CURABLE COMPOSITION, CURED PRODUCT, COLOR FILTER, METHOD FOR PRODUCING COLOR FILTER, SOLID-STATE IMAGING DEVICE, AND IMAGE DISPLAY DEVICE

Abstract

To provide a curable composition having excellent deep curing properties. The present invention provides a curable composition comprising a pigment, a resin having a structural unit represented by formula 1, and a photopolymerization initiator. 1 is a group represented by formula 2 or formula 3. JPEG2022065057000064.jpg7471

Description

Technical Field

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

Background Art

[0002] Members such as color filters are made into a colored photosensitive composition by containing a polyfunctional monomer, a photopolymerization initiator, an alkali-soluble resin, and other components in a pigment dispersion composition in which an organic pigment or an inorganic pigment is dispersed, and are manufactured by photolithography or the like using this.

[0003] Examples of the composition 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 containing (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]

Chemical Formula

[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, wherein the binder resin has the following formula (I)

[0007]

Chemical Formula

[0008] (R1 represents hydrogen or an alkyl group having 1 to 6 carbon atoms, and R2 represents a divalent linking group.) A copolymer containing a repeating unit represented by, and (1) a part of the carboxyl groups possessed by the binder resin forms a -COO-Y1-R6 (where Y1 is a divalent linking group and R6 represents a group having an ethylenically unsaturated group) structure, or (2) at least a part of the hydroxyl groups possessed by the binder resin is -O-Y2-R 13 (where Y2 is a divalent linking group and R 13 represents a group having an ethylenically unsaturated group). A photopolymerizable composition is described, which is characterized in that

[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). 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 a triazine compound, an acetophenone compound, and a biimidazole compound. A colored photosensitive resin composition is described, which is characterized in that

[0010]

Chemical formula

[0011] Patent Document 4 describes a photosensitive composition containing a photosensitive resin obtained by reacting 0.2 to 0.9 moles of an epoxy group in an ethylenically unsaturated monomer (c) containing an epoxy group with respect to 1 mole of a carboxyl group 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 a formula weight of 70 to 120 and not having a carboxyl group 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: Japanese Patent Application Laid-Open No. 2004-138950 Patent Document 4: Japanese Patent Application Laid-Open No. 2014-81639

Summary of the Invention

Problems to be Solved by the Invention

[0013] The problem to be solved by the embodiments of the present invention is to provide a curable composition excellent in deep part curability. Another problem to be solved by another embodiment of the present invention is to provide a cured product obtained by curing the above curable composition, a color filter including the above cured product, a method for manufacturing the above color filter, or a solid-state imaging device or an image display device including the above color filter.

Means for Solving the Problems

[0014] Means for solving the above problems include the following aspects. <1> A curable composition containing a pigment, a resin having a structural unit represented by the following Formula 1, and a photopolymerization initiator.

[0015]

Chemical formula

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

[0017]

Chemical formula

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

[0019] <2> The curable composition according to <1>, wherein the resin further has a structural unit represented by the following Formula 4.

[0020]

Chemical formula

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

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

[0023] [Chemical formula]

[0024] In formula 5, R 7 represents a hydrogen atom or an alkyl group, X 6 represents an oxygen atom or -NR C -, 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 represent an alkyleneoxy group or an alkylene carbonyloxy 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 more, and the value of p + q is 1 or more.

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

[0026]

Chemical formula

[0027] Note that * represents the bonding position with other structures.

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

Advantages of the Invention

[0029] According to an embodiment of the present invention, a curable composition excellent in deep part curability can be provided. Moreover, according to another embodiment of the present invention, a cured product obtained by curing the curable composition, a color filter including the cured product, a method for manufacturing the color filter, a solid-state imaging device including the color filter, or an image display device can be provided.

Brief Description of the Drawings

[0030]

Figure 1

Modes for Carrying Out the Invention

[0031] Hereinafter, the content of the present disclosure will be described in detail. The description of the constituent elements described below may be based on typical embodiments of the present disclosure, but the present disclosure is not limited to such embodiments. In the present disclosure, the symbol "~" indicating a numerical range is used to mean including the numerical values described before and after it as the lower limit value and the upper limit value, respectively. In the numerical ranges described step by step in this specification, the upper limit value or the lower limit value described in one numerical range may be replaced with the upper limit value or the lower limit value of the numerical range described in other step-by-step descriptions. Also, in the numerical ranges described in this specification, the upper limit value or the lower limit value of the numerical range may be replaced with the value shown in the examples. In addition, in the notation of groups (atomic groups) in the present disclosure, the notation that does not describe substitution and non-substitution includes both those having no substituent and those having a substituent. For example, the term "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group). In the present 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, respectively. In this specification, "(meth)acrylic" is a term used in the 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 "step" includes not only an independent step but also a case where it cannot be clearly distinguished from other steps, as long as the intended purpose of the step 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, a combination of two or more preferred embodiments is a more preferred embodiment. In addition, unless otherwise specified, the weight-average molecular weight (Mw) and number-average molecular weight (Mn) in the present disclosure are molecular weights converted using a gel permeation chromatography (GPC) analyzer equipped with columns of TSKgel GMHxL, TSKgel G4000HxL, and TSKgel G2000HxL (all are product names manufactured by Tosoh Corporation), detected by a differential refractometer using the solvent THF (tetrahydrofuran), and polystyrene as a standard substance. Hereinafter, the present disclosure will be described in detail.

[0032] (Curable composition) The curable composition according to the present disclosure (hereinafter also referred to as "composition") contains a pigment, a resin having a structural unit represented by the following formula 1, and a photopolymerization initiator. In addition, 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] [Chemical formula]

[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 formula 3, R 5 represents an (n + 1)-valent linking group, X 2 represents an oxygen atom or -NR A -, R A represents a hydrogen atom, an alkyl group or an aryl group, and n represents an integer of 1 or more.

