 represents -COO-, -CONR- or an arylene group, R represents a hydrogen atom, an alkyl group or an aryl group, R 4 represents a divalent linking group; L 1 represents a group represented by the following formula 2 or 3, R 5 represents a (n+1)-valent linking group, X 2 is an oxygen atom or -NR A - represents R A represents a hydrogen atom, an alkyl group or an aryl group, and n represents an integer of 1 or more.

[0017] [ka]

[0018] In formula 2 and formula 3, X 3 represents an oxygen atom or -NH-; X 4 represents an oxygen atom or -COO-; R e1 ~R e3 each independently represents a hydrogen atom or an alkyl group; R e1 ~R e3 At least two of the may be bonded to form a ring structure, and * indicates the position of bonding to another structure.

[0019] <2> The resin further has a constitutional unit represented by the following formula 4: <1> The curable composition according to claim 1.

[0020] [ka]

[0021] In formula 4, R 6 represents a hydrogen atom or an alkyl group; X 5 -COO-, -CONR B - or an arylene group; R B represents a hydrogen atom, an alkyl group, or an aryl group; L 2represents an aliphatic hydrocarbon group having 1 to 10 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms, or a group in which two or more groups selected from the group consisting of an aliphatic hydrocarbon group having 1 to 10 carbon atoms and an aromatic hydrocarbon group having 6 to 20 carbon atoms are bonded to one or more structures selected from the group consisting of an ether bond and an ester bond; 2 X 5 When is an arylene group, it may be a single bond.

[0022] <3> The resin further has a constitutional unit represented by the following formula 5: <1> or <2> The curable composition according to claim 1.

[0023] [ka]

[0024] In formula 5, R 7 represents a hydrogen atom or an alkyl group; X 6 is an oxygen atom or -NR C - represents R C represents a hydrogen atom, an alkyl group, or an aryl group; L 3 represents a divalent linking group; Y 1 and Y 2 each independently represents an alkyleneoxy group or an alkylenecarbonyloxy group; Z 1 represents an aliphatic hydrocarbon group having 1 to 20 carbon atoms or an aromatic hydrocarbon group having 6 to 20 carbon atoms; p and q each independently represent an integer of 0 or greater, and the value of p+q is 1 or greater.

[0025] <4> The ethylenically unsaturated bond value of the resin is 0.1 mmol / g to 2.0 mmol / g. <1> ~ <3> 13. The curable composition according to claim 12, <5> Further contains a polymerization inhibitor <1> ~ <4> 13. The curable composition according to claim 12, <6> The polymerization inhibitor contains a compound having an N-oxyl radical structure. <5> The curable composition according to claim 1. <7> The above L 1is a group represented by the above formula 2 <1> ~ <6> 13. The curable composition according to claim 12, <8> Above X 3 is an oxygen atom <7> The curable composition according to claim 1. <9> Above R 4 is a group selected from the group consisting of an ethylene group, an n-propylene group, an isopropylene group, an n-butylene group, and an isobutylene group, and 5 is an ethylene group <7> or <8> The curable composition according to claim 1. <10> The above L 1 is a group represented by the above formula 3 <1> ~ <6> 13. The curable composition according to claim 12, <11> Above X 4 is -COO- <10> The curable composition according to claim 1. <12> Above R 4 is a hydrocarbon group, a group in which two or more hydrocarbon groups are bonded to one or more structures selected from the group consisting of an ether bond and an ester bond, or a group selected from the group consisting of any of the groups represented by the following structures, and 5 is an alkylene group or a group in which two or more alkylene groups are bonded to one or more structures selected from the group consisting of an ether bond and an ester bond. <10> or <11> The curable composition according to claim 1.

[0026] [ka]

[0027] In addition, * indicates the bonding position with other structures.

[0028] <13> The photopolymerization initiator is a compound having an oxime structure. <1> ~ <12> 13. The curable composition according to claim 12, <14> A curable composition for forming a colored layer of a color filter. <1> ~ <13> 13. The curable composition according to claim 12, <15> <1> ~ <14> 2. A cured product obtained by curing the curable composition according to claim 1. <16> <15> A color filter comprising the cured product according to claim 1. <17> <1> ~ <14> 1. A method for producing a color filter, comprising the steps of: applying the curable composition according to any one of claims 1 to 9 on a support to form a composition film; exposing the formed composition film to light in a pattern; and developing the exposed composition film to form a colored pattern. <18> <1> ~ <14> a step of applying the curable composition according to any one of the above items onto a support and curing the composition to form a cured product; a step of forming a photoresist layer on the cured product; a step of exposing the photoresist layer in a pattern and developing it to form a resist pattern; and a step of etching the cured product through the resist pattern. <19> <16> A solid-state imaging device having the color filter according to claim 1. <20> <16> An image display device comprising the color filter according to claim 1. Effect of the Invention

[0029] According to an embodiment of the present invention, it is possible to provide a curable composition having excellent deep curing properties. According to another embodiment of the present invention, there can be provided a cured product obtained by curing the curable composition, a color filter including the cured product, a method for producing the color filter, or a solid-state imaging element or an image display device including the color filter. [Brief description of the drawings]

[0030] [Figure 1] FIG. 2 is a schematic diagram showing measurement positions of an undercut width in a cured product on a pattern in the Examples. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0031] The contents of the present disclosure will be described in detail below. The following description of the configuration elements may be based on a representative embodiment of the present disclosure, but the present disclosure is not limited to such an embodiment. The present invention is not limited to the embodiment. In the present disclosure, the use of "to" indicating a numerical range means that the numerical values ​​before and after it are included as the lower limit and upper limit. In the present specification, the upper or lower limit of one numerical range may be replaced with the upper or lower limit of another numerical range. In addition, in the present specification, the upper or lower limit of the numerical range may be replaced with a value shown in the examples. In addition, in the description of groups (atomic groups) in the present disclosure, descriptions that do not indicate whether they are substituted or unsubstituted include those that have no substituents as well as those that have a substituent. For example, an "alkyl group" includes not only an alkyl group that has no substituents (unsubstituted alkyl groups) but also an alkyl group that has a substituent (substituted alkyl groups). In this disclosure, unless otherwise specified, "Me" represents a methyl group, "Et" represents an ethyl group, "Pr" represents a propyl group, "Bu" represents a butyl group, and "Ph" represents a phenyl group. In this specification, "(meth)acrylic" is a term used as a concept including both acrylic and methacrylic, and "(meth)acryloyl" is a term used as a concept including both acryloyl and methacryloyl. In addition, in the present disclosure, the term "process" refers not only to an independent process, but also to a process that cannot be clearly distinguished from other processes, as long as the intended purpose of the process is achieved. In the present disclosure, "mass %" and "weight %" are synonymous, and "parts by mass" and "parts by weight" are synonymous. Furthermore, in the present disclosure, combinations of two or more preferred embodiments are more preferred embodiments. In addition, unless otherwise specified, the weight average molecular weight (Mw) and number average molecular weight (Mn) in the present disclosure are molecular weights detected by a gel permeation chromatography (GPC) analyzer using columns of TSKgel GMHxL, TSKgel G4000HxL, or TSKgel G2000HxL (all product names manufactured by Tosoh Corporation) in a solvent of THF (tetrahydrofuran) and a differential refractometer, and converted using polystyrene as a standard substance. The present disclosure will be described in detail below.

[0032] (Curable composition) The curable composition (hereinafter also referred to as "composition") according to the present disclosure contains a pigment, a resin having a constitutional unit represented by the following formula 1, and a photopolymerization initiator. Moreover, the curable composition according to the present disclosure can be suitably used as a curable composition for forming a colored layer of a color filter.

[0033] [ka]

[0034] In formula 1, R 1 ~R 3 each independently represents a hydrogen atom or an alkyl group; X 1 represents -COO-, -CONR- or an arylene group, R represents a hydrogen atom, an alkyl group or an aryl group, R 4 represents a divalent linking group; L 1 represents a group represented by the following formula 2 or 3, R 5 represents a (n+1)-valent linking group, X 2 is an oxygen atom or -NR A - represents R A represents a hydrogen atom, an alkyl group or an aryl group, and n represents an integer of 1 or more.

[0035] [ka]

[0036] In formula 2 and formula 3, X3 represents an oxygen atom or -NH-; X 4 represents an oxygen atom or -COO-; R e1 ~R e3 each independently represents a hydrogen atom or an alkyl group; R e1 ~R e3 At least two of the may be bonded to form a ring structure, and * indicates the position of bonding to another structure.

[0037] By using the curable composition according to the present disclosure, a cured product having excellent deep curing properties can be obtained. The reason why the above effect is obtained is unclear, but is presumed to be as follows. By having a polar group represented by formula 2 or 3 in the side chain of the resin having the structural unit represented by formula 1, the range of movement of the acrylic group in the composition is increased, resulting in excellent reactivity. In addition, by having the group represented by formula 2 or 3, aggregation of resins is suppressed, resulting in excellent dispersibility, and the acrylic group becomes more likely to react, thereby providing a curable composition with excellent depth curing. Furthermore, by having a structural unit represented by formula 1, a highly reactive acrylic group can be introduced into a position away from the main chain via a group represented by formula 2 or formula 3. This increases the probability that the acrylic groups in the polymer molecules will react with each other, but will not react with each other, and will instead react between polymer molecules or with other crosslinking components in the composition. This allows the crosslinking reaction to proceed efficiently even in a composition with a high pigment concentration, improving deep section curing properties and pattern shape. In addition, the structural unit represented by formula 1 has a relatively long side chain structure and has a polar group represented by formula 2 or formula 3 in the side chain, thereby exhibiting steric repulsion that enhances the adsorption to the pigment and suppresses the aggregation of pigment particles, thereby improving dispersibility. Furthermore, by having the structural unit represented by the above formula 4, a carboxylic acid that serves as an adsorptive group can be introduced into a position away from the main chain, thereby increasing pigment adsorptivity and improving dispersion stability. In addition, by introducing the structural unit represented by formula 1, the substrate adhesion and pattern shape can be improved due to excellent depth curing properties, and further, by having the structural unit represented by formula 4 above, the dispersion stability can be improved.

[0038] <Resin Having a Constitutional Unit Represented by Formula 1> The curable composition according to the present disclosure contains a resin having a constitutional unit represented by formula 1 above. R in Equation 1 1 ~R 3 are each independently preferably a hydrogen atom or a methyl group, and particularly preferably a hydrogen atom, from the viewpoint of deep section curing. In addition, from the viewpoint of deep curing, R 1 is a hydrogen atom or a methyl group, and R 2 and R 3 More preferably, L is a hydrogen atom. 1 is a group represented by formula 2, R 1 More preferably, L is a methyl group. 1 is a group represented by formula 3, R 1 is more preferably a hydrogen atom. X in Equation 1 1 From the viewpoint of deep section curing, is preferably -COO- or -CONR-, and more preferably -COO-. R is preferably a hydrogen atom or an alkyl group, and more preferably a hydrogen atom. R in Equation 1 4 is preferably a hydrocarbon group or a group in which two or more hydrocarbon groups are bonded to one or more structures selected from the group consisting of an ether bond and an ester bond, and more preferably a hydrocarbon group or a group in which two or more hydrocarbon groups are bonded to one or more ester bonds, from the viewpoint of deep section curability. In addition, R in Equation 1 4 From the viewpoint of deep section curing, preferably a group having a total of 2 to 60 atoms, more preferably a group having a total of 2 to 50 atoms, and particularly preferably a group having a total of 2 to 40 atoms. Furthermore, from the viewpoint of deep hardening, R4 is a group selected from the group consisting of a hydrocarbon group, an alkyleneoxyalkylenecarboxyl group, and any group represented by the following structure, and the above R 5 is particularly preferably an alkylene group or a group in which two or more alkylene groups are bonded to one or more structures selected from the group consisting of an ether bond and an ester bond.

[0039] [ka]

[0040] In addition, * indicates the bonding position with other structures.

[0041] In formula 1, n is preferably an integer of 1 to 6, more preferably an integer of 1 to 3, and particularly preferably 1, from the viewpoint of deep section curability. R in Equation 1 5 From the viewpoint of deep section curing, is preferably a divalent linking group, more preferably an alkylene group or a group in which two or more alkylene groups are bonded to one or more structures selected from the group consisting of ether bonds and ester bonds, further preferably an alkyleneoxyalkylene group, and particularly preferably a methyleneoxy-n-butylene group. In addition, R in Equation 1 5 From the viewpoint of deep section curing, preferably a group having a total of 2 to 40 atoms, more preferably a group having a total of 2 to 30 atoms, and particularly preferably a group having a total of 2 to 20 atoms. X in Equation 1 2 From the viewpoint of deep curing, is preferably an oxygen atom. R A is preferably a hydrogen atom or an alkyl group, and more preferably a hydrogen atom.

[0042] L in Equation 1 1 From the viewpoint of dispersibility, it is preferably a group represented by the above formula 2, and from the viewpoints of pattern shape and suppression of development residues, it is preferably a group represented by the above formula 3. I wish. X in Equation 2 3 is preferably an oxygen atom from the viewpoints of deep curing and dispersibility. Also, L 1 is a group represented by formula 2, from the viewpoints of deep curing property and dispersibility, R 4 is a group selected from the group consisting of an ethylene group, an n-propylene group, an isopropylene group, an n-butylene group, and an isobutylene group, and R 5 However, an ethylene group is particularly preferred. X in Equation 3 4 is preferably -COO- from the viewpoints of deep curing, pattern shape, and suppression of development residues. R in Equation 3 e1 ~R e3 is preferably a hydrogen atom from the viewpoints of deep curing properties, pattern shape, and suppression of development residues. Also, L 1 When R is a group represented by formula 3, from the viewpoints of deep curing, pattern shape, and suppression of development residues, 4 is a hydrocarbon group, a group in which two or more hydrocarbon groups are bonded to one or more structures selected from the group consisting of an ether bond and an ester bond, or any group represented by the following structure, and R 5 is particularly preferably an alkylene group or a group in which two or more alkylene groups are bonded to one or more structures selected from the group consisting of an ether bond and an ester bond.

[0043] Preferred examples of the group represented by formula 2 include groups represented by the following formula 2-1 or 2-2. Preferred examples of the group represented by formula 3 include groups represented by the following formula 3-1 or 3-2.

[0044] [ka]

[0045] In addition, * indicates the bonding position with other structures.

[0046] Preferred examples of the constitutional unit represented by formula 1 include the structures shown below, but it goes without saying that the constitutional unit is not limited to these.

[0047] [ka]

[0048] [ka]

[0049] Here, m represents an integer of 2 or more, and n represents an integer of 1 or more.

[0050] The above resin may have one type of constitutional unit represented by formula 1 alone, or may have two or more types. From the viewpoints of developability, pattern shape, dispersion stability, and deep curing ability, the content of the structural unit represented by formula 1 is preferably 1 mass % to 80 mass %, more preferably 1 mass % to 70 mass %, and particularly preferably 1 mass % to 60 mass %, relative to the total mass of the resin.

[0051] -Constituent unit represented by formula 4- From the viewpoints of dispersion stability and developability, the above resin preferably further contains a constitutional unit represented by the following formula 4.

[0052] [ka]

[0053] In formula 4, R 6 represents a hydrogen atom or an alkyl group; X 5 -COO-, -CONR B - or an arylene group; R B represents a hydrogen atom, an alkyl group, or an aryl group; L 2 is an aliphatic hydrocarbon group having 1 to 10 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms, or represents a group formed by bonding two or more groups selected from the group consisting of an aliphatic hydrocarbon group having 1 to 10 carbon atoms and an aromatic hydrocarbon group having 6 to 20 carbon atoms to one or more structures selected from the group consisting of an ether bond and an ester bond, and further, L 2 X 5 When is an arylene group, it may be a single bond.

[0054] R in Equation 4 6 is preferably a hydrogen atom. X in Equation 4 5 From the viewpoint of dispersion stability, -COO- or -CONR B is preferable, and -COO- is more preferable. R B is preferably a hydrogen atom or an alkyl group, and more preferably a hydrogen atom. L in Equation 4 2 From the viewpoint of dispersion stability, is preferably an aliphatic hydrocarbon group having 1 to 10 carbon atoms or a group in which two or more aliphatic hydrocarbon groups having 1 to 10 carbon atoms are bonded to one or more ester bonds, is more preferably an aliphatic hydrocarbon group having 1 to 10 carbon atoms, and is particularly preferably an alkylene group having 1 to 10 carbon atoms.

[0055] Preferred examples of the constitutional unit represented by formula 4 include the structures shown below, but it goes without saying that the constitutional unit is not limited to these.

[0056] [ka]

[0057] Here, n represents an integer of 1 or more.

[0058] The above resin may have one type of constitutional unit represented by formula 4 alone, or may have two or more types. From the viewpoints of developability, pattern shape, and dispersion stability, the content of the structural unit represented by formula 4 is preferably 20% by mass to 80% by mass, more preferably 20% by mass to 70% by mass, and particularly preferably 20% by mass to 60% by mass, relative to the total mass of the resin.

[0059] -Structural unit represented by formula 5- From the viewpoint of dispersion stability, the above resin preferably further has a constitutional unit represented by the following formula 5, and from the viewpoints of dispersion stability and developability, it is more preferable that the resin further has a constitutional unit represented by the above formula 4 and a constitutional unit represented by the following formula 5.

[0060] [ka]

[0061] In formula 5, R 7 represents a hydrogen atom or an alkyl group; X 6 is an oxygen atom or -NR C - represents R C represents a hydrogen atom, an alkyl group, or an aryl group; L 3 represents a divalent linking group; Y 1 and Y 2 each independently represents an alkyleneoxy group or an alkylenecarbonyloxy group; Z 1 represents an aliphatic hydrocarbon group having 1 to 20 carbon atoms or an aromatic hydrocarbon group having 6 to 20 carbon atoms; p and q each independently represent an integer of 0 or greater, and the value of p+q is 1 or greater.

[0062] R in Equation 5 7 is preferably a hydrogen atom or a methyl group, and more preferably a methyl group. X in Equation 5 6 is preferably an oxygen atom from the viewpoint of dispersion stability. R C is preferably a hydrogen atom or an alkyl group, and more preferably a hydrogen atom. L in Equation 5 3From the viewpoint of dispersion stability, is preferably a group having a total of 2 to 30 atoms, more preferably a group having a total of 3 to 20 atoms, and particularly preferably a group having a total of 4 to 10 atoms. Also, L in Equation 5 3 From the viewpoint of dispersion stability, is preferably a group having a urethane bond or a urea bond, more preferably a group having a urethane bond, and particularly preferably a group in which an alkylene group is bonded to a urethane bond.

[0063] Y in Equation 5 1 and Y 2 are each independently preferably an alkylenecarbonyloxy group from the viewpoint of dispersion stability, and Y 1 and Y 2 More preferably, are different alkylenecarbonyloxy groups. The alkylenecarbonyloxy group preferably has 2 to 30 carbon atoms, more preferably 3 to 10 carbon atoms, and particularly preferably 5 to 8 carbon atoms, from the viewpoint of dispersion stability. From the viewpoint of dispersion stability, it is preferable that p is an integer of 1 or more and q is an integer of 0 or more, it is more preferable that p is an integer of 1 or more and q is an integer of 1 or more, and it is particularly preferable that p is an integer of 3 or more and q is an integer of 3 or more. Furthermore, p and q are each independently preferably 50 or less, more preferably 30 or less, and particularly preferably 20 or less. Z in Equation 5 1 From the viewpoint of dispersion stability, is preferably an aliphatic hydrocarbon group having 1 to 20 carbon atoms, more preferably an alkyl group having 4 to 20 carbon atoms, and particularly preferably an alkyl group having 6 to 20 carbon atoms. Also, Z 1 In terms of dispersion stability, the alkyl group in the formula (I) is a branched alkyl group. It is preferable.

[0064] Preferred examples of the constitutional unit represented by formula 5 include the structures shown below, but it goes without saying that the constitutional unit is not limited to these.

[0065] [ka]

[0066] Here, n represents an integer of 1 or more, and a and b each independently represent an integer of 1 or more.

[0067] The above resin may have one type of constitutional unit represented by formula 5 alone, or may have two or more types. From the viewpoints of developability and dispersion stability, the content of the structural unit represented by formula 5 is preferably 5% by mass to 80% by mass, more preferably 5% by mass to 70% by mass, and particularly preferably 5% by mass to 60% by mass, relative to the total mass of the resin.

[0068] -Other building blocks- The above resin may have other structural units than the structural units represented by formula 1, formula 4 or formula 5 above. The other structural units are not particularly limited, and may include known structural units.

[0069] The weight average molecular weight (Mw) of the resin is preferably 1,000 or more, more preferably 1,000 to 200,000, and particularly preferably 1,000 to 100,000.

[0070] From the viewpoints of deep curing ability, pattern shape, and substrate adhesion, the ethylenically unsaturated bond valence of the resin is preferably 0.01 mmol / g to 2.5 mmol / g, more preferably 0.05 mmol / g to 2.3 mmol / g, even more preferably 0.1 mmol / g to 2.2 mmol / g, and particularly preferably 0.1 mmol / g to 2.0 mmol / g. The ethylenically unsaturated bond value of a resin represents the molar amount of ethylenically unsaturated groups per 1 g of solid content of the resin. A low molecular weight component (a) of an ethylenically unsaturated group site (e.g., acrylic acid when the structural unit of the resin represented by formula 1 has an acryloxy group) is extracted from the resin by alkali treatment, and its content is measured by high performance liquid chromatography (HPLC). Based on the measured value, the ethylenically unsaturated bond value is calculated according to the following formula: Specifically, 0.1 g of the measurement sample was dissolved in a tetrahydrofuran / methanol mixed solution (50 mL / 15 mL), 10 mL of 4 mol / L sodium hydroxide aqueous solution was added, and the mixture was reacted at 40° C. for 2 hours. The reaction solution was neutralized with 10.2 mL of 4 mol / L methanesulfonic acid aqueous solution, and then the mixture was transferred to a 100 mL measuring flask and filled up with methanol to prepare an HPLC measurement sample, which was measured under the following conditions. The content of the low molecular weight component (a) was calculated from a separately prepared calibration curve of the low molecular weight component (a), and the ethylenically unsaturated bond value was calculated from the following formula. -Calculation formula for ethylenically unsaturated bond value- Ethylenically unsaturated bond value [mmol / g] = (Low molecular weight component (a) content [ppm] / Molecular weight of low molecular weight component (a) [g / mol]) / (Weight value of prepared polymer solution [g] × (Solid content concentration of polymer solution [%] / 100) × 10) -HPLC measurement conditions- Measurement equipment: Agilent-1200 (Agilent Technologies, Inc.) Column: Phenomenex Synergi 4u Polar-RP 80A, 250mm x 4.60mm (inner diameter) + guard column Column temperature: 40℃ Analysis time: 15 minutes Flow rate: 1.0mL / min (Max. liquid pressure: 182bar) Injection volume: 5μl Detection wavelength: 210nm Eluent: Tetrahydrofuran (for HPLC without stabilizers) / buffer solution (ion exchange aqueous solution containing 0.2 vol% phosphoric acid and 0.2 vol% triethylamine) = 55 / 45 (vol%)

[0071] Specific examples of the resin include those prepared in the examples described below.

[0072] The curable composition may contain only one type of the resin, or two or more types of the resin. From the viewpoints of deep curability and dispersion stability, the content of the resin is preferably 10% by mass to 45% by mass, more preferably 12% by mass to 40% by mass, and particularly preferably 14% by mass to 35% by mass, based on the total solid content of the curable composition. In this specification, the total solid content refers to the total amount of all components of the composition excluding the solvent. In addition, from the viewpoints of deep curing and dispersion stability, the content of the above resin is preferably 20 parts by mass to 60 parts by mass, more preferably 22 parts by mass to 55 parts by mass, and particularly preferably 24 parts by mass to 50 parts by mass, relative to 100 parts by mass of the pigment content.

[0073] The method for synthesizing a resin having a constitutional unit represented by formula 1 is not particularly limited, and the resin can be synthesized by a known method or by application of a known method. For example, a method can be mentioned in which a precursor of the above resin is synthesized by a known method, and then a group having an acrylic group is introduced by a polymer reaction into the structural unit represented by the above formula 1. Examples of the polymer reaction include a reaction between a carboxy group of the precursor of the above resin and a compound having an epoxy group and an acrylic group, and a reaction between a hydroxy group of the precursor of the above resin and a compound having an isocyanato group and an acrylic group.

[0074] Furthermore, the resin is composed of different repeating units, such as a repeating unit responsible for developability, a repeating unit responsible for dispersibility, and a repeating unit responsible for curing property, and in order to effectively exert the different functions, it is preferable that the composition of the resin is uniform. As a method for homogenizing the composition of the resin, for example, a method of dropping monomers into the reaction system so as to match the consumption rates of different monomer species can be mentioned. In general, the reaction rates can be matched by increasing the initial concentration of a monomer species with a slow consumption rate in the reaction system and dropping a monomer species with a fast consumption rate to create a concentration difference in the reaction system.

[0075] <Pigments> The curable composition according to the present disclosure includes a pigment. The pigment may be an inorganic pigment or an organic pigment. Examples of inorganic pigments include black pigments such as carbon black and titanium black, and oxides and metal complexes of metals such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, and antimony. Examples of organic or inorganic pigments include the following.

[0076] Color Index (CI) Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35:1, 36, 36:1, 37, 37:1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116 ,117,118,119,120,123,125,126,127,128,129,137,138,139,147,148,150,151,152,153,154,155,156,161,162,164,166,167,168,169,170,171,172,173,174,175,176,177,179,180,181,182,185,187,188,193,194,199,213,214 (all yellow pigments); CI Pigment Orange 2, 5, 13, 16, 17: 1, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 71, 73 (orange pigments); CI Pigment Red 1,2,3,4,5,6,7,9,10,14,17,22,23,31,38,41,48:1,48:2,48:3,48:4,49,49:1,49:2,52:1,52:2,53:1,57:1,60:1,63:1,66,67,81:1,81:2,81:3,83,88,90,105,112,119,122,123,144,146, 149, 150, 155, 166, 168, 169, 170, 171, 172, 175, 176, 177, 178, 179, 184, 185, 187, 188, 190, 200, 202, 206, 207, 208, 209, 210, 216, 220, 224, 226, 242, 246, 254, 255, 264, 270, 272, 279 (all red pigments); CI Pigment Green 7, 10, 36, 37, 58, 59 (all green pigments); CI Pigment Violet 1, 19, 23, 27, 32, 37, 42, 58, 59 (all purple pigments); CI Pigment Blue 1, 2, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 22, 60, 64, 66, 79, 80 (all blue pigments).

[0077] In addition, as the green pigment, it is also possible to use a halogenated zinc phthalocyanine pigment having an average of 10 to 14 halogen atoms in the molecule, an average of 8 to 12 bromine atoms, and an average of 2 to 5 chlorine atoms. Specific examples include the compounds described in WO 2015 / 118720.

[0078] In addition, an aluminum phthalocyanine compound having a phosphorus atom can also be used as a blue pigment. No. 030, and the compounds described in paragraph 0047 of JP-A No. 2011-157478.