[0035] [Chemical formula]

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

[0037] By using the curable composition according to the present disclosure, a cured product excellent in deep curability can be obtained. The reason for obtaining the above effects is unclear, but it is presumed as follows. By having a group represented by Formula 2 or Formula 3, which is a polar group, in the side chain of the resin having a structural unit represented by Formula 1 above, in the composition, the moving range of the above acrylic group becomes large, and it is excellent in reactivity. Also, by having a group represented by Formula 2 or Formula 3, the aggregation of the resins is suppressed, and the dispersibility is excellent. Since the above acrylic group becomes more likely to react, a curable composition excellent in deep curability can be obtained. In addition, by having a structural unit represented by Formula 1, a highly reactive acrylic group can be introduced via a group represented by Formula 2 or Formula 3 at a position away from the main chain. Instead of reacting between acrylic groups within the polymer molecule, the probability of reacting between polymer molecules or with other crosslinking components in the composition is increased, and the crosslinking reaction proceeds efficiently even in a composition with a high pigment concentration, and the deep curability and pattern shape can be improved. Moreover, 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, so it exhibits a steric repulsive property that enhances the adsorbability to the pigment and suppresses the aggregation of pigment particles. As a result, the dispersibility can be improved. Furthermore, by having a structural unit represented by the above Formula 4, a carboxylic acid serving as an adsorbing group can be introduced at a position away from the main chain, and the pigment adsorbability can be enhanced and the dispersion stability can be improved. In addition, by introducing the structural unit represented by Formula 1, the substrate adhesion and the pattern shape can also be improved because of excellent deep curability. Furthermore, by having the structural unit represented by the above Formula 4, the dispersion stability can also be improved.

[0038] <Resin having the structural unit represented by Formula 1> The curable composition according to the present disclosure contains a resin having the structural unit represented by the above Formula 1. R in Formula 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 curability. Also, from the viewpoint of deep curability, R 1 is a hydrogen atom or a methyl group, and it is more preferable that R 2 and R 3 are hydrogen atoms. Further, when L 1 is a group represented by Formula 2, it is more preferable that R 1 is a methyl group, and when L 1 is a group represented by Formula 3, it is more preferable that R 1 is a hydrogen atom. X in Formula 1 1 is preferably -COO- or -CONR- from the viewpoint of deep curability, and more preferably -COO-. R is preferably a hydrogen atom or an alkyl group, and more preferably a hydrogen atom. R in Formula 1 4 is preferably a hydrocarbon group, or a group in which one or more structures selected from the group consisting of an ether bond and an ester bond are bonded to two or more hydrocarbon groups, from the viewpoint of deep curability, and more preferably a hydrocarbon group, or a group in which one or more ester bonds are bonded to two or more hydrocarbon groups. Also, R in Formula 1 4 is preferably a group having a total number of atoms of 2 to 60, more preferably a group having a total number of atoms of 2 to 50, and particularly preferably a group having a total number of atoms of 2 to 40, from the viewpoint of deep curability. Furthermore, from the viewpoint of deep curability, R4 is a group selected from the group consisting of a hydrocarbon group, an alkyleneoxyalkylene carboxyl group, and any group represented by the following structure, and the above R 5 is preferably an alkylene group, or a group in which one or more structures selected from the group consisting of an ether bond and an ester bond are bonded to two or more alkylene groups.

[0039]

Chemical formula

[0040] Note that * represents the bonding position with other structures.

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

[0042] L in Formula 1 1 is preferably a group represented by the above Formula 2 from the viewpoint of dispersibility, and preferably a group represented by the above Formula 3 from the viewpoints of pattern shape and development residue suppression. X in Formula 2 3 is preferably an oxygen atom from the viewpoints of deep hardening property and dispersibility. In addition, when L 1 is a group represented by Formula 2, from the viewpoints of deep hardening 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 it is particularly preferable that R 5 is an ethylene group. X in Formula 3 4 is preferably -COO- from the viewpoints of deep hardening property, pattern shape and development residue suppression. R in Formula 3 e1 ~R e3 are preferably hydrogen atoms from the viewpoints of deep hardening property, pattern shape and development residue suppression. In addition, when L 1 is a group represented by Formula 3, from the viewpoints of deep hardening property, pattern shape and development residue suppression, R 4 is a hydrocarbon group, a group in which one or more structures selected from the group consisting of two or more hydrocarbon groups, an ether bond and an ester bond are bonded, or any group represented by the following structure, and it is particularly preferable that R 5 is an alkylene group, or a group in which one or more structures selected from the group consisting of two or more alkylene groups, an ether bond and an ester bond are bonded.

[0043] Examples of the group represented by Formula 2 preferably include a group represented by the following Formula 2-1 or Formula 2-2. In addition, examples of the group represented by Formula 3 preferably include a group represented by the following Formula 3-1 or Formula 3-2.

[0044]

Chemical formula

[0045] Note that * represents the bonding position with another structure.

[0046] Examples of the structural unit represented by Formula 1 include, but are not limited to, the structures shown below.

[0047] [Chemical formula]

[0048] [Chemical formula]

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

[0050] The above resin may contain the structural unit represented by Formula 1 alone or in combination of two or more. From the viewpoints of developability, pattern shape, dispersion stability, and deep part curability, the content of the structural unit represented by Formula 1 is preferably 1% by mass to 80% by mass, more preferably 1% by mass to 70% by mass, and particularly preferably 1% by mass to 60% by mass based on the total mass of the resin.

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

[0052] [Chemical formula]

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

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

[0055] Examples of the structural unit represented by Formula 4 include, but are not limited to, the structures shown below.

[0056]

Chemical formula

[0057] Note that n represents an integer of 1 or more.

[0058] The above resin may have the structural unit represented by Formula 4 alone or in combination of two or more. 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 based on the total mass of the resin from the viewpoints of developability, pattern shape, and dispersion stability.

[0059] - the structural unit represented by Formula 5 - From the viewpoint of dispersion stability, the resin preferably further has a structural unit represented by the following Formula 5, and more preferably further has the structural unit represented by Formula 4 and the structural unit represented by the following Formula 5 from the viewpoints of dispersion stability and developability.

[0060]

Chemical formula

[0061] In Formula 5, R 7 represents a hydrogen atom or an alkyl group, X 6 represents an oxygen atom or -NR C -, 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 represent an alkyleneoxy group or an alkylene carbonyloxy 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 more, and the value of p + q is 1 or more.

[0062] R 7 in Formula 5 is preferably a hydrogen atom or a methyl group, and more preferably a methyl group. X 6 in Formula 5 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 3From the viewpoint of dispersion stability, it is preferably a group having a total number of atoms of 2 to 30, more preferably a group having a total number of atoms of 3 to 20, and particularly preferably a group having a total number of atoms of 4 to 10. In addition, L in Formula 5 3 From the viewpoint of dispersion stability, it 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 and a urethane bond are bonded.

[0063] Y in Formula 5 1 and Y 2 are each independently preferably an alkylene carbonyloxy group from the viewpoint of dispersion stability, and 1 Y 2 and Y are more preferably different alkylene carbonyloxy groups. From the viewpoint of dispersion stability, the number of carbon atoms of the above alkylene carbonyloxy group is preferably 2 to 30, more preferably 3 to 10, and particularly preferably 5 to 8. From the viewpoint of dispersion stability, p is preferably an integer of 1 or more, and q is preferably an integer of 0 or more, more preferably p is an integer of 1 or more and q is an integer of 1 or more, and particularly preferably p is an integer of 3 or more and q is an integer of 3 or more. In addition, p and q are each independently preferably 50 or less, more preferably 30 or less, and particularly preferably 20 or less. Z in Formula 5 1 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 from the viewpoint of dispersion stability. In addition, the above alkyl group in Z 1 is preferably a branched alkyl group from the viewpoint of dispersion stability.

[0064] Examples of the structural unit represented by Formula 5 preferably include, but are not limited to, the structures shown below.

[0065] [Chemical formula]

[0066] Note that 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 the structural unit represented by Formula 5 alone or in combination of two or more. 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 based on the total mass of the resin.

[0068] - Other structural units - The above resin may have other structural units other than the structural units represented by Formula 1, Formula 4 or Formula 5 described above. There is no particular limitation on the other structural units, and known structural units can be used.

[0069] The weight average molecular weight (Mw) of the above 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 curability, pattern shape, and substrate adhesion, the ethylenically unsaturated bond value of the above resin is preferably 0.01 mmol / g to 2.5 mmol / g, more preferably 0.05 mmol / g to 2.3 mmol / g, still 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 the resin represents the molar amount of ethylenically unsaturated groups per 1 g of the solid content of the resin. By alkali treatment, low-molecular components (a) of ethylenically unsaturated group sites (for example, in the structural unit represented by Formula 1 of the above resin, when having an acryloxy group, acrylic acid) are removed from the resin, and their content is measured by high-performance liquid chromatography (HPLC). Based on the measured value, the ethylenically unsaturated bond value is calculated from 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 a 4 mol / L aqueous sodium hydroxide solution was added, and the mixture was reacted at 40 °C for 2 hours. The reaction solution was neutralized with 10.2 mL of a 4 mol / L methanesulfonic acid aqueous solution, and then a mixed solution containing 5 mL of ion-exchanged water and 2 mL of methanol was transferred to a 100 mL volumetric flask and made up to the mark with methanol to prepare an HPLC measurement sample, which was measured under the following conditions. The content of the low-molecular component (a) was calculated from a calibration curve of the low-molecular component (a) prepared separately, and the ethylenically unsaturated bond value was calculated from the following formula. -Ethylenically Unsaturated Bond Value Calculation Formula- Ethylenically unsaturated bond value [mmol / g] = (Content of low-molecular component (a) [ppm] / Molecular weight of low-molecular component (a) [g / mol]) / (Weighing value of the adjusted solution polymer [g] × (Solid content concentration of the polymer solution [%] / 100) × 10) -HPLC Measurement Conditions- Measuring instrument: Agilent-1200 (manufactured by Agilent Technologies, Inc.) Column: Synergi 4u Polar-RP 80A, 250 mm × 4.60 mm (inner diameter) manufactured by Phenomenex + guard column Column temperature: 40 °C Analysis time: 15 minutes Flow rate: 1.0 mL / min (maximum liquid delivery pressure: 182 bar) Injection volume: 5 μL Detection wavelength: 210 nm Eluent: Tetrahydrofuran (for HPLC without stabilizer) / buffer solution (ion-exchanged aqueous solution containing 0.2 vol% of phosphoric acid and 0.2 vol% of triethylamine) = 55 / 45 (vol%)

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

[0072] The above resin may contain only one kind or two or more kinds in the curable composition. From the viewpoints of deep part curability and dispersion stability, the content of the above 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 with respect to the total solid content of the curable composition. In this specification, the total solid content means the total amount of components obtained by removing the solvent from all components of the composition. Further, from the viewpoints of deep part curability 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 with respect to 100 parts by mass of the content of the pigment.

[0073] The method for synthesizing the resin having the structural unit represented by Formula 1 is not particularly limited, and it can be synthesized by known methods and by applying known methods. For example, after synthesizing the precursor of the above resin by a known method, a method of introducing a group having an acrylic group in the structural unit represented by the above Formula 1 by a polymer reaction can be mentioned. Examples of the above 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] Further, the above resin is composed of different structural repeating units such as a structural repeating unit responsible for developability, a structural repeating unit responsible for dispersibility, and a structural repeating unit responsible for curability. In order to effectively exhibit different functions, it is preferable that the composition of the above resin is uniform. As a method for homogenizing the composition of the above 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. Generally, it is possible to match the reaction rates by increasing the initial concentration in the reaction system of the monomer species with a slow consumption rate and creating a concentration difference in the reaction system by dropping the monomer species with a fast consumption rate.

[0075] <Pigment> The curable composition according to the present disclosure contains a pigment. Examples of the pigment include inorganic pigments and organic pigments. Examples of the inorganic pigment include black pigments such as carbon black and titanium black; metal oxides such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony, and metal complex salts. The following can be mentioned as organic pigments or inorganic pigments.

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

[0077] Also, as the green pigment, it is also possible to use a zinc phthalocyanine pigment in which the average number of halogen atoms in the molecule is 10 to 14, the average number of bromine atoms is 8 to 12, and the average number of chlorine atoms is 2 to 5. Specific examples include the compounds described in International Publication No. 2015 / 118720.

[0078] Also, as the blue pigment, an aluminum phthalocyanine compound having a phosphorus atom can also be used. Specific examples include the compounds described in paragraphs 0022 to 0030 of JP-A No. 2012-247591 and paragraph 0047 of JP-A No. 2011-157478.