[0079] -Pigment derivatives- The curable composition according to the present disclosure may further comprise a pigment derivative. Examples of the pigment derivative include compounds having a structure in which a part of an organic pigment is replaced with an acidic group, a basic group, or a phthalimidomethyl group. Examples of organic pigments for constituting the pigment derivative include diketopyrrolopyrrole pigments, azo pigments, phthalocyanine pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, perinone pigments, perylene pigments, thioindigo pigments, isoindoline pigments, isoindolinone pigments, quinophthalone pigments, threne pigments, and metal complex pigments. In addition, the acidic group of the pigment derivative is preferably a sulfonic acid group, a carboxylic acid group, and a quaternary ammonium salt thereof, more preferably a carboxylic acid group and a sulfonic acid group, and particularly preferably a sulfonic acid group. The basic group of the pigment derivative is preferably an amino group, and particularly preferably a tertiary amino group. Specific examples of the pigment derivative include the following compounds. Also, the disclosure of paragraphs 0162 to 0183 of JP 2011-252065 A may be referred to, the contents of which are incorporated herein by reference.

[0080] [ka]

[0081] As the pigment, an infrared absorbing pigment can be suitably used. The infrared absorbing pigment is not particularly limited, and a known infrared absorbing pigment can be used. For example, a diiminium compound, a squarylium compound, a cyanine compound, a phthalocyanine compound, a naphthalocyanine compound, a quaterrylene compound, an aminium compound, an iminium compound, an azo compound, an anthraquinone compound, a porphyrin compound, a pyrrolopyrrole compound, an oxonol compound, a croconium compound, a hexaphyrin compound, a metal dithiol compound, a copper compound, a tungsten compound, and a metal boride are preferred, a diiminium compound, a squarylium compound, a cyanine compound, a phthalocyanine compound, a naphthalocyanine compound, a quaterrylene compound, a pyrrolopyrrole compound, a metal dithiol compound, a copper compound, and a tungsten compound are more preferred, a squarylium compound, a cyanine compound, a phthalocyanine compound, and a pyrrolopyrrole compound are even more preferred, and a squarylium compound and a pyrrolopyrrole compound are particularly preferred. Examples of the infrared absorbing pigment include infrared absorbing pigments such as the infrared absorbents described in JP-A-2009-263614, JP-A-2011-68731, WO 2015 / 166873, etc. Specific examples include compounds having the following structures.

[0082] [ka]

[0083] The infrared absorbing pigment is preferably a compound having absorption in the wavelength range of, for example, 700 nm to 2,000 nm, and more preferably a compound having a maximum absorption wavelength in the wavelength range of 700 nm to 2,000 nm. The volume average particle size of the pigment, preferably the infrared absorbing pigment, is not particularly limited, but is preferably 0.01 μm to 0.1 μm, and more preferably 0.01 μm to 0.05 μm.

[0084] The pigments may be used alone or in combination of two or more kinds. From the viewpoints of colorability, developability, and curability, the content of the pigment is preferably 10% by mass to 80% by mass, more preferably 40% by mass to 70% by mass, further preferably 50% by mass to 70% by mass, and particularly preferably 60% by mass to 70% by mass, based on the total solid content of the curable composition.

[0085] <Photopolymerization initiator> The curable composition according to the present disclosure includes a photoinitiator. The photopolymerization initiator is not particularly limited as long as it has the ability to initiate polymerization, and can be appropriately selected from known photopolymerization initiators. For example, a compound having photosensitivity to light in the ultraviolet to visible range is preferable. In addition, it may be a compound that reacts with a photoexcited sensitizer to generate active radicals. From the viewpoints of curability and sensitivity, the photopolymerization initiator is preferably a photoradical polymerization initiator, and more preferably a compound having an oxime structure.

[0086] Examples of the photopolymerization initiator include halogenated hydrocarbon derivatives (e.g., compounds having a triazine skeleton, compounds having an oxadiazole skeleton, etc.), acylphosphine compounds, hexaarylbiimidazole, oxime compounds, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, α-hydroxyketone compounds, and α-aminoketone compounds. From the viewpoint of exposure sensitivity, the photopolymerization initiator is preferably at least one compound selected from the group consisting of a trihalomethyltriazine compound, a benzyl dimethyl ketal compound, an α-hydroxyketone compound, an α-aminoketone compound, an acylphosphine compound, a phosphine oxide compound, a metallocene compound, an oxime compound, a triarylimidazole dimer, an onium compound, a benzothiazole compound, a benzophenone compound, an acetophenone compound, a cyclopentadiene-benzene-iron complex, a halomethyloxadiazole compound, and a 3-aryl-substituted coumarin compound, more preferably at least one compound selected from the group consisting of an oxime compound, an α-hydroxyketone compound, an α-aminoketone compound, and an acylphosphine compound, and even more preferably an oxime compound. For the photopolymerization initiator, the descriptions in paragraphs

[0065] to

[0111] of JP2014-130173A and paragraphs

[0274] to

[0306] of JP2013-29760A can be referred to, the contents of which are incorporated herein by reference.

[0087] Commercially available α-hydroxyketone compounds include IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, and IRGACURE-127 (all manufactured by BASF). Commercially available α-aminoketone compounds include IRGACURE-907, IRGACURE-369, IRGACURE-379, and IRGACURE-379EG (all manufactured by BASF). Commercially available acylphosphine compounds include IRGACURE-819 and DAROCUR-TPO (all manufactured by BASF).

[0088] Examples of the oxime compound include compounds described in JP-A-2001-233842, compounds described in JP-A-2000-80068, compounds described in JP-A-2006-342166, compounds described in J.C.S. Perkin II (1979, pp. 1653-1660), compounds described in J.C.S. Perkin II (1979, pp. 156-162), compounds described in Journal of Photopolymer Science and Technology (1995, pp. 202-232), compounds described in JP 2000-66385 A, compounds described in JP 2000-80068 A, compounds described in JP-T-2004-534797 A, compounds described in JP 2006-342166 A, compounds described in JP 2017-19766 A, compounds described in Japanese Patent No. 6065596, compounds described in WO 2015 / 152153, compounds described in WO 2017 / 051680, and the like. Specific examples of the oxime compound include 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3-(4-toluenesulfonyloxy)iminobutan-2-one, and 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one. As commercially available oxime compounds, IRGACURE-OXE01, IRGACURE-OXE02, IRGACURE-OXE03, and IRGACURE-OXE04 (all manufactured by BASF) are also suitably used. Other examples include TRONLY TR-PBG-304, TRONLY TR-PBG-309, TRONLY TR-PBG-305 (manufactured by CHANGZHOU TRONLY NEW ELECTRONIC MATERIALS CO., LTD.), ADEKA ARCLES NCI-930, and ADEKA OPTOMER N-1919 (photopolymerization initiator 2 in JP 2012-14052 A) (all manufactured by ADEKA CORPORATION).

[0089] In addition, examples of oxime compounds that may be used include the compound described in JP-T-2009-519904 A in which an oxime is linked to the N-position of a carbazole ring, the compound described in U.S. Pat. No. 7,626,957 A in which a heterosubstituent is introduced at the benzophenone moiety, the compounds described in JP-A-2010-15025 A and U.S. Patent Application Publication No. 2009-292039 A in which a nitro group is introduced at the dye moiety, the ketoxime compounds described in WO 2009 / 131189, the compound described in U.S. Pat. No. 7,556,910 A which contains a triazine skeleton and an oxime skeleton in the same molecule, and the compound described in JP-A-2009-221114 A which has an absorption maximum at 405 nm and good sensitivity to a g-line light source.

[0090] As the photopolymerization initiator, an oxime compound having a fluorene ring can also be used. Specific examples of the oxime compound having a fluorene ring include the compounds described in JP 2014-137466 A, the contents of which are incorporated herein by reference.

[0091] As the photopolymerization initiator, an oxime compound having a benzofuran skeleton can also be used. Specific examples include compounds OE-01 to OE-75 described in WO 2015 / 036910.

[0092] As the photopolymerization initiator, an oxime compound having a skeleton in which at least one benzene ring of a carbazole ring is replaced with a naphthalene ring can also be used. Specific examples of such oxime compounds include the compounds described in WO 2013 / 083505.

[0093] As the photopolymerization initiator, an oxime compound having a fluorine atom can also be used.Specific examples of the oxime compound having a fluorine atom include the compounds described in JP-A-2010-262028, compounds 24, 36 to 40 described in JP-T-2014-500852, and compound (C-3) described in JP-A-2013-164471.The contents of these compounds are incorporated herein by reference.

[0094] As the photopolymerization initiator, an oxime compound having a nitro group can be used. It is also preferable that the oxime compound having a nitro group is a dimer. Specific examples of the oxime compound having a nitro group include the compounds described in paragraphs 0031 to 0047 of JP 2013-114249 A, paragraphs 0008 to 0012, and 0070 to 0079 of JP 2014-137466 A, the compounds described in paragraphs 0007 to 0025 of Japanese Patent No. 4223071 A, and Adeka Arcles NCI-831 (manufactured by ADEKA Corporation).

[0095] Preferred specific examples of the oxime compound are shown below, but the invention is not limited thereto.

[0096] [ka]

[0097] [ka]

[0098] The oxime compound is preferably a compound having a maximum absorption wavelength in the wavelength region of 350 nm to 500 nm, more preferably a compound having a maximum absorption wavelength in the wavelength region of 360 nm to 480 nm, and more preferably a compound having high absorbance at wavelengths of 365 nm and 405 nm.

[0099] From the viewpoint of sensitivity, the molar absorption coefficient of the oxime compound at a wavelength of 365 nm or 405 nm is preferably 1,000 to 300,000, more preferably 2,000 to 300,000, and particularly preferably 5,000 to 200,000. The molar absorption coefficient of the compound can be measured using a known method. For example, it is preferable to measure using an ultraviolet-visible spectrophotometer (Varian Cary-5 spectrophotometer) at a concentration of 0.01 g / L using ethyl acetate as a solvent.

[0100] As the photopolymerization initiator, a bifunctional or trifunctional or higher functional photopolymerization initiator may be used. Specific examples of such photopolymerization initiators include dimers of oxime compounds described in JP-T-2010-527339, JP-T-2011-524436, WO-2015 / 004565, WO-2016-532675, paragraphs 0412 to 0417, and WO-2017 / 033680, paragraphs 0039 to 0055, and WO-2013-522445 and Compound (E) and Compound (G) described in WO 2016 / 034963, and Cmpd1 to 7 described in WO 2016 / 034963.

[0101] The photopolymerization initiator may be used alone or in combination of two or more kinds. From the viewpoints of sensitivity and pattern formability, the content of the photopolymerization initiator is preferably 0.1% by mass to 50% by mass, more preferably 0.5% by mass to 30% by mass, and particularly preferably 1% by mass to 20% by mass, based on the total solid content of the curable composition.

[0102] <Polymerization inhibitor> From the viewpoint of storage stability, the curable composition according to the present disclosure preferably contains a polymerization inhibitor. Examples of the polymerization inhibitor include 2,2,6,6-tetramethylpiperidine-1-oxyl, 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl, 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-tert-butylphenol), and N-nitrosophenylhydroxyamine salts (ammonium salts, cerous salts, etc.). Among these, from the viewpoint of storage stability, compounds having an N-oxyl radical structure are preferred, and 2,2,6,6-tetramethylpiperidine-1-oxyl is particularly preferred. The polymerization inhibitor may also function as an antioxidant. The molecular weight of the polymerization inhibitor is preferably 200 or less, more preferably 180 or less, further preferably 160 or less, and particularly preferably 120 or more and 160 or less, from the viewpoints of curability and pattern shape. From the viewpoints of curability and pattern shape, the polymerization inhibitor is preferably a compound having no aromatic ring.

[0103] The polymerization inhibitor may be used alone or in combination of two or more kinds. From the viewpoint of storage stability, the content of the polymerization inhibitor is preferably from 0.1 ppm to 1,000 ppm, more preferably from 1 ppm to 500 ppm, and particularly preferably from 1 ppm to 100 ppm, based on the total solid content of the curable composition.

[0104] <Other ingredients> The curable composition according to the present disclosure is preferably a composition that ultimately cures to give a cured film. In addition, the curable composition according to the present disclosure is preferably a composition that can form a pattern of a cured film by, for example, patterned exposure, and may be a negative composition or a positive composition as long as a cured film is finally obtained. When the curable composition according to the present disclosure is a negative composition, for example, an embodiment including a polymerization initiator, a polymerizable compound, and an alkali-soluble resin is preferable. In addition, when the curable composition according to the present disclosure is a positive type composition, for example, it may include an embodiment including a photoacid generator, a polymer having a structural unit having a group in which an acid group is protected by an acid-decomposable group, and a polymer having a structural unit having a crosslinkable group. Hereinafter, each component contained in an embodiment in which the curable composition according to the present disclosure is a negative composition will be described. In an embodiment in which the curable composition according to the present disclosure is a positive composition, the components contained therein include those described in WO 2014 / 003111, and the same applies to preferred embodiments.

[0105] -Polymerizable compound- The curable composition according to the present disclosure preferably contains a polymerizable compound. As the polymerizable compound that can be used in the present disclosure, an ethylenically unsaturated compound is preferable, and a compound having a terminal ethylenically unsaturated group is more preferable. As such a compound group, any known compound can be used without any particular limitation. These have chemical forms such as monomers, prepolymers, i.e., dimers, trimers and oligomers, or mixtures thereof and copolymers thereof. Examples of monomers and copolymers thereof include unsaturated carboxylic acids (e.g., acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), their esters and amides, and preferably, esters of unsaturated carboxylic acids and aliphatic polyhydric alcohol compounds, and amides of unsaturated carboxylic acids and aliphatic polyamine compounds are used. In addition, addition reaction products of unsaturated carboxylic acid esters or amides having nucleophilic substituents such as hydroxyl groups, amino groups, and mercapto groups with monofunctional or polyfunctional isocyanates or epoxies, and dehydration condensation reaction products of monofunctional or polyfunctional carboxylic acids are also preferably used. Also suitable are addition reaction products of unsaturated carboxylic acid esters or amides having electrophilic substituents such as isocyanate groups or epoxy groups with monofunctional or polyfunctional alcohols, amines, or thiols, and substitution reaction products of unsaturated carboxylic acid esters or amides having a leaving substituent such as halogen groups or tosyloxy groups with monofunctional or polyfunctional alcohols, amines, or thiols. As another example, it is also possible to use a compound group in which the above unsaturated carboxylic acids are replaced with unsaturated phosphonic acids, styrene, vinyl ether, etc.

[0106] Specific examples of monomers of esters of aliphatic polyhydric alcohol compounds and unsaturated carboxylic acids include acrylic esters such as ethylene glycol diacrylate, triethylene glycol diacrylate, 1,3-butanediol diacrylate, tetramethylene glycol diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane tri(acryloyloxypropyl)ether, trimethylolethane triacrylate, hexanediol diacrylate, 1,4-cyclohexanediol diacrylate, ethylene glycol ... Examples of such acrylates include hexanediol diacrylate, tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tri(acryloyloxyethyl)isocyanurate, polyester acrylate oligomer, and isocyanuric acid EO modified triacrylate.

[0107] Examples of methacrylic acid esters include tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, ethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, hexanediol dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol dimethacrylate, dipentaerythritol hexamethacrylate, sorbitol trimethacrylate, sorbitol tetramethacrylate, bis[p-(3-methacryloxy-2-hydroxypropoxy)phenyl]dimethylmethane, and bis-[p-(methacryloxyethoxy)phenyl]dimethylmethane.

[0108] Also suitable are urethane-based addition polymerizable compounds produced by the addition reaction of isocyanate with a hydroxyl group. Specific examples of such compounds include polyisocyanates having two or more isocyanate groups in one molecule, as described in JP-B-48-41708. Examples of the compound include a vinyl urethane compound having two or more polymerizable vinyl groups in one molecule, which is obtained by adding a vinyl monomer having a hydroxyl group represented by the following general formula (I).

[0109] CH2=C(R)COOCH2CH(R')OH (I) (wherein R and R' represent H or CH3.)

[0110] Also suitable are urethane acrylates as described in JP-A-51-37193, JP-B-2-32293, and JP-B-2-16765, and urethane compounds having an ethylene oxide skeleton as described in JP-B-58-49860, JP-B-56-17654, JP-B-62-39417, and JP-B-62-39418. Furthermore, by using addition polymerizable compounds having an amino structure or a sulfide structure in the molecule as described in JP-A-63-277653, JP-A-63-260909, and JP-A-1-105238, a curable composition having an extremely excellent photosensitivity speed can be obtained.

[0111] Other examples of the polymerizable compound include the compounds described in paragraphs 0178 to 0190 of JP-A No. 2007-277514.

[0112] From the viewpoints of colorability, developability, and curability, the content of the polymerizable compound is preferably 0% by mass to 90% by mass, more preferably 0% by mass to 25% by mass, even more preferably 0% by mass to 20% by mass, and still more preferably 0% by mass to 15% by mass, relative to the total solid content of the curable composition.

[0113] -Alkali-soluble resin- The curable composition according to the present disclosure preferably contains an alkali-soluble resin. The alkali-soluble resin can be appropriately selected from alkali-soluble resins that are high molecular weight polymers and have at least one group (e.g., carboxyl group, phosphoric acid group, sulfonic acid group, etc.) that promotes alkali solubility in the molecule (preferably a molecule having an acrylic copolymer or a styrene copolymer as the main chain). Among these, more preferred are those that are soluble in organic solvents and can be developed with a weak alkaline aqueous solution.

[0114] The alkali-soluble resin can be produced, for example, by a known radical polymerization method. The polymerization conditions, such as temperature, pressure, type and amount of radical initiator, type of solvent, etc., when producing the alkali-soluble resin by radical polymerization can be easily set by a person skilled in the art, or the conditions can be determined experimentally. As the above-mentioned high molecular weight polymer, the polymer having carboxylic acid in the side chain is preferred.For example, as described in each of JP-A-59-44615, JP-B-54-34327, JP-B-58-12577, JP-B-54-25957, JP-A-59-53836, JP-A-59-71048, methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid copolymer, etc., as well as the acidic cellulose derivative having carboxylic acid in the side chain, the one obtained by adding acid anhydride to the polymer having hydroxyl group, etc., and furthermore, the high molecular weight polymer having (meth)acryloyl group in the side chain is also preferred.

[0115] Specifically, the alkali-soluble resin is preferably a copolymer of (meth)acrylic acid and another monomer copolymerizable therewith. Examples of other monomers copolymerizable with the above-mentioned (meth)acrylic acid include (meth)acrylic acid esters, crotonic acid esters, vinyl esters, maleic acid diesters, fumaric acid diesters, itaconic acid diesters, (meth)acrylamides, styrenes, vinyl ethers, vinyl ketones, olefins, maleimides, (meth)acrylonitrile Examples include

[0116] Examples of (meth)acrylic acid esters include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, amyl (meth)acrylate, n-hexyl (meth)acrylate, cyclohexyl (meth)acrylate, t-butylcyclohexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, t-octyl (meth)acrylate, dodecyl (meth)acrylate, octadecyl (meth)acrylate, Acetoxyethyl (meth)acrylate, phenyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, 2-(2-methoxyethoxy)ethyl (meth)acrylate, 3-phenoxy-2-hydroxypropyl (meth)acrylate, 2-chloroethyl (meth)acrylate, glycidyl (meth)acrylate, 3,4-Epoxycyclohexylmethyl, vinyl (meth)acrylate, 2-phenylvinyl (meth)acrylate, 1-propenyl (meth)acrylate, allyl (meth)acrylate, 2-allyloxyethyl (meth)acrylate, propargyl (meth)acrylate, benzyl (meth)acrylate, diethylene glycol monomethyl ether (meth)acrylate, diethylene glycol monoethyl ether (meth)acrylate, triethylene glycol monomethyl ether (meth)acrylate, triethylene glycol monoethyl ether (meth)acrylate, polyethylene glycol monomethyl ether (meth)acrylate , polyethylene glycol monoethyl ether (meth)acrylate, β-phenoxyethoxyethyl (meth)acrylate, nonylphenoxy polyethylene glycol (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, trifluoroethyl (meth)acrylate, octafluoropentyl (meth)acrylate, perfluorooctylethyl (meth)acrylate, dicyclopentanyl (meth)acrylate, tribromophenyl (meth)acrylate, tribromophenyloxyethyl (meth)acrylate, and γ-butyrolactone (meth)acrylate.

[0117] The weight average molecular weight of the alkali-soluble resin usable in the present disclosure is preferably 5,000 or more, more preferably in the range of 10,000 to 300,000, and the number average molecular weight is preferably 1,000 or more, more preferably in the range of 2,000 to 250,000. The polydispersity (weight average molecular weight / number average molecular weight) is preferably in the range of 1.1 to 10, more preferably in the range of 1.2 to 5. These alkali-soluble resins may be any of random polymers, block polymers, graft polymers, and the like.

[0118] Other examples of the alkali-soluble resin include the compounds described in paragraphs 0162 to 0175 of JP-A No. 2007-277514.

[0119] At least one selected from the group consisting of the first polymer compound and the second polymer compound according to the present disclosure can also be used as the alkali-soluble resin.

[0120] The content of the alkali-soluble resin is preferably 1 mass % to 20 mass %, more preferably 2 mass % to 15 mass %, and particularly preferably 3 mass % to 12 mass %, based on the total solid content of the curable composition.

[0121] -solvent- The curable composition according to the present disclosure may contain a solvent. Examples of the solvent include esters, such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, alkyl esters, methyl lactate, ethyl lactate, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, and 3-oxypropionic acid alkyl esters such as methyl 3-oxypropionate and ethyl 3-oxypropionate (e.g., methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate), and 2-oxypropionic acid alkyl esters such as methyl 2-oxypropionate, ethyl 2-oxypropionate, and propyl 2-oxypropionate (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-oxy-2-methylpropionate, ethyl 2-oxy-2-methylpropionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate), as well as methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, and the like; Ethers, such as diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, and the like; Ketones, such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, etc.; Aromatic hydrocarbons, such as toluene, xylene, and the like, can be mentioned.

[0122] Of these, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether acetate, and the like are preferred.

[0123] The content of the solvent is preferably an amount such that the total solid content of the curable composition is 10% by mass to 90% by mass. The lower limit is more preferably 15% by mass or more, and even more preferably 20% by mass or more. The upper limit is more preferably 80% by mass or less, and even more preferably 70% by mass or less. The solvent may be one type or two or more types, and when two or more types are used, the total amount is preferably within the above range.

[0124] -Sensitizer- The curable composition according to the present disclosure may contain a sensitizer for the purpose of improving the radical generation efficiency of the radical initiator and increasing the photosensitive wavelength. The sensitizer that can be used in the present disclosure is preferably one that sensitizes the above-mentioned photopolymerization initiator by an electron transfer mechanism or an energy transfer mechanism.

[0125] Sensitizers that can be used in the present disclosure include those that belong to the compounds listed below and have an absorption wavelength in the wavelength region of 300 nm to 450 nm. Preferred examples of the sensitizer include those belonging to the following compound classes and having an absorption wavelength in the range of 330 nm to 450 nm. For example, polynuclear aromatics (e.g., phenanthrene, anthracene, pyrene, perylene, triphenylene, 9,10-dialkoxyanthracene), xanthenes (e.g., fluorescein, eosin, erythrosine, rhodamine B, rose bengal), thioxanthones (e.g., isopropylthioxanthone, diethylthioxanthone, chlorothioxanthone), cyanines (e.g., thiacarbocyanine, oxacarbocyanine), merocyanines (e.g., merocyanine, carbomerocyanine), phthalocyanines, thiazines (e.g., thionine, methylene blue, toluidine blue), acridines (e.g., acridine orange, chloroflavine, acriflavine), anthraquinones (e.g., anthraquinone), squaliums (e.g., Examples of suitable aromatic ketone compounds include squalium, acridine orange, coumarins (e.g., 7-diethylamino-4-methylcoumarin), ketocoumarin, phenothiazines, phenazines, styrylbenzenes, azo compounds, diphenylmethane, triphenylmethane, distyrylbenzenes, carbazoles, porphyrin, spiro compounds, quinacridone, indigo, styryl, pyrylium compounds, pyrromethene compounds, pyrazolotriazole compounds, benzothiazole compounds, barbituric acid derivatives, thiobarbituric acid derivatives, aromatic ketone compounds such as acetophenone, benzophenone, and Michler's ketone, and heterocyclic compounds such as N-aryloxazolidinone. Further examples include compounds described in European Patent No. 568,993, U.S. Pat. Nos. 4,508,811 and 5,227,227, JP-A Nos. 2001-125255 and 11-271969.

[0126] The sensitizer may be used alone or in combination of two or more kinds. The content of the sensitizer in the curable composition according to the present disclosure is preferably 0.1% by mass to 20% by mass, and more preferably 0.5% by mass to 15% by mass, relative to the total solid content of the curable composition, from the viewpoints of deep light absorption efficiency and initiation decomposition efficiency.

[0127] -Co-sensitizer- The curable composition according to the present disclosure may contain a co-sensitizer. The co-sensitizer has the effect of further improving the sensitivity of the sensitizing dye or the initiator to actinic radiation, or suppressing the polymerization inhibition of the polymerizable compound caused by oxygen, etc.

[0128] Other examples of the co-sensitizer include the compounds described in paragraphs 0233 to 0241 of JP-A No. 2007-277514.

[0129] From the viewpoint of improving the curing rate by balancing the polymerization propagation rate and chain transfer, the content of these co-sensitizers is preferably in the range of 0.1% by mass to 30% by mass, more preferably in the range of 1% by mass to 25% by mass, and further preferably in the range of 0.5% by mass to 20% by mass, based on the mass of the total solid content of the curable composition.

[0130] -Other colorants- The curable composition according to the present disclosure may further contain colorants other than the above-mentioned particles. Other colorants include, for example, dyes.

[0131] Examples of the dye include those disclosed in JP-A-64-90403, JP-A-64-91102, JP-A-1-94301, JP-A-6-11614, U.S. Pat. No. 4,808,501, U.S. Pat. No. 505,950, U.S. Pat. No. 5,667,920, JP-A-5-333207, JP-A-6-35183, JP-A-6-51115, and JP-A-6-194828. When classified by chemical structure, examples of the compounds include pyrazole azo compounds, pyrromethene compounds, anilinoazo compounds, triarylmethane compounds, anthraquinone compounds, benzylidene compounds, oxonol compounds, pyrazolotriazole azo compounds, pyridone azo compounds, cyanine compounds, phenothiazine compounds, and pyrrolopyrazole azomethine compounds.

[0132] A dye multimer may also be used as a colorant. The dye multimer is preferably a dye dissolved in a solvent for use, but may be in the form of particles. When the dye multimer is in the form of particles, the dye multimer is dispersed in a solvent or the like for use. The dye multimer in the form of particles can be obtained, for example, by emulsion polymerization. Examples of the dye multimer in the form of particles include compounds described in JP-A-2015-214682. In addition, compounds described in JP-A-2011-213925, JP-A-2013-041097, JP-A-2015-028144, JP-A-2015-030742, and the like can also be used as the dye multimer.

[0133] The curable composition according to the present disclosure may contain various additives, such as a fluorine-based organic compound, other fillers, a polymer compound other than the resin having the structural unit represented by the above formula 1 and the alkali-soluble resin, a surfactant, an adhesion promoter, an antioxidant, an ultraviolet absorber, and an anti-aggregation agent, as necessary.

[0134] Examples of other components include the compounds described in paragraphs 0238 to 0249 of JP-A No. 2007-277514.