[0079] - Pigment Derivative - The curable composition according to the present disclosure may further contain a pigment derivative. Examples of the pigment derivative include compounds having a structure in which a part of an organic pigment is substituted with an acidic group, a basic group, or a phthalimidomethyl group. Examples of the organic pigment for constituting the pigment derivative include diketopyrrolopyrrole-based pigments, azo-based pigments, phthalocyanine-based pigments, anthraquinone-based pigments, quinacridone-based pigments, dioxazine-based pigments, perinone-based pigments, perylene-based pigments, thioindigo-based pigments, isoindoline-based pigments, isoindolinone-based pigments, quinophthalone-based pigments, fluorene-based pigments, metal complex-based pigments, and the like. Further, as the acidic group that the pigment derivative has, a sulfonic acid group, a carboxylic acid group, and a quaternary ammonium base thereof are preferable, a carboxylic acid group and a sulfonic acid group are more preferable, and a sulfonic acid group is particularly preferable. As the basic group that the pigment derivative has, an amino group is preferable, and a tertiary amino group is particularly preferable. Specific examples of the pigment derivative include, for example, the following compounds. Further, the descriptions in paragraphs 0162 to 0183 of JP-A-2011-252065 can be referred to, and this content is incorporated herein.

[0080] [Chemical formula]

[0081] Further, as the pigment, an infrared absorbing pigment can be preferably used. The infrared absorbing pigment is not particularly limited, and known infrared absorbing pigments are used. For example, diiminium compounds, squarylium compounds, cyanine compounds, phthalocyanine compounds, naphthalocyanine compounds, quaterrylene compounds, ammonium compounds, iminium compounds, azo compounds, anthraquinone compounds, porphyrin compounds, pyrrolopyrrole compounds, oxonol compounds, croconium compounds, hexaphilin compounds, metal dithiol compounds, copper compounds, tungsten compounds, and metal borides are preferred. Diiminium compounds, squarylium compounds, cyanine compounds, phthalocyanine compounds, naphthalocyanine compounds, quaterrylene compounds, pyrrolopyrrole compounds, metal dithiol compounds, copper compounds, and tungsten compounds are more preferred. Squarylium compounds, cyanine compounds, phthalocyanine compounds, and pyrrolopyrrole compounds are even more preferred. Squarylium compounds and pyrrolopyrrole compounds are particularly preferred. In addition, examples of the infrared absorbing pigment include infrared absorbing pigments such as the infrared absorbers described in JP-A-2009-263614, JP-A-2011-68731, International Publication No. 2015 / 166873, etc. Specifically, compounds having the following structures can be mentioned.

[0082] [Chemical formula]

[0083] The infrared absorbing pigment is preferably a compound having absorption in the wavelength range of 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. There is no particular limitation on the volume average particle diameter of the pigment, preferably the infrared absorbing pigment, but 0.01 μm to 0.1 μm is preferred, and 0.01 μm to 0.05 μm is more preferred.

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

[0085] <Photoinitiator> The curable composition according to the present disclosure contains a photoinitiator. The photoinitiator is not particularly limited as long as it has the ability to initiate polymerization, and can be appropriately selected from known photoinitiators. For example, a compound having photosensitivity to light rays in the ultraviolet region to the visible region is preferable. Also, a compound that causes some action with a photoexcited sensitizer and generates active radicals may be used. From the viewpoints of curability and sensitivity, the photoinitiator is preferably a photo radical polymerization initiator, and more preferably a compound having an oxime structure.

[0086] Examples of the photoinitiator include halogenated hydrocarbon derivatives (for example, 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, α-aminoketone compounds, and the like. From the viewpoint of exposure sensitivity, the photoinitiator is preferably at least one compound selected from the group consisting of trihalomethyltriazine compounds, benzyldimethylketal compounds, α-hydroxyketone compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, onium compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds, cyclopentadiene-benzene-iron complexes, halomethyloxadiazole compounds, and 3-aryl-substituted coumarin compounds. More preferably, it is at least one compound selected from the group consisting of oxime compounds, α-hydroxyketone compounds, α-aminoketone compounds, and acylphosphine compounds. Even more preferably, it is an oxime compound. Regarding the photoinitiator, the descriptions in paragraphs 0065 to 0111 of JP-A-2014-130173 and paragraphs 0274 to 0306 of JP-A-2013-29760 can be referred to, and these contents are incorporated herein.

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

[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-A-2000-66385, compounds described in JP-A-2000-80068, compounds described in JP-T-2004-534797, compounds described in JP-A-2006-342166, compounds described in JP-A-2017-19766, compounds described in Patent No. 6065596, compounds described in International Publication No. 2015 / 152153, compounds described in International Publication No. 2017 / 051680, and the like. Specific examples of the oxime compound include, for example, 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 products of the oxime compound, IRGACURE-OXE01, IRGACURE-OXE02, IRGACURE-OXE03, IRGACURE-OXE04 (manufactured by BASF) are also preferably used. Further, 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, Adeka Optomer N-1919 (photoinitiator 2 in JP-A-2012-14052) (manufactured by ADEKA CORPORATION) can be mentioned.

[0089] As oxime compounds other than those described above, compounds described in JP-T-2009-519904 in which an oxime is linked to the N-position of a carbazole ring, compounds described in US Patent No. 7,626,957 in which a hetero substituent is introduced into a benzophenone moiety, compounds described in JP-A-2010-15025 and US Patent Application Publication No. 2009-292039 in which a nitro group is introduced into a dye moiety, keto-oxime compounds described in WO 2009 / 131189, compounds described in US Patent No. 7,556,910 containing a triazine skeleton and an oxime skeleton in the same molecule, compounds described in JP-A-2009-221114 having a maximum absorption at 405 nm and having good sensitivity to a g-line light source, etc. may also be used.

[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-A-2014-137466. This content is incorporated herein.

[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 a naphthalene ring can also be used. Specific examples of such an oxime compound 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, compound (C-3) described in JP-A-2013-164471, etc. This content is incorporated herein.

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

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

[0096] [Chemical formula]

[0097] [Chemical formula]

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

[0099] From the viewpoint of sensitivity, the molar extinction 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 extinction coefficient of the compound can be measured using a known method. For example, it is preferably measured at a concentration of 0.01 g / L using an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian) in an ethyl acetate 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 those described in JP-T-2010-527339, JP-T-2011-524436, WO 2015 / 004565, paragraphs 0412 to 0417 of JP-T-2016-532675, dimers of oxime compounds described in paragraphs 0039 to 0055 of WO 2017 / 033680, compound (E) and compound (G) described in JP-T-2013-522445, Cmpd1 to 7 described in WO 2016 / 034963, and the like.