[0135] <Preparation of Curable Composition> The method for preparing the curable composition according to the present disclosure is not particularly limited, and the curable composition can be obtained by mixing each component contained in the curable composition by a known method. In addition, in order to improve the dispersibility of the particles in the curable composition according to the present disclosure, the particles may be mixed with at least one of the first polymer compound and the second polymer compound to prepare a particle dispersion, and then other components may be further added and mixed. Furthermore, the mixture may be filtered through a filter for the purpose of removing foreign matter, reducing defects, etc. As the filter, any filter that has been conventionally used for filtering or the like can be used without any particular limitation.

[0136] (cured product) The cured product according to the present disclosure is a cured product obtained by curing the curable composition according to the present disclosure. The curing method is not particularly limited, but examples thereof include curing by exposure to actinic rays such as ultraviolet light, and curing by heating. The cured product according to the present disclosure is preferably in the form of a thin film, for example. The cured product according to the present disclosure is suitably used as a color filter, an infrared absorbing filter, a black matrix provided between pixels of a color filter, a refractive index adjustment film, and the like, and is particularly suitably used as a color filter.

[0137] (Color filter and its manufacturing method) The color filter according to the present disclosure comprises the cured product according to the present disclosure. The color filter according to the present disclosure preferably comprises a cured product according to the present disclosure on a support. The cured product according to the present disclosure may be a pixel of a color filter in a color filter, or may be a black matrix provided between pixels of a color filter, or both the pixels and the black matrix of the color filter may be a cured product according to the present disclosure. The color filter according to the present disclosure will be described in detail below with reference to its manufacturing method.

[0138] (First embodiment of the method for producing a color filter) A first aspect of the method for producing a color filter according to the present disclosure includes a step of applying the curable composition according to the present disclosure onto a support to form a composition film (a composition film forming step), and The method includes a step of exposing a composition film to light in a pattern (hereinafter, appropriately abbreviated as "exposure step"), and a step of developing the composition film after exposure to form a colored pattern (hereinafter, appropriately abbreviated as "development step"). Each step will be described below.

[0139] <Composition film formation process> In the composition film forming step, the curable composition according to the present disclosure is applied onto a support to form a composition film.

[0140] Examples of supports that can be used in this step include soda glass, Pyrex (registered trademark) glass, quartz glass, and these with a transparent conductive film attached thereto, which are used in liquid crystal display elements, etc., and photoelectric conversion element substrates used in image pickup elements, etc., such as silicon substrates and complementary metal oxide semiconductors (CMOS), etc. These substrates may have black stripes formed thereon to separate each pixel. If necessary, an undercoat layer (another layer) may be provided on the substrate to improve adhesion with the upper layer, prevent diffusion of substances, or flatten the substrate surface.

[0141] As a method for applying the curable composition according to the present disclosure onto a support, various coating methods such as slit coating, inkjet method, spin coating, casting coating, roll coating, and screen printing can be applied. The coating thickness of the curable composition is preferably from 0.1 μm to 10 μm, more preferably from 0.2 μm to 5 μm, and even more preferably from 0.2 μm to 3 μm.

[0142] The composition film coated on the support may be dried (prebaked) using a hot plate, an oven, or the like, preferably at a temperature of 50° C. to 140° C. for 10 to 300 seconds.

[0143] <Exposure process> In the exposure step, the composition film formed in the composition film forming step is exposed to light in a pattern. As a method for patternwise exposure, for example, a method of exposure through a mask having a predetermined mask pattern can be mentioned. In this step, when the curable composition according to the present disclosure is a negative curable composition, the light irradiated portion can be cured, whereas when the curable composition according to the present disclosure is a positive curable composition, the solubility of the light irradiated portion in a developer increases.

[0144] As radiation that can be used for exposure, ultraviolet rays such as g-line and i-line are particularly preferred. The exposure dose is 5 mJ / cm 2 ~1500mJ / cm 2 is preferably 10 mJ / cm 2 ~1000mJ / cm 2 More preferably, 10 mJ / cm 2 ~500mJ / cm 2 is particularly preferred. When the color filter according to the present disclosure is for use in a liquid crystal display device, the optical intensity is 5 to 200 mJ / cm 2 within the above range. 2 is preferably 10 mJ / cm 2 ~150mJ / cm 2 More preferably, 10 mJ / cm 2 ~100mJ / cm 2 is particularly preferred. In addition, when the color filter according to the present disclosure is for use in a solid-state imaging device, within the above range, 30 mJ / cm 2 ~1,500mJ / cm 2 is preferably 50 mJ / cm 2 ~1,000mJ / cm 2 More preferably, 80 mJ / cm 2 ~500mJ / cm 2 is particularly preferred.

[0145] <Developing process> Then, by carrying out a development process, the unexposed portion in the exposure step is dissolved into a developer, and the photocured portion is obtained as a colored pattern. The developer is not particularly limited as long as it can remove the curable composition in the uncured portion, and a known developer can be used. Specifically, a combination of various organic solvents or an alkaline aqueous solution can be used. The development temperature is preferably 20° C. to 30° C., and the development time is preferably 20 seconds to 90 seconds.

[0146] Examples of the organic solvent include the solvents already described that can be used when preparing the curable composition according to the present disclosure. As the alkaline aqueous solution, for example, an alkaline aqueous solution obtained by diluting an alkaline compound such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, sodium silicate, sodium metasilicate, ammonia water, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, or 1,8-diazabicyclo-[5.4.0]-7-undecene with pure water to a concentration of 0.001% by mass to 10% by mass, preferably 0.01% by mass to 1% by mass, is preferably used as the developer. When such a developer made of an alkaline aqueous solution is used, a preferred embodiment includes washing (rinsing) with pure water after development.

[0147] After the development step, excess developer may be removed by washing, and the resulting film may be dried and then heated (post-baked). Post-baking is a heat treatment after development, and is preferably a thermal curing treatment at 100° C. to 240° C. When the substrate is a glass substrate or a silicon substrate, a temperature of 200° C. to 240° C. is more preferable within the above temperature range. The post-baking treatment can be carried out continuously or batchwise by using a heating means such as a hot plate, a convection oven (hot air circulation dryer), or a high-frequency heater to heat the coating film after development so as to satisfy the above conditions.

[0148] The above-described composition film forming step, exposure step, and development step (and further heat treatment, if necessary) are repeated a desired number of times to produce a color filter having a desired hue.

[0149] When the curable composition according to the present disclosure is applied onto a substrate to form a film, the dry thickness of the film is preferably 0.3 μm to 5.0 μm, more preferably 0.5 μm to 3.5 μm, and even more preferably 1.0 μm to 2.5 μm.

[0150] Examples of the substrate include non-alkali glass, soda glass, Pyrex (registered trademark) glass, quartz glass, and those with a transparent conductive film attached thereto, which are used in liquid crystal display elements, etc., photoelectric conversion element substrates, such as silicon substrates, and plastic substrates, which are used in solid-state imaging elements, etc. It is preferable that black stripes are formed on these substrates to isolate each pixel. The plastic substrate preferably has a gas barrier layer and / or a solvent-resistant layer on its surface.

[0151] The above-mentioned manufacturing method is a method for manufacturing pixels of a color filter, but the curable composition according to the present disclosure can also manufacture, for example, a black matrix provided between pixels of a color filter. The black matrix can be formed by performing pattern exposure, alkali development, and then post-baking to promote curing of the film in the same manner as the above-mentioned pixel manufacturing method, except that the curable composition according to the present disclosure is used to which a black colorant such as carbon black or titanium black is added as a colorant.

[0152] (Second embodiment of the method for producing a color filter) A second aspect of the method for producing a color filter according to the present disclosure includes a step of applying the curable composition according to the present disclosure onto a support and curing the composition to form a cured product (cured product formation step); The method includes a step of forming a photoresist layer on a substrate (photoresist layer forming step), a step of exposing the photoresist layer in a pattern and developing it to form a resist pattern (resist pattern forming step), and a step of etching the cured product through the resist pattern (etching step). Each step will be described below.

[0153] <Cured product formation process> In the cured product forming step, the curable composition according to the present disclosure is applied onto a support and cured to form a cured product. As the support, the support used in the composition film forming step described above is preferably used. As a method for applying the curable composition, the above-mentioned method for applying the composition film in the step of forming the composition is preferably used. The method for curing the applied curable composition is not particularly limited, and curing by light or heat is preferred. When curing is performed by light, the light may be appropriately selected depending on the initiator contained in the composition, but for example, ultraviolet rays such as g-rays and i-rays are preferably used. The exposure dose is 5 mJ / cm. 2 ~1500mJ / cm 2 is preferred, and 10 mJ / cm 2 ~1000mJ / cm 2 More preferably, 10 mJ / cm 2 ~500mJ / cm 2 is most preferred. When curing is performed by heat, the heating temperature is preferably 120° C. to 250° C., and more preferably 160° C. to 230° C. The heating time varies depending on the heating means, but when heating on a hot plate, it is preferably about 3 minutes to 30 minutes, and when heating in an oven, it is preferably about 30 minutes to 90 minutes.

[0154] <Photoresist layer formation process> In the photoresist layer forming step, a photoresist layer is formed on the cured product. In forming the photoresist layer, for example, a known negative or positive photosensitive composition is used, with a positive photosensitive composition being preferred. The photosensitive composition is applied onto the cured product, and then dried as necessary to obtain a photoresist layer. The method for forming the photoresist layer is not particularly limited, and may be a known method. The thickness of the photoresist layer is preferably from 0.1 μm to 3 μm, more preferably from 0.2 μm to 2.5 μm, and even more preferably from 0.3 μm to 2 μm.

[0155] <Resist pattern formation process> In the resist pattern forming step, the photoresist layer is exposed to light in a pattern and developed to form a resist pattern. The above exposure and development are not particularly limited and can be carried out by known methods.

[0156] <Etching process> In the etching step, the cured product is etched through the resist pattern. The etching method is not particularly limited and may be a known method, for example, a dry etching method.

[0157] <Step of Stripping Resist Pattern> A second aspect of the method for producing a color filter according to the present disclosure may further include a step of peeling off the resist pattern after the etching step. The method for removing the resist pattern is not particularly limited, and any known method can be used.

[0158] (Solid-state imaging element) A solid-state imaging device according to the present disclosure (for example, an image sensor such as a charge coupled device (CCD) or a complementary metal oxide semiconductor (CMOS)) has a color filter according to the present disclosure. For example, a solid-state imaging element according to the present disclosure can be obtained by forming a color filter on a light receiving element. Specifically, a configuration can be exemplified in which a substrate has a plurality of photodiodes constituting a light receiving area of ​​a solid-state imaging element (CCD image sensor, CMOS image sensor, etc.) and a transfer electrode made of polysilicon or the like, a light-shielding film made of tungsten or the like with only the light receiving portion of the photodiode exposed on the photodiodes and the transfer electrode, a device protection film made of silicon nitride or the like formed on the light-shielding film so as to cover the entire light-shielding film and the light receiving portion of the photodiode, and a color filter for solid-state imaging elements according to the present disclosure is disposed on the device protection film. Furthermore, the device may have a light collecting means (such as a microlens, hereinafter the same) on the device protection layer and below the color filter (on the side closer to the support), or the light collecting means may be on the color filter.

[0159] (Image display device) An image display device according to the present disclosure (for example, a liquid crystal display device, an organic EL (electroluminescence) display device, electronic paper, or the like) has a color filter according to the present disclosure. Specifically, for example, an alignment film is formed on the inner surface side of a color filter, which is then opposed to an electrode substrate, and liquid crystal is filled in the gap and sealed, thereby obtaining a liquid crystal panel which is an image display device according to the present disclosure.

[0160] The definition of liquid crystal display devices and details of each display device are described, for example, in "Electronic Display Devices" (written by Sasaki Akio, published by Kogyo Chosakai Co., Ltd. in 1990) and "Display Devices" (written by Ibuki Junsho, published by Sangyo Tosho Co., Ltd. in 1989). Liquid crystal display devices are described, for example, in "Next Generation Liquid Crystal Display Technology" (edited by Uchida Tatsuo, published by Kogyo Chosakai Co., Ltd. in 1994). There are no particular limitations on the liquid crystal display devices to which the present disclosure can be applied, and the present disclosure can be applied, for example, to various types of liquid crystal display devices described in the above "Next Generation Liquid Crystal Display Technology." EXAMPLES

[0161] The present disclosure will be described in detail below with reference to examples, but the present disclosure is not limited to these examples. In the present examples, "%" and "parts" mean "% by mass" and "parts by mass", respectively, unless otherwise specified. In addition, in polymer compounds, unless otherwise specified, the molecular weight is the weight average molecular weight (Mw), and the ratio of the constituent repeating units is the molar percentage. The weight average molecular weight (Mw) is a value measured in terms of polystyrene by gel permeation chromatography (GPC).

[0162] <Synthesis Example A1: Synthesis of Macromonomer B-1> A method for synthesizing a macromonomer B-1 capable of forming the constitutional unit represented by formula 5 is shown below. Into a three-neck flask, ε-caprolactone (1,044.2 parts, corresponding to a cyclic compound), δ-valerolactone (184.3 parts, corresponding to a cyclic compound), and 2-ethyl-1-hexanol (71.6 parts, corresponding to a ring-opening polymerization initiator) were introduced to obtain a mixture. Next, the mixture was stirred while blowing in nitrogen. Monobutyltin oxide (0.61 parts) was then added to the mixture and the resulting mixture was heated to 90° C. After 6 hours 1 Using H-NMR (nuclear magnetic resonance), the signal derived from 2-ethyl-1-hexanol in the mixture was After confirming that the ethanol had disappeared, the mixture was heated to 110° C. The polymerization reaction was continued at 110° C. for 12 hours under nitrogen, and then 1 The disappearance of signals derived from ε-caprolactone and δ-valerolactone was confirmed by H-NMR, and the molecular weight of the obtained compound was measured by GPC (gel permeation chromatography, under the measurement conditions described below). After it was confirmed that the molecular weight of the compound reached the desired value, 2,6-di-t-butyl-4-methylphenol (0.35 parts) was added to the mixture containing the above compound, and then 2-methacryloyloxyethyl isocyanate (87.0 parts) was added dropwise to the obtained mixture over 30 minutes. Six hours after the end of the dropwise addition,1 After confirming the disappearance of the signal derived from 2-methacryloyloxyethyl isocyanate (MOI) by H-NMR, propylene glycol monomethyl ether acetate (PGMEA) (1,387.0 parts) was added to the mixture to obtain a macromonomer B-1 solution (2,770 parts) with a concentration of 50% by mass. The structure of macromonomer B-1 is as follows: 1 The weight average molecular weight of the obtained macromonomer B-1 was confirmed by H-NMR, and was found to be 3,000.