[0101] The photopolymerization initiator may be used alone or in combination of two or more. 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), N-nitrosophenylhydroxyamine salts (ammonium salts, cerous salts, etc.). Among them, from the viewpoint of storage stability, a compound having an N-oxyl radical structure is preferable, and 2,2,6,6-tetramethylpiperidine-1-oxyl is particularly preferable. Note that the polymerization inhibitor may also function as an antioxidant. From the viewpoints of curability and pattern shape, the molecular weight of the polymerization inhibitor is preferably 200 or less, more preferably 180 or less, still more preferably 160 or less, and particularly preferably 120 or more and 160 or less. Also, 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. From the viewpoint of storage stability, the content of the polymerization inhibitor is preferably 0.1 ppm to 1,000 ppm, more preferably 1 ppm to 500 ppm, and particularly preferably 1 ppm to 100 ppm with respect to the total solid content of the curable composition.

[0104] <Other components> The curable composition according to the present disclosure is preferably a composition that finally cures to obtain a cured film. Also, the curable composition according to the present disclosure is preferably a composition that can form a pattern of a cured film by, for example, pattern exposure, and as long as a cured film is finally obtained, it may be a negative-type composition or a positive-type composition. When the curable composition according to the present disclosure is a negative-type composition, for example, an embodiment containing a polymerization initiator, a polymerizable compound, and an alkali-soluble resin is preferable. Also, when the curable composition according to the present disclosure is a positive-type composition, for example, an embodiment containing 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 crosslinkable group can be mentioned. Hereinafter, each component contained in the embodiment in which the curable composition according to the present disclosure is a negative-type composition will be described. Regarding each component contained in the embodiment in which the curable composition according to the present disclosure is a positive-type composition, examples of each component described in International Publication No. 2014 / 003111 can be mentioned, and the preferred embodiments are the same.

[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 group of compounds, known ones can be used without particular limitation. These have chemical forms such as, for example, monomers, prepolymers, that is, dimers, trimers and oligomers, or mixtures thereof and their copolymers. Examples of monomers and their copolymers include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), esters and amides thereof. Preferably, esters of unsaturated carboxylic acids and aliphatic polyhydric alcohol compounds, and amides of unsaturated carboxylic acids and aliphatic polyvalent amine 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 and monofunctional or polyfunctional isocyanates or epoxies, and dehydration condensation reaction products with monofunctional or polyfunctional carboxylic acids are also preferably used. Further, addition reaction products of unsaturated carboxylic acid esters or amides having electrophilic substituents such as isocyanate groups and epoxy groups and monofunctional or polyfunctional alcohols, amines, and thiols, and substitution reaction products of unsaturated carboxylic acid esters or amides having leaving substituents such as halogen groups and tosyloxy groups and monofunctional or polyfunctional alcohols, amines, and thiols are also suitable. Also, as another example, it is also possible to use a group of compounds in which the above unsaturated carboxylic acid is replaced with an unsaturated phosphonic acid, styrene, vinyl ether, etc.

[0106] Specific examples of the monomer of the ester of an aliphatic polyhydric alcohol compound and an unsaturated carboxylic acid include, as acrylic acid esters, 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, 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, EO-modified triacrylate of isocyanuric acid, and the like.

[0107] Specific examples of the 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, bis-[p-(methacryloxyethoxy)phenyl]dimethylmethane, and the like.

[0108] Also, urethane-based addition-polymerizable compounds produced using the addition reaction of isocyanate and a hydroxyl group are also suitable. Specific examples thereof include, for example, a vinyl urethane compound containing two or more polymerizable vinyl groups in one molecule obtained by adding a vinyl monomer containing a hydroxyl group represented by the following general formula (I) to a polyisocyanate compound having two or more isocyanate groups in one molecule described in Japanese Patent Publication No. 48-41708.

[0109] CH2=C(R)COOCH2CH(R’)OH (I) (However, R and R’ represent H or CH3.)

[0110] In addition, urethane acrylates as described in each of Japanese Patent Laid-Open Nos. 51-37193, 2-32293, and 2-16765, and urethane compounds having an ethylene oxide-based skeleton described in each of Japanese Patent Publication Nos. 58-49860, 56-17654, 62-39417, and 62-39418 are also suitable. Furthermore, by using addition-polymerizable compounds having an amino structure or a sulfide structure in the molecule described in each of Japanese Patent Laid-Open Nos. 63-277653, 63-260909, and 1-105238, a curable composition with extremely excellent photosensitivity can be obtained.

[0111] In addition, examples of the polymerizable compound include the compounds described in paragraphs 0178 to 0190 of Japanese Patent Laid-Open No. 2007-277514.

[0112] From the viewpoints of colorability, developability, and curability, the content of the polymerizable compound is preferably 0 mass% to 90 mass%, more preferably 0 mass% to 25 mass%, still more preferably 0 mass% to 20 mass%, and still more preferably 0 mass% to 15 mass% with respect 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. As the alkali-soluble resin, a polymer can be appropriately selected from among alkali-soluble resins which are polymers and have at least one group that promotes alkali solubility (such as a carboxyl group, a phosphoric acid group, a sulfonic acid group, etc.) in the molecule (preferably a molecule having a main chain of an acrylic copolymer or a styrene copolymer). Among these, those which are more preferably soluble in an organic solvent and developable with a weak alkaline aqueous solution are selected.

[0114] For the production of the alkali-soluble resin, for example, a known method by a radical polymerization method can be applied. Polymerization conditions such as temperature, pressure, type and amount of radical initiator, type of solvent, etc. when producing the alkali-soluble resin by the radical polymerization method can be easily set by those skilled in the art, and conditions can also be determined experimentally. As the above polymer, a polymer having a carboxylic acid in the side chain is preferable. For example, methacrylic acid copolymers, acrylic acid copolymers, itaconic acid copolymers, crotonic acid copolymers, maleic acid copolymers, partially esterified maleic acid copolymers, etc. as described in JP-A-59-44615, JP-B-54-34327, JP-B-58-12577, JP-B-54-25957, JP-A-59-53836, JP-A-59-71048, etc., and acidic cellulose derivatives having a carboxylic acid in the side chain, those obtained by adding an acid anhydride to a polymer having a hydroxyl group, etc. can be mentioned, and further, polymers having a (meth)acryloyl group in the side chain are also preferably mentioned.

[0115] Specifically, as the alkali-soluble resin, a copolymer of (meth)acrylic acid and another monomer copolymerizable therewith is particularly suitable. As the other monomer copolymerizable with the above (meth)acrylic acid, (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, etc. can be mentioned.

[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, nonylphenoxypolyethylene glycol (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyl oxyethyl (meth)acrylate, trifluoroethyl (meth)acrylate, octafluoropentyl (meth)acrylate, perfluorooctylethyl (meth)acrylate, dicyclopentanyl (meth)acrylate, tribromophenyl (meth)acrylate, tribromophenyloxyethyl (meth)acrylate, γ-butyrolactone (meth)acrylate, and the like can be mentioned.,

[0117] The weight average molecular weight of the alkali-soluble resin that can be used 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, etc.,

[0118] In addition, examples of the alkali-soluble resin include the compounds described in paragraphs 0162 to 0175 of JP-A-2007-277514.,

[0119] In addition, 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 an alkali-soluble resin.

[0120] The content of the alkali-soluble resin is preferably 1% by mass to 20% by mass, more preferably 2% by mass to 15% by mass, and particularly preferably 3% by mass to 12% by mass with respect to 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 alkyl 3-oxypropionates such as methyl 3-oxypropionate and ethyl 3-oxypropionate (for example, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate), and alkyl 2-oxypropionates such as methyl 2-oxypropionate, ethyl 2-oxypropionate, and propyl 2-oxypropionate (for example, 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), and also methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, etc. 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, etc.; Ketones, such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, etc.; Aromatic hydrocarbons, such as toluene, xylene, etc. can be mentioned.

[0122] Among 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, etc. 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 only one type or two or more types. In the case of two or more types, it is preferable that the total amount is 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 shifting the photosensitive wavelength to a longer wavelength. As the sensitizer that can be used in the present disclosure, those that sensitize the above-mentioned photopolymerization initiator by an electron transfer mechanism or an energy transfer mechanism are preferred.

[0125] Sensitizers that can be used in the present disclosure belong to the compound classes listed below and have an absorption wavelength in the wavelength range of 300 nm to 450 nm. Examples of preferred sensitizers 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., isopropyl thioxanthone, diethyl thioxanthone, chlorothioxanthone), cyanines (e.g., thiacarbocyanine, oxacarbocyanine), merocyanines (e.g., merocyanine, carbomerocyanine), phthalocyanines, thiazines (e.g., thionin, methylene blue, toluidine blue), acridines (e.g., acridine orange, chlorflavine, acriflavine), anthraquinones (e.g., anthraquinone), squariliums (e.g., squarilium), acridine orange, coumarins (e.g., 7-diethylamino-4-methylcoumarin), ketocoumarin, phenothiazines, phenazines, stilbenzenes, azo compounds, diphenylmethane, triphenylmethane, distyrylbenzenes, carbazoles, porphyrin, spiro compounds, quinacridone, indigo, styryl, pyrylium compounds, pyromethene compounds, pyrazolotriazole compounds, benzothiazole compounds, barbituric acid derivatives, thiobarbituric acid derivatives, aromatic ketone compounds such as acetophenone, benzophenone, Michler's ketone, heterocyclic compounds such as N-aryloxazolidinone, etc. Further, compounds described in European Patent No. 568,993, U.S. Patent No. 4,508,811, No. 5,227,227, JP-A-2001-125255, JP-A-11-271969, etc. are included.

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

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

[0128] In addition, examples of the co-sensitizer include the compounds described in paragraphs 0233 to 0241 of JP-A-2007-277514.

[0129] From the viewpoint of improving the curing rate based on the balance between the polymerization growth 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 still more 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 other colorants other than the above-described particles. Examples of other colorants include dyes.

[0131] Examples of the dyes include those disclosed in, for example, JP-A-64-90403, JP-A-64-91102, JP-A-1-94301, JP-A-6-11614, US Patent No. 4,808,501, US Patent No. 505,950, US Patent No. 5,667,920, JP-A-5-333207, JP-A-6-35183, JP-A-6-51115, JP-A-6-194828, etc. When classified by chemical structure, pyrazole azo compounds, pyromethene compounds, anilino azo compounds, triarylmethane compounds, anthraquinone compounds, benzylidene compounds, oxonol compounds, pyrazolotriazole azo compounds, pyridone azo compounds, cyanine compounds, phenothiazine compounds, pyrrolopyrazole azomethine compounds, etc. can be mentioned.

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

[0133] The curable composition according to the present disclosure can contain, if necessary, various additives such as fluorine-based organic compounds, other fillers, polymer compounds other than the resin having the structural unit represented by the above formula 1 and the alkali-soluble resin, surfactants, adhesion promoters, antioxidants, ultraviolet absorbers, anti-aggregation agents, etc.

[0134] Examples of the other components include the compounds described in paragraphs 0238 to 0249 of JP-A-2007-277514.

[0135] <Preparation of Curable Composition> The method for preparing the curable composition according to the present disclosure is not particularly limited and 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, the curable composition according to the present disclosure may be prepared by mixing the particles with at least one of a first polymer compound and a second polymer compound to prepare a dispersion of the particles, and then further adding and mixing other components. Further, for the purpose of removing foreign matters and reducing defects, etc., it may be filtered with a filter. The filter can be used without particular limitation as long as it has been conventionally used for filtration purposes and the like.

[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 method of curing is not particularly limited, and examples 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 absorption filter, a black matrix provided between pixels of a color filter, a refractive index adjustment film, etc., and is particularly suitably used as a color filter.

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

[0138] (First aspect of method for manufacturing color filter) The first aspect of the method for manufacturing a color filter according to the present disclosure includes a step of applying a curable composition according to the present disclosure onto a support to form a composition film (composition film forming step), a step of exposing the formed composition film onto 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"). Hereinafter, each step will be described.

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

[0140] Examples of the support that can be used in this step include 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 and the like, a photoelectric conversion element substrate used in imaging elements, such as a silicon substrate, and complementary metal oxide semiconductor (CMOS), etc. These substrates may have black stripes formed to isolate each pixel. Further, if necessary, an undercoat layer (other layer) may be provided on these substrates for improving adhesion to the upper layer, preventing diffusion of substances, or flattening the substrate surface.

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

[0142] The drying (pre-baking) of the composition film coated on the support may be performed on a hot plate, in an oven, etc., preferably at a temperature of 50°C to 140°C for 10 seconds to 300 seconds.