[0163] <Synthesis Examples A2 and A3: Synthesis of Macromonomers B-2 and B-3> The synthesis was carried out in the same manner as in Synthesis Example A1, except that the monomers and the amounts used were changed to those shown in Table 1.

[0164] [Table 1]

[0165] The structures of B-1 to B-3, and B-4 to B-6 described later, are shown below. B-4: Blenmer PSE1300 (NOF Corporation, stearoxy polyethylene glycol monomethacrylate) B-5: Blenmer 75ANEP-600 (manufactured by NOF Corporation, nonylphenoxy (polyethylene glycol-polypropylene glycol) monoacrylate) B-6: Blenmer 50POEP800B (NOF Corporation, octoxy polyethylene glycol-polypropylene glycol monomethacrylate, m≒8, n≒6)

[0166] [ka]

[0167] <Synthesis of Resin PA-1> A three-neck flask was charged with 52.2 parts of a macromonomer B-1 solution having a concentration (solid content) of 50% by mass (PGMEA: 26.1 parts, Macromonomer B-1: 26.1 parts), ω-carboxy-polycaprolactone monoacrylate: 33.9 parts, PGMEA: 114 parts) to obtain a mixture. The mixture was stirred while blowing in nitrogen. Next, the mixture was heated to 75°C while flowing nitrogen into the flask. Next, dodecyl mercaptan (0.96 parts) was added to the mixture, followed by 0.24 parts of 2,2'-azobis(methyl 2-methylpropionate), hereinafter also referred to as "V-601", to initiate the polymerization reaction. The mixture was heated at 75° C. for 2 hours, after which an additional 0.24 parts of V-601 was added to the mixture. After 2 hours, an additional 0.24 parts of V-601 was added to the mixture. After reacting for an additional 2 hours, the mixture was heated to 90° C. and stirred for 3 hours. The polymerization reaction was then completed. After the reaction was completed, dimethyldodecylamine (1.8 parts) and 2,2,6,6-tetramethylpiperidine 1-oxyl (TEMPO, 0.38 parts) were added in air, and then 4-hydroxybutyl acrylate glycidyl ether (C-1) (5.21 parts) was added dropwise. After the dropwise addition, the reaction was continued in air at 90° C. for 24 hours, and the completion of the reaction was confirmed by measuring the acid value. PGMEA (9.3 parts) was added to the obtained mixture to obtain a 30% by mass solution of resin PA-1. The resulting resin PA-1 had a weight average molecular weight of 16,200 and an acid value of 75 mgKOH / g.

[0168] <Synthesis of resin PB-2> Into a three-neck flask, 59.9 parts of a macromonomer B-1 solution having a concentration (solid content) of 50% by mass (PGMEA: 29.95 parts, macromonomer A-1: ​​29.95 parts), ω-carboxy-polycaprolactone monoacrylate: 26.4 parts, 2-hydroxypropyl Methacrylate: 3.7 parts, PGMEA: 110 parts) were introduced to obtain a mixture. The mixture was stirred while blowing in nitrogen. Next, the mixture was heated to 75°C while flowing nitrogen into the flask. Next, dodecyl mercaptan (1.34 parts) was added to the mixture, followed by 0.5 parts of 2,2'-azobis(methyl 2-methylpropionate), hereinafter also referred to as "V-601", to initiate the polymerization reaction. The mixture was heated at 75° C. for 2 hours, after which an additional 0.5 part of V-601 was added to the mixture. After 2 hours, an additional 0.5 part of V-601 was added to the mixture. After reacting for an additional 2 hours, the mixture was heated to 90° C. and stirred for 3 hours. The polymerization reaction was then completed. After the reaction was completed, Neostan U-600 (manufactured by Nitto Kasei Co., Ltd.) (0.11 parts) and 2,2,6,6-tetramethylpiperidine 1-oxyl (TEMPO, 0.38 parts) were added under air, and then 2-isocyanatoethyl acrylate (C-9) (3.24 parts) was added dropwise. After the dropwise addition was completed, the reaction was continued in air for 24 hours at 60° C. PGMEA (5.8 parts) was added to the obtained mixture to obtain a 30% by mass solution of resin PB-2. The resulting resin PB-2 had a weight average molecular weight of 17,800 and an acid value of 75 mgKOH / g.

[0169] The weight average molecular weight (Mw) of each macromonomer and resin was calculated by GPC (gel permeation chromatography) measurement under the following measurement conditions. Equipment: HLC-8220GPC (Tosoh Corporation) Detector: Differential refractometer (RI detector) Precolumn TSKGUARDCOLUMN MP(XL)6mm×40mm (Tosoh Corporation) Sample column: The following four columns are directly connected (all manufactured by Tosoh Corporation) TSK-GEL Multipore-HXL-M 7.8mm×300mm Reference column: Same as sample column Constant temperature bath temperature: 40℃ Mobile phase: Tetrahydrofuran Sample side mobile phase flow rate: 1.0 mL / min Reference mobile phase flow rate: 0.3 mL / min Sample concentration: 0.1% by mass Sample injection volume: 100 μL Data collection time: 16 to 46 minutes after sample injection Sampling pitch: 300msec

[0170] The acid value of each resin was determined by neutralization titration using an aqueous solution of sodium hydroxide. Specifically, the resin was dissolved in a solvent, and the solution was titrated with an aqueous solution of sodium hydroxide using a potentiometric method to calculate the number of millimoles of acid contained in 1 g of solid resin, and then multiplied by the molecular weight of KOH, 56.1, to obtain the acid value.

[0171] The ethylenically unsaturated bond valence of each resin is as follows: 1 After confirming the completion of the reaction of 4-hydroxybutyl acrylate glycidyl ether, 2-isocyanatoethyl acrylate, or the like by H-NMR measurement, the amount was calculated from the ratio of the amount of 4-hydroxybutyl acrylate glycidyl ether, 2-isocyanatoethyl acrylate, or the like charged to the amount of charged solids.

[0172] <Synthesis of Resins PA-2 to 23 and 25, PZ-1 to 4, and PB-1 and 3 to 18> Except for changing the monomers, raw materials, and amounts thereof shown in Tables 2 to 5, the resins were synthesized in the same manner as in the synthesis of Resin PA-1 or PB-2.

[0173] <Synthesis of resin PA-24> Into a three-neck flask, 16.95 parts of ω-carboxy-polycaprolactone monoacrylate, 0.27 parts of dodecyl mercaptan, and 63.1 parts of PGMEA were introduced, and the mixture was heated to 75° C. while flowing nitrogen into the flask. In addition, in a separate container, 52.2 parts of a macromonomer B-1 solution having a concentration (solid content) of 50% by mass (PGMEA: 26.1 parts, macromonomer B-1: 26.1 parts), 16.95 parts of ω-carboxy-polycaprolactone monoacrylate, 50.9 parts of PGMEA, 0.69 parts of dodecyl mercaptan, and 0.484 parts of 2,2'-azobis(methyl 2-methylpropionate) (hereinafter also referred to as "V-601") were mixed to prepare a solution, and this solution was dropped into the three-neck flask over 4 hours. After the mixture was heated at 75° C. for 2 hours, V-601 (0.24 parts) was further added to the mixture, and the mixture was heated to 90° C. and stirred for 3 hours. The polymerization reaction was completed by the above operation. After the reaction was completed, dimethyldodecylamine (1.8 parts) and 2,2,6,6-tetramethylpiperidine 1-oxyl (TEMPO, 0.38 parts) were added in air, and then 4-hydroxybutyl acrylate glycidyl ether (5.21 parts) was added dropwise. After the dropwise addition, the reaction was continued in air at 90° C. for 24 hours, and the completion of the reaction was confirmed by measuring the acid value. PGMEA (9.3 parts) was added to the resulting mixture to obtain a 30% by mass solution of resin PA-24. The resulting resin PA-24 had a weight average molecular weight of 16,800 and an acid value of 75 mgKOH / g.

[0174] [Table 2]

[0175] [Table 3]

[0176] [Table 4]

[0177] [Table 5]

[0178] Details of the abbreviations used in Tables 2 to 5 other than those mentioned above are shown below. A-1: Aronix M-5300 (ω-carboxy-polycaprolactone monoacrylate, manufactured by Toagosei Co., Ltd.) A-2: Light Ester HO-MS (2-methacryloyloxyethyl succinate, manufactured by Kyoeisha Chemical Co., Ltd.) A-3: Light Ester HOA-HH (2-acryloyloxyethylhexahydrophthalic acid, manufactured by Kyoeisha Chemical Co., Ltd.) A-4: β-Carboxyethyl acrylate (β-CEA, manufactured by Daicel Allnex Co., Ltd.) A-5: Vinyl benzoic acid (Tokyo Chemical Industry Co., Ltd.) A-6: CB-1 (2-methacryloyloxyethyl phthalate, manufactured by Shin-Nakamura Chemical Co., Ltd.) A-7:12-methacrylamidododecanoic acid A-8:4-(4-(acryloyloxy)butoxy)benzoic acid A-9: Methacrylic acid (MAA)

[0179] C-1: 4-Hydroxybutyl acrylate glycidyl ether (4HBAGE, manufactured by Nippon Kasei Co., Ltd.) C-2: 3,4-epoxycyclohexylmethyl acrylate (manufactured by Daicel Corporation) C-3: Glycidyl acrylate (Tokyo Chemical Industry Co., Ltd.) C-4: 9-(oxiran-2-yl)nonyl acrylate (synthetic product) C-5: 3-(oxiran-2-ylmethoxy)-3-oxopropyl acrylate (synthetic product) C-6: 2-methyl-2-(((oxiran-2-ylmethoxy)carbonyl)amino)propane-1,3-diyl diacrylate (synthetic product, compound shown below)

[0180]

Chem.

[0181] C-7: Glycidyl methacrylate (GMA, manufactured by Tokyo Chemical Industry Co., Ltd.) C-8: 2-((3-chloropropanoyl)oxy)ethyl methacrylate C-9: Karenz AOI (2-isocyanatoethyl acrylate, manufactured by Showa Denko K.K.) C-10: Karenz BEI (1,1-(bisacryloyloxymethyl)ethyl isocyanate, manufactured by Showa Denko K.K.) C-11: Karenz MOI (2-isocyanatoethyl methacrylate, manufactured by Showa Denko K.K.) C-12: N-methyl-N-hydroxyethylacrylamide glycidyl ether

[0182] <Synthesis Example of C-4>

[0183]

Chem.

[0184] 200 g of 10-undecen-1-ol (manufactured by Tokyo Chemical Industry Co., Ltd.) and 1,378 g of DMAc: dimethylacetamide were placed in a flask, and 153.65 g of 3-chloropropionyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise while cooling the flask with ice, and the mixture was stirred under ice cooling for 1.5 hours. 1 The disappearance of the starting alcohol and the target product were confirmed by 1H-NMR, and the stirring was stopped. 2,000 mL of ethyl acetate was added, and the mixture was washed twice with 2,000 mL of a 3.5 mass% hydrochloric acid aqueous solution and twice with 2,000 mL of a 5 mass% aqueous sodium bicarbonate solution. The organic layer was dried over magnesium sulfate, and the solvent was distilled off under reduced pressure to obtain 296 g of an intermediate. To a flask containing 192 g of the intermediate and 918 g of dichloromethane, 200 g of metachloroperbenzoic acid: mCPBA was added in 5 portions at 1-hour intervals under a water bath, and the mixture was stirred overnight. 1 It was confirmed by \(^1H\)-NMR that the peak of the terminal double bond of the raw material disappeared. 1487 g of 5% by mass aqueous sodium bicarbonate solution was added to the reaction solution, and the mixture was stirred for 2 hours. Then, 500 mL of ethyl acetate was added for extraction, 500 mL of 5% by mass aqueous sodium thiosulfate solution was added and stirred for 1 hour, the aqueous layer was discarded, and the organic layer was concentrated under reduced pressure to obtain 211.5 g of the intermediate. 210 g of the intermediate, 822 g of methylene chloride, and 182.3 mg of p-methoxyphenol were added. While cooling with ice, a mixed solution of 231 g of DBU and 441 g of methylene chloride was added dropwise while maintaining the temperature at 10 °C or lower. 1 The product was confirmed by \(^1H\)-NMR. A mixed solution of 91.1 g of acetic acid and 147 g of methylene chloride was added dropwise while maintaining the temperature at 10 °C or lower, and the mixture was stirred at room temperature for 2 hours. Methylene chloride was concentrated under reduced pressure, 1050 g of hexane was added, washed with 420 g of water, washed with 420 g of 5% by mass aqueous sodium bicarbonate solution, and 137.9 g of the target product was obtained.

[0185] <Synthesis of C-5> 23.3 g of β-carboxyethyl acrylate, 87 mg of p-methoxyphenol, 117 g of chloroform, 16.8 g of glycidol, and 1.98 g of N,N-dimethylaminopyridine were added to a flask. While cooling with ice, 37.26 g of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride was added portionwise and stirred for 1 hour. Then, it was washed with 150 mL of 0.1 N hydrochloric acid solution and also washed with 150 mL of water, and the organic layer was concentrated under reduced pressure to obtain 20 g of the target product.