[0143] <Exposure step> In the exposure process, the composition film formed in the above composition film forming process is exposed in a pattern. Examples of the method of exposing in a pattern include a method of exposing through a mask having a predetermined mask pattern. In this process, when the curable composition according to the present disclosure is a negative curable composition, the irradiated portion can be cured. When it is a positive curable composition, the solubility of the irradiated portion in the developer increases.

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

[0145] <Development process> Next, by performing development processing, the unexposed portions in the exposure step are eluted into the developer, and the photocured portions are 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 known developers can be used. Specifically, combinations of various organic solvents or alkaline aqueous solutions 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 aforementioned solvents that can be used when preparing the curable composition according to the present disclosure. Examples of the alkaline aqueous solution include alkaline compounds such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, and 1,8-diazabicyclo-[5.4.0]-7-undecene. An alkaline aqueous solution diluted with pure water so that the concentration is 0.001% by mass to 10% by mass, preferably 0.01% by mass to 1% by mass, is preferably used as the developer. When a developer composed of such an alkaline aqueous solution is used, a mode of washing (rinsing) with pure water after development is also preferably mentioned.

[0147] After the development step, the excess developer may be washed away, dried, and then heat-treated (post-baked). Post-baking is a heat treatment after development, and preferably a heat curing treatment at 100°C to 240°C is performed. When the substrate is a glass substrate or a silicon substrate, 200°C to 240°C is more preferable within the above temperature range. The post-baking treatment can be performed continuously or batchwise on the coated film after development using heating means such as a hot plate, a convection oven (hot air circulation dryer), or a high-frequency heater so as to meet the above conditions.

[0148] By repeating the composition film formation step, exposure step, and development step (further heat treatment if necessary) as described above the desired number of times, a color filter having the desired hue is produced.

[0149] When the curable composition according to the present disclosure is applied onto a substrate to form a film, the dry film thickness is preferably 0.3 μm to 5.0 μm, more preferably 0.5 μm to 3.5 μm, and still 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 for liquid crystal display elements and the like, a photoelectric conversion element substrate used for solid-state imaging devices, such as a silicon substrate, and a plastic substrate. It is preferable that black stripes for isolating each pixel are formed on these substrates. The plastic substrate preferably has a gas barrier layer and / or a solvent-resistant layer on its surface.

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

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

[0153] <Cured product forming step> In the cured product forming step, a 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 above-described composition film forming step is preferably used. Also, as the method for applying the curable composition, the application method used in the above-described composition film forming step is preferably used. The method for curing the applied curable composition is not particularly limited, and it is preferably cured by light or heat. When curing is performed by light, the light may be appropriately selected according to the disclosure agent contained in the composition. For example, ultraviolet rays such as g-line and i-line are preferably used. The exposure amount is 5 mJ / cm 2 ~1500 mJ / cm 2 is preferable, 10 mJ / cm 2 ~1000 mJ / cm 2 is more preferable, and 10 mJ / cm 2 ~500 mJ / cm 2 is most preferable. 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. 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 forming step> In the photoresist layer formation step, a photoresist layer is formed on the cured product. In the formation of the photoresist layer, for example, a known negative-type or positive-type photosensitive composition is used, and a positive-type photosensitive composition is preferred. By applying the photosensitive composition on the cured product and drying it as necessary, a photoresist layer is obtained. The method for forming the photoresist layer is not particularly limited and may be performed by a known method. The thickness of the photoresist layer is preferably 0.1 μm to 3 μm, more preferably 0.2 μm to 2.5 μm, and still more preferably 0.3 μm to 2 μm.

[0155] <Resist pattern formation step> In the resist pattern formation step, the resist pattern is formed by exposing and developing the photoresist layer in a pattern. The exposure and development are not particularly limited and are performed by a known method.

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

[0157] <Step of peeling the resist pattern> The second aspect of the method for manufacturing a color filter according to the present disclosure may further include a step of peeling the resist pattern after the etching step. The method for peeling the resist pattern is not particularly limited, and a known method is used.

[0158] (Solid-state imaging device) The solid-state imaging device according to the present disclosure (for example, an image sensor such as a CCD (Charge Coupled Device) or a CMOS (complementary metal oxide semiconductor)) has a color filter according to the present disclosure. For example, the solid-state imaging device according to the present disclosure can be obtained by forming a color filter on a light-receiving element. Specifically, on a substrate, there are a plurality of photodiodes constituting a light-receiving area of a solid-state imaging device (such as a CCD image sensor or a CMOS image sensor) and transfer electrodes made of polysilicon or the like. There is a light-shielding film made of tungsten or the like with an opening only in the light-receiving portion of the photodiode on the photodiode and the transfer electrode. There is a device protection film made of silicon nitride or the like formed so as to cover the entire surface of the light-shielding film and the light-receiving portion of the photodiode. A configuration having a color filter for a solid-state imaging device according to the present disclosure on the device protection film can be mentioned. Furthermore, a configuration having a condensing means (for example, a microlens or the like. The same applies hereinafter) on the device protection layer and below the color filter (on the side closer to the support), or a configuration having a condensing means on the color filter may be used.

[0159] (Image display device) The image display device according to the present disclosure (for example, a liquid crystal display device, an organic EL (electroluminescence) display device, electronic paper, etc.) has a color filter according to the present disclosure. Specifically, for example, an alignment film is formed on the inner surface side of the color filter, opposed to an electrode substrate, and a liquid crystal panel which is an image display device according to the present disclosure can be obtained by filling and sealing a liquid crystal in a gap portion.

[0160] For the definition of the liquid crystal display device and details of each display device, see, for example, "Electronic Display Device (written by Akio Sasaki, published by Kogyo Chosa Kai in 1990)", "Display Device (written by Junsho Ibuki, published by Sangyo Tosho Co., Ltd. in 1990)", etc. Also, for liquid crystal display devices, see, for example, "Next-Generation Liquid Crystal Display Technology (edited by Tatsuo Uchida, published by Kogyo Chosa Kai in 1994)". There are no particular restrictions on the liquid crystal display devices to which the present disclosure can be applied, and it can be applied to various types of liquid crystal display devices described in the above "Next-Generation Liquid Crystal Display Technology", for example.

Example

[0161] Hereinafter, the present disclosure will be described in detail by way of examples, but the present disclosure is not limited thereto. In this example, unless otherwise specified, "%" and "parts" mean "mass %" and "parts by mass", respectively. In the case of a polymer compound, unless otherwise specified, the molecular weight is the weight-average molecular weight (Mw), and the ratio of the constituent repeating units is the mole percentage. The weight-average molecular weight (Mw) is a value measured as a polystyrene-equivalent value by gel permeation chromatography (GPC) method.