[0186] <Synthesis of C-6> To a 200 mL three-necked flask, 5.0 g of glycidol (manufactured by Aldrich), 53 g of butyl acetate, 0.04 g of p-methoxyphenol, 14.5 g of Karenz BEI (manufactured by Showa Denko K.K.), and 0.04 g of Neostan U600 (manufactured by Nitto Kasei Co., Ltd.) were added, and the temperature was slowly raised to 60 °C. After continuing the polymerization reaction at 60 °C for 4 hours, 1The disappearance of the signal derived from Karenz BEI was confirmed by H-NMR, and 50 g of water was added and stirred. The organic layer obtained by separating and discarding the aqueous layer was washed again with 50 g of water. 3 g of magnesium sulfate was added to the washed organic layer, which was then filtered. After that, 2,6-di-t-butyl-4-methylphenol (0.4 g) was added and concentrated to obtain 12 g of C-6.

[0187] D-1: Acrylic ester HO (2-hydroxyethyl methacrylate, manufactured by Mitsubishi Chemical Corporation) D-2: Light Ester HOP (2-hydroxypropyl methacrylate, manufactured by Kyoeisha Chemical Co., Ltd.) D-3: Light Ester HOB (2-hydroxybutyl methacrylate, manufactured by Kyoeisha Chemical Co., Ltd.) D-4: Blenmer PE-90 (polyethylene glycol monomethacrylate, n≒2, manufactured by NOF Corporation) D-5: Blenmar PP1000 (polypropylene glycol monomethacrylate, n≒4-6, NOF Corp.) D-6: Plaxel FM2D (unsaturated fatty acid hydroxyalkyl ester modified ε-caprolactone, CH2=C(CH3)COO(CH2)2O[CO(CH2)5O] n H, manufactured by Daicel Corporation) D-7: Blenmer GLM (glycerin monomethacrylate, manufactured by NOF Corporation)

[0188] E-1: Cyclohexyl methacrylate (Tokyo Chemical Industry Co., Ltd.) E-2: Blenmer TBCHMA (4-t-butylcyclohexyl methacrylate, manufactured by NOF Corporation) E-3: 2-Ethylhexyl methacrylate (Tokyo Chemical Industry Co., Ltd.) E-4: Aronix M120 (2-(2-((2-ethylhexyl)oxy)ethoxy)ethyl acrylate, Manufactured by Toagosei Co., Ltd.) E-5: Dicyclopentanyl methacrylate (Tokyo Chemical Industry Co., Ltd.) E-6: 2-Methoxyethyl acrylate (Tokyo Chemical Industry Co., Ltd.)

[0189] F-1: Dimethyldodecylamine F-2: Dimethylbutylamine F-3: Dimethylbenzylamine F-4: Tetrabutylammonium bromide F-5: Triphenylphosphine F-6: Neostan U-600 (bismuth tris(2-ethylhexanoate), manufactured by Nitto Kasei Co., Ltd.)

[0190] Q-1: 2,2,6,6-Tetramethylpiperidine 1-oxyl (TEMPO) Q-2: 4-Hydroxy-2,2,6,6-tetramethylpiperidine 2-oxyl (4-hydroxy-TEMPO) Q-3: p-Methoxyphenol

[0191] <Preparation of pigment dispersion> The raw materials shown in Table 6 or Table 7 below were mixed, and then 230 parts by mass of zirconia beads having a diameter of 0.3 mm were added. The mixture was dispersed for 5 hours using a paint shaker, and the beads were separated by filtration to produce each pigment dispersion.

[0192] [Table 6]

[0193] [Table 7]

[0194] Details of the abbreviations in Table 6 or Table 7 other than those mentioned above are shown below. PR254: CI Pigment Red 254 PR264: CI Pigment Red 264 PR272: CI Pigment Red 272 PY139: CI Pigment Yellow 139 PY150: CI Pigment Yellow 150 PY185: CI Pigment Yellow 185 PB15:6:CI Pigment Blue 15:6 PV23: CI Pigment Violet 23 PG36: CI Pigment Green 36 PG58: CI Pigment Green 58 TiON: Titanium black K1: The following compound K2: The following compound K3: The following compound B1: The following compound B2: The following compound B3: The following compound

[0195] [ka]

[0196] [ka]

[0197] Q1: 2,2,6,6-Tetramethylpiperidine 1-oxyl (TEMPO) Q2: 4-Hydroxy-2,2,6,6-tetramethylpiperidine 2-oxyl (4-hydroxy-TEMPO) J1: Propylene glycol monomethyl ether acetate (PGMEA) J2: Cyclohexanone J3: Cyclopentanone J4: Propylene glycol monomethyl ether (PGME)

[0198] (Examples 1 to 51 and Comparative Examples 1 to 4) <Preparation of Curable Composition> Each of the curable compositions was prepared by mixing the components shown in Tables 8 to 10 in the amounts shown in Tables 8 to 10 below.

[0199] <Evaluation> The curable compositions were evaluated by the following methods. The evaluation results are shown in Tables 8 to 10.

[0200] -Evaluation of pattern adhesion- The curable composition obtained above was applied using a spin coater onto an 8-inch silicon wafer that had been sprayed with hexamethyldisilazane in advance, so that the film thickness after drying would be the film thickness (μm) described above, and the wafer was pre-baked at 100°C for 120 seconds. The coated substrate was exposed to light at a wavelength of 365 nm through a mask having an island pattern of 1.1 μm square using an i-line stepper exposure system FPA-i5+ (Canon Inc.) at 50 mJ / cm 2 ~1,700mJ / cm 2 After exposure, the film was developed at 25°C for 40 seconds using an alkaline developer CD-2000 (manufactured by FUJIFILM Electronic Materials Co., Ltd.). After rinsing with running water for 30 seconds, the film was spray-dried to obtain a colored pattern. The resulting island pattern, 1.1 μm square, was observed from above using a scanning electron microscope (S-9220, Hitachi, Ltd.) to measure the pattern size. Adhesion was also evaluated using an optical microscope. The pattern size when all the patterns were in close contact was evaluated using the following five-point scale. A rating of 3 or above is preferred, with ratings of 4 and 5 being considered to have excellent performance. 5: 0.9μm or more and less than 1.0μm, close contact 4: Adhesion between 1.0μm and 1.05μm 3: Adhesion between 1.05μm and 1.1μm 2: Adhesion between 1.1μm and 1.2μm 1: If the thickness is less than 1.2μm, adhesion will not occur.

[0201] -Deep curing evaluation (evaluation of edge shape of cured material)- The edge shape of a patterned cured product formed using each curable composition was evaluated by the following method.

[0202] [Curable composition film forming process] A curable composition film (composition film) was formed on a silicon wafer so that the film thickness after drying was 0.9 μm. The curable composition film was formed by spin coating. The rotation speed of the spin coater was adjusted so that the film thickness was as described above. The applied curable composition film was placed on a hot plate with the silicon wafer facing down and dried. The surface temperature of the hot plate was 100° C., and the drying time was 120 seconds.

[0203] [Exposure process] The obtained curable composition film was exposed under the following conditions. The exposure was carried out using an i-line stepper (product name "FPA-3000iS+", manufactured by Canon Inc.). The curable composition film was exposed to 400 mJ / cm 2 through a mask having a linear shape of 20 μm (width 20 μm, length 4 mm). 2 (exposure time: 0.5 seconds).

[0204] [Development process] The cured curable composition film was developed under the following conditions to obtain a patterned cured film. The cured curable composition film was subjected to paddle development for 60 seconds at 23° C., five times, using a 0.3% by mass aqueous solution of tetramethylammonium hydroxide (TMAH), to obtain a patterned cured product. The patterned cured product was then rinsed using a spin shower and further washed with pure water.

[0205] [Post-bake process] The patterned cured product obtained above was heated at 220° C. for 300 seconds in a clean oven CLH-21CDH (manufactured by Koyo Thermo Systems Co., Ltd.). Furthermore, the patterned cured product after heating was placed on a hot plate with a surface temperature of 220° C. and heated for 300 seconds.

[0206] 〔evaluation〕 The above patterned cured product was photographed with a scanning electron microscope, and the edge shape of the 1.5 μm pattern cross section was evaluated according to the following criteria. As shown in Figure 1, the length T of the notch at the bottom of a pattern edge portion 2 of a patterned cured product formed on a wafer 4 was measured. In Figure 1, L1 corresponds to the exposed region, and L2 corresponds to the unexposed region. Evaluation was performed according to the following criteria. A rating of A or above is preferred, with a rating of AA being considered to have excellent performance. -Evaluation criteria- AA: The undercut width was greater than 0 μm and less than 0.05 μm. A: The undercut width was more than 0.05 μm and less than 0.15 μm. B: The undercut width was more than 0.15 μm and less than 0.25 μm. C: The undercut width was more than 0.25 μm.

[0207] -Evaluation of storage stability- [1. Exposure sensitivity of curable composition (initial stage)] In each Example or Comparative Example, each curable composition immediately after preparation was applied onto a glass substrate by spin coating, and dried to form a curable composition film having a thickness of 1.0 μm. The spin coating conditions were first a rotation speed of 300 rpm (rotation per minute) for 5 seconds, then 800 rpm for 20 seconds. The drying conditions were 100° C. for 80 seconds. The coating film obtained above was exposed to light with a wavelength of 365 nm at 10 mJ / cm2 through a pattern mask having 1 μm lines and spaces using an i-line stepper exposure system FPA-3000i5+ (Canon Inc.). 2 ~1,600mJ / cm 2 The exposure dose was 1000. The exposed curable composition film was then developed at 25°C for 60 seconds using a 60% CD-2000 (manufactured by FUJIFILM Electronic Materials Co., Ltd.) developer to obtain a patterned cured film. The patterned cured film was then rinsed with running water for 20 seconds and air-dried. In the above exposure step, the minimum exposure amount at which the pattern line width of the light-irradiated area after development was 1.0 μm or more was defined as the exposure sensitivity, and this exposure sensitivity was defined as the initial exposure sensitivity.

[0208] 2. Exposure sensitivity of curable composition (after aging: after 30 days at 45°C) The curable composition immediately after preparation was sealed in an airtight container, kept in an incubator (EYELA / LTI-700) with the temperature inside the container set at 45°C, and taken out after 30 days. The taken-out curable composition was used to carry out the same test as that carried out using the curable composition immediately after preparation, and the exposure sensitivity was determined. This was defined as the exposure sensitivity after aging.

[0209] 〔evaluation〕 The fluctuation rate (%) of the exposure sensitivity was calculated from the initial exposure sensitivity and the exposure sensitivity after aging according to the following formula. The smaller the fluctuation rate (%), the more excellent the storage stability of the curable composition. (Formula) Fluctuation rate = [(Exposure sensitivity after aging - Initial exposure sensitivity) / Initial exposure sensitivity] x 100 A rating of 3 or above is preferred, with ratings of 4 and 5 being considered to have excellent performance.

[0210] -Evaluation criteria- 5: The fluctuation rate was 0% to 3%. 4: The fluctuation rate was greater than 3% and less than 6%. 3: The fluctuation rate was more than 6% but less than 10%. 2: The fluctuation rate was greater than 10% and less than 15%. 1: The fluctuation rate exceeded 15%.

[0211] -Evaluation of development residues (residues in unexposed areas)- In the above test of [1. Exposure sensitivity (initial)], the cured film obtained with the minimum exposure dose that resulted in a pattern line width of 1.0 μm or more after development was heated together with the glass substrate in an oven at 220° C. for 1 hour. After heating the cured film, the number of residues present in the region (unexposed area) on the glass substrate that was not irradiated with light in the exposure process was observed with a SEM (Scanning Electron Microscope, magnification: 20,000 times) to evaluate the residues in the unexposed area. The evaluation was performed according to the following criteria. In practical terms, a rating of 3 or higher is preferable, and ratings 4 and 5 are evaluated as having excellent performance.

[0212] -Evaluation criteria- 5: A pattern was formed, and no residue was observed in the unexposed areas. 4: A pattern was formed, and 1 to 3 residues were observed in a 1.0 μm square unexposed area. 3: A pattern was formed, and 4 to 10 residues were observed in an area of ​​1.0 μm square in the unexposed area. 2: A pattern was formed, and 11 or more residues were observed within a 1.0 μm square area of ​​the unexposed area. 1: No pattern was formed due to poor development.

[0213] [Table 8]

[0214] [Table 9]

[0215] [Table 10]

[0216] Details of the abbreviations used in Tables 8 to 10 other than those mentioned above are shown below. I1: Oxime-based polymerization initiator, IRGACURE OXE-02 (manufactured by BASF) I2: Oxime polymerization initiator, IRGACURE OXE-03 (manufactured by BASF) I3: Oxime polymerization initiator, IRGACURE OXE-04 (manufactured by BASF) I4: The following compound I5: Oxime-based polymerization initiator, Adeka Arcles NCI-831 (manufactured by ADEKA Corporation, contains a nitro group) I6: 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-1-butanone, IRGACURE 369 (BASF)

[0217] [ka]

[0218] M1: the following compound where a+b+c=3 M2: the following compound where a+b+c=4 M3: KAYARAD DPHA (a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate, manufactured by Nippon Kayaku Co., Ltd.)

[0219] [ka]

[0220] M4: UA-7200 (urethane acrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.) M5: The following compound M6: Mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (mass ratio 7:3)

[0221] [ka]

[0222] P1: Resin having the following structure. The numbers in the parentheses indicate the mass ratio. P2: Resin with the following structure H1: Fluorosurfactant, Megafac F-781F (DIC Corporation)

[0223] [ka]

[0224] [ka]

[0225] (Examples 101 to 147) Any one of the green composition, blue composition, and red composition was applied by spin coating so that the film thickness after film formation was 1.0 μm so as not to overlap with the color of the curable composition. For example, the color of the curable composition of Examples 1 to 43 is red, the color of the curable composition of Example 44 is blue, and the color of the curable composition of Examples 45 to 47 is green. Next, the film was heated at 100° C. for 2 minutes using a hot plate. Then, an i-line stepper exposure apparatus FPA-3000i5+ (Canon Inc.) was used to expose the film at 1,000 mJ / cm 2 The substrate was exposed to light through a mask with a dot pattern of 2 μm square at 200° C. Then, paddle development was performed for 60 seconds at 23° C. using a 0.3% by mass aqueous solution of tetramethylammonium hydroxide (TMAH). After that, the substrate was rinsed with a spin shower and further washed with pure water. Next, the substrate was heated at 200° C. for 5 minutes using a hot plate to pattern the Red composition on the infrared cut filter pattern. Similarly, the Green composition, the Blue composition, and the remaining one of the Red compositions were patterned in sequence to form a red, green, and blue colored pattern (Bayer pattern). The Bayer pattern is a repeated 2 x 2 array of color filter elements, each having one red element, two green elements, and one blue element, as disclosed in U.S. Pat. No. 3,971,065. The solid-state imaging device thus obtained was used to capture images, and image performance was evaluated. When any of the compositions obtained in Examples 1 to 47 was used, the images were clearly recognizable even in a low-illumination environment.

[0226] The red composition, green composition, blue composition, and composition for forming an infrared transmission filter used in Examples 101 to 147 are as follows.

[0227] -Red composition- The following components were mixed and stirred, and then filtered through a nylon filter having a pore size of 0.45 μm (manufactured by Nippon Pall Co., Ltd.) to prepare a Red composition. Red pigment dispersion: 51.7 parts by weight Resin 4 (40% by mass PGMEA solution): 0.6 parts by mass Polymerizable compound 4: 0.6 parts by mass Photopolymerization initiator 1: 0.3 parts by weight Surfactant 1: 4.2 parts by weight PGMEA: 42.6 parts by mass

[0228] -Green composition- The following components were mixed and stirred, and then filtered through a nylon filter having a pore size of 0.45 μm (manufactured by Nippon Pall Co., Ltd.) to prepare a Green composition. Green pigment dispersion: 73.7 parts by mass Resin 4 (40% by mass PGMEA solution): 0.3 parts by mass Polymerizable compound 1: 1.2 parts by mass Photopolymerization initiator 1: 0.6 parts by weight Surfactant 1: 4.2 parts by weight Ultraviolet absorber (UV-503, manufactured by Daito Chemical Co., Ltd.): 0.5 parts by mass PGMEA: 19.5 parts by mass

[0229] -Blue composition- The following components were mixed and stirred, and then filtered through a nylon filter having a pore size of 0.45 μm (manufactured by Nippon Pall Co., Ltd.) to prepare a Blue composition. Blue pigment dispersion: 44.9 parts by mass Resin 4 (40% by mass PGMEA solution): 2.1 parts by mass Polymerizable compound 1: 1.5 parts by mass Polymerizable compound 4: 0.7 parts by mass Photopolymerization initiator 1: 0.8 parts by weight Surfactant 1: 4.2 parts by weight PGMEA: 45.8 parts by mass

[0230] -Composition for forming infrared transmission filter- The components in the following composition were mixed and stirred, and then filtered through a nylon filter having a pore size of 0.45 μm (manufactured by Nippon Pall Co., Ltd.) to prepare a composition for forming an infrared transmission filter.

[0231] <Composition 100> Pigment dispersion 1-1: 46.5 parts by weight Pigment dispersion 1-2: 37.1 parts by weight Polymerizable compound 5: 1.8 parts by mass Resin 4: 1.1 parts by mass Photopolymerization initiator 2: 0.9 parts by mass Surfactant 1: 4.2 parts by weight Polymerization inhibitor (p-methoxyphenol): 0.001 parts by mass Silane coupling agent: 0.6 parts by mass PGMEA: 7.8 parts by mass

[0232] <Composition 101> Pigment dispersion 2-1: 1,000 parts by weight Polymerizable compound (dipentaerythritol hexaacrylate): 50 parts by mass Resin: 17 parts by mass Photopolymerization initiator (1-[4-(phenylthio)]-1,2-octanedione-2-(O-benzoyloxime)): 10 parts by mass PGMEA: 179 parts by mass Alkali-soluble polymer F-1: 17 parts by mass (solid content 35% by mass)

[0233] <Synthesis Example of Alkali-Soluble Polymer F-1> In a reaction vessel, 14 parts of benzyl methacrylate, 12 parts of N-phenylmaleimide, 15 parts of 2-hydroxyethyl methacrylate, 10 parts of styrene and 20 parts of methacrylic acid were dissolved in 200 parts of propylene glycol monomethyl ether acetate, and 3 parts of 2,2'-azoisobutyronitrile and 5 parts of α-methylstyrene dimer were further added. After purging the reaction vessel with nitrogen, the mixture was heated at 80°C for 5 hours while stirring and bubbling with nitrogen to obtain a solution containing an alkali-soluble polymer F-1 (solid concentration 35% by mass). This polymer had a weight average molecular weight of 9,700 and a number average molecular weight of 5,700 in terms of polystyrene, and Mw / Mn was 1.70.

[0234] <Pigment dispersion 2-1> 60 parts of CI Pigment Black 32, 20 parts of CI Pigment Blue 15:6, 20 parts of CI Pigment Yellow 139, 80 parts of Solsperse 76500 manufactured by Lubrizol Japan Co., Ltd. (solids concentration: 50% by mass), 120 parts of a solution containing alkali-soluble polymer F-1 (solids concentration: 35% by mass), and 700 parts of propylene glycol monomethyl ether acetate were mixed and dispersed for 8 hours using a paint shaker to obtain colorant dispersion 2-1.

[0235] The raw materials used for the Red composition, the Green composition, the Blue composition, and the composition for forming an infrared transmission filter are as follows.

[0236] ·Red pigment dispersion A mixture of 9.6 parts by mass of CI Pigment Red 254, 4.3 parts by mass of CI Pigment Yellow 139, 6.8 parts by mass of a dispersant (Disperbyk-161, manufactured by BYK Chemie), and 79.3 parts by mass of PGMEA was mixed and dispersed for 3 hours using a bead mill (zirconia beads, 0.3 mm diameter) to prepare a pigment dispersion. Thereafter, the mixture was mixed and dispersed at 2,000 kg / cm using a high-pressure disperser NANO-3000-10 equipped with a pressure reducing mechanism (manufactured by Japan BEE Co., Ltd.). 2The dispersion treatment was carried out at a flow rate of 500 g / min under a pressure of 1000 g / min. This dispersion treatment was repeated 10 times to obtain a red pigment dispersion liquid.

[0237] ·Green pigment dispersion 6.4 parts by weight of CI Pigment Green 36, CI Pigment A mixture of 5.3 parts by mass of Yellow 150, 5.2 parts by mass of a dispersant (Disperbyk-161, manufactured by BYK Chemie), and 83.1 parts by mass of PGMEA was mixed and dispersed for 3 hours using a bead mill (zirconia beads, 0.3 mm diameter) to prepare a pigment dispersion. Thereafter, the mixture was mixed and dispersed at 2,000 kg / cm using a high-pressure disperser NANO-3000-10 equipped with a pressure reducing mechanism (manufactured by Japan BEE Co., Ltd.). 2 The dispersion treatment was carried out at a flow rate of 500 g / min under a pressure of 1000 g / min. This dispersion treatment was repeated 10 times to obtain a green pigment dispersion.

[0238] ·Blue pigment dispersion A mixture of 9.7 parts by mass of CI Pigment Blue 15:6, 2.4 parts by mass of CI Pigment Violet 23, 5.5 parts of a dispersant (Disperbyk-161, manufactured by BYK Chemie), and 82.4 parts of PGMEA was mixed and dispersed for 3 hours using a bead mill (zirconia beads, 0.3 mm diameter) to prepare a pigment dispersion. Thereafter, the mixture was mixed and dispersed at 2,000 kg / cm using a high-pressure disperser NANO-3000-10 equipped with a pressure reducing mechanism (manufactured by Japan BEE Co., Ltd.). 2 Flow rate of 500g / min under pressure of This dispersion process was repeated 10 times to obtain a blue pigment dispersion.

[0239] Pigment Dispersion 1-1 A mixture of the following composition was mixed and dispersed for 3 hours using zirconia beads with a diameter of 0.3 mm in a bead mill (high pressure disperser with pressure reducing mechanism NANO-3000-10 (manufactured by Japan BEE Co., Ltd.)) to prepare pigment dispersion 1-1. Mixed pigment consisting of red pigment (CI Pigment Red 254) and yellow pigment (CI Pigment Yellow 139): 11.8 parts by weight Resin (Disperbyk-111, manufactured by BYK Chemie): 9.1 parts by weight ·PGMEA: 79.1 parts by mass

[0240] Pigment Dispersion 1-2 The mixture of the following composition was mixed and dispersed for 3 hours in a bead mill (high pressure disperser with pressure reducing mechanism NANO-3000-10 (manufactured by Nippon BEE Co., Ltd.)) using zirconia beads with a diameter of 0.3 mm to prepare pigment dispersion 1-2. Mixed pigment consisting of blue pigment (CI Pigment Blue 15:6) and purple pigment (CI Pigment Violet 23): 12.6 parts by weight Resin (Disperbyk-111, manufactured by BYK Chemie): 2.0 parts by weight ·Resin A: 3.3 parts by mass Cyclohexanone: 31.2 parts by weight ·PGMEA: 50.9 parts by mass

[0241] Resin A: Structure shown below (Mw=14,000, the ratio of each structural unit is a molar ratio.)

[0242] [ka]

[0243] Polymerizable compound 1: KAYARAD DPHA (a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate, manufactured by Nippon Kayaku Co., Ltd.) Polymerizable compound 4: structure shown below

[0244] [ka]

[0245] Polymerizable compound 5: Structure shown below (a mixture of the compound on the left and the compound on the right in a molar ratio of 7:3)

[0246] [ka]

[0247] Resin 4: Structure shown below (acid value: 70 mg KOH / g, Mw=11,000, ratio of each structural unit is molar ratio)

[0248] [ka]

[0249] Photopolymerization initiator 1: IRGACURE-OXE01 (1-[4-(phenylthio)]-1,2-octanedione-2-(O-benzoyloxime), manufactured by BASF) Photopolymerization initiator 2: Structure shown below

[0250] [ka]

[0251] Surfactant 1: 1 mass % PGMEA solution of the following mixture (Mw = 14,000). In the following formula, the units of % (62% and 38%) indicating the proportion of the constituent units are % by mass.

[0252] [ka]

[0253] Silane coupling agent: a compound having the following structure: In the following structural formula, Et represents an ethyl group.

[0254] [ka]

[0255] The disclosure of Japanese Patent Application No. 2018-029219, filed on February 21, 2018, is incorporated herein by reference in its entirety. All publications, patent applications, and technical standards mentioned in this specification are herein incorporated by reference to the same extent as if each individual publication, patent application, or technical standard was specifically and individually indicated to be incorporated by reference. [Explanation of symbols]

[0256] 2: Pattern edge of the cured product 4: Wafer T: Length of the bottom notch at the edge of the pattern of the cured product L1: Exposure area L2: Unexposed area

Claims

1. pigments, A resin having a structural unit represented by the following formula 1, and a photopolymerization initiator, and Contains a polymerization inhibitor having an N-oxyl radical structure Curable composition. 【Chemical 1】 In formula 1, R １ ~R ３ each independently represents a hydrogen atom or an alkyl group; X １ represents —COO—, and R ４ represents a group in which two or more hydrocarbon groups and one or more ester bonds are bonded, and L １ represents a group represented by the following formula 3-1, and R ５ represents an alkyleneoxyalkylene group, and X ２ represents an oxygen atom, and n represents 1. 【Chemistry 2】 In formula 3-1, * indicates the bonding position to other structures.

2. The curable composition according to claim 1 , wherein the resin further comprises a structural unit represented by the following formula 5: 【Chemistry 3】 In formula 5, R ７ represents a hydrogen atom or an alkyl group, and X ６ represents an oxygen atom or -NR Ｃ represents -, and R Ｃ represents a hydrogen atom, an alkyl group, or an aryl group; L ３ represents a divalent linking group, Y １ and Y ２ each independently represents an alkyleneoxy group or an alkylenecarbonyloxy group; Z １ represents an aliphatic hydrocarbon group having 1 to 20 carbon atoms or an aromatic hydrocarbon group having 6 to 20 carbon atoms; p and q each independently represent an integer of 0 or greater, and the value of p+q is 1 or greater.

3. 3. The curable composition according to claim 1, wherein the resin has an ethylenically unsaturated bond valence of 0.1 mmol / g to 2.0 mmol / g.

4. The curable composition according to any one of claims 1 to 3, wherein the photopolymerization initiator is a compound having an oxime structure.

5. The curable composition according to any one of claims 1 to 4, which is a curable composition for forming a colored layer of a color filter.

6. A cured product obtained by curing the curable composition according to any one of claims 1 to 5.

7. A color filter comprising the cured product according to claim 6.

8. A step of applying the curable composition according to any one of claims 1 to 5 onto a support to form a composition film; exposing the formed composition film to light in a pattern; and developing the composition film after exposure to form a colored pattern. A method for manufacturing a color filter.

9. A step of applying the curable composition according to any one of claims 1 to 5 onto a support and curing it to form a cured product; forming a photoresist layer on the cured product; forming a resist pattern by patternwise exposing and developing the photoresist layer; and etching the cured product through the resist pattern. A method for manufacturing a color filter.

10. A solid-state imaging device comprising the color filter according to claim 7.

11. An image display device comprising the color filter according to claim 7.

Images