[0162] <Synthesis Example A1: Synthesis of Macromonomer B-1> The synthesis method of macromonomer B-1 capable of forming a structural unit represented by Formula 5 is shown below. Into a three-necked 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, while blowing nitrogen, the above mixture was stirred. Next, monobutyltin oxide (0.61 part) was added to the mixture, and the resulting mixture was heated to 90 °C. After 6 hours, 1After confirming the disappearance of the signal derived from 2-ethyl-1-hexanol in the mixture using H-NMR (nuclear magnetic resonance), the mixture was heated to 110°C. After continuing the polymerization reaction at 110°C for 12 hours under nitrogen, 1 The disappearance of the 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 method (Gel permeation chromatography, under the measurement conditions described later). After confirming that the molecular weight of the compound reached the desired value, 2,6-di-t-butyl-4-methylphenol (0.35 part) was added to the mixture containing the above compound, and then, to the obtained mixture, 2-methacryloyloxyethyl isocyanate (87.0 parts) was added dropwise over 30 minutes. Six hours after the completion 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 50 mass% macromonomer B-1 solution (2,770 parts). The structure of macromonomer B-1 is 1 Confirmed by H-NMR. The weight average molecular weight of the obtained macromonomer B-1 was 3,000.

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

[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: Brenmer PSE1300 (manufactured by NOF Corporation, stearoxy polyethylene glycol monomethacrylate) B-5: Brenmer 75 ANEP-600 (manufactured by NOF Corporation, nonylphenoxy (polyethylene glycol - polypropylene glycol) monoacrylate) B-6: Brenmer 50 POEP800B (manufactured by NOF Corporation, octoxypolyethylene glycol - polypropylene glycol monomethacrylate, m≈8, n≈6)

[0166] [Chemical formula]

[0167] [Synthesis of Resin PA-1] Into a three-necked flask, 52.2 parts of a macromonomer B-1 solution with 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) were introduced to obtain a mixture. While blowing nitrogen, the above mixture was stirred. Next, while flowing nitrogen into the flask, the mixture was heated to 75°C. Next, into the mixture, dodecyl mercaptan (0.96 part), Then, 0.24 part of 2,2'-azobis(2-methylpropionic acid methyl), hereinafter also referred to as "V-601", was added to initiate the polymerization reaction. After heating the mixture at 75°C for 2 hours, an additional 0.24 part of V-601 was added to the mixture. After 2 hours, an additional 0.24 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. By the above operation, the polymerization reaction was completed. After completion of the reaction, under air, dimethyldodecylamine (1.8 parts) and 2,2,6,6-tetramethylpiperidine 1-oxyl (TEMPO, 0.38 part) were added, and then 4-hydroxybutyl acrylate glycidyl ether (C-1) (5.21 parts) was added dropwise. After completion of the dropwise addition, the reaction was continued at 90°C for 24 hours under air, and the completion of the reaction was confirmed by measuring the acid value. By adding PGMEA (9.3 parts) to the obtained mixture, a 30% by mass solution of resin PA-1 was obtained. The weight-average molecular weight of the obtained resin PA-1 was 16,200, and the acid value was 75 mgKOH / g.

[0168] <Synthesis of Resin PB-2> Into a three-necked flask, a macromonomer B-1 solution with a concentration (solid content) of 50% by mass was introduced: 59.9 parts (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) to obtain a mixture. While blowing nitrogen, the above mixture was stirred. Next, while flowing nitrogen into the flask, the mixture was heated to 75 °C. Next, dodecyl mercaptan (1.34 parts) was added to the mixture, and then 0.5 part of 2,2'-azobis(2-methylpropionic acid methyl) (hereinafter also referred to as "V-601") was added to initiate the polymerization reaction. After heating the mixture at 75 °C for 2 hours, 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 another 2 hours, the mixture was heated to 90 °C and stirred for 3 hours. By the above operation, the polymerization reaction was completed. After completion of the reaction, under air, Neo-stan U-600 (manufactured by Nitto Kasei Co., Ltd.) (0.11 part) and 2,2,6,6,-tetramethylpiperidine 1-oxyl (TEMPO, 0.38 part) were added, and then 2-isocyanatoethyl acrylate (C-9) (3.24 parts) was added dropwise. After completion of the dropwise addition, the reaction was continued at 60 °C for 24 hours under air. By adding PGMEA (5.8 parts) to the obtained mixture, a 30% by mass solution of resin PB-2 was obtained. The weight-average molecular weight of the obtained resin PB-2 was 17,800, and the acid value was 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. Apparatus: HLC-8220GPC (manufactured by Tosoh Corporation) Detector: Differential Refractometer (RI Detector) Pre-column: TSKGUARDCOLUMN MP(XL) 6 mm × 40 mm (manufactured by Tosoh Corporation) Sample-side column: The following 4 columns are directly connected (all manufactured by Tosoh Corporation) TSK-GEL Multipore-HXL-M 7.8 mm × 300 mm Reference-side column: The same as the sample-side column Thermostat temperature: 40 °C Mobile phase: Tetrahydrofuran Sample-side mobile phase flow rate: 1.0 mL / min Reference-side mobile phase flow rate: 0.3 mL / min Sample concentration: 0.1 mass% Sample injection volume: 100 μL Data acquisition time: 16 minutes to 46 minutes after sample injection Sampling pitch: 300 msec

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

[0171] In addition, the ethylenic unsaturated bond value of each resin was 1 calculated from the proportion of the charged amount of 4-hydroxybutyl acrylate glycidyl ether or 2-isocyanatoethyl acrylate, etc. in the charged solid content after confirming the completion of the reaction such as 4-hydroxybutyl acrylate glycidyl ether or 2-isocyanatoethyl acrylate from 1H-NMR measurement.

[0172] <Synthesis of Resins PA-2 to 23 and 25, PZ-1 to 4, and PB-1 and 3 to 18> They were synthesized by the same method as the synthesis of the above resin PA-1 or PB-2, except that the monomers, raw materials, and their usage amounts described in Tables 2 to 5 were changed.

[0173] <Synthesis of Resin PA-24> Into a three-necked flask, 16.95 parts of ω-carboxy-polycaprolactone monoacrylate, 0.27 part of dodecyl mercaptan, and 63.1 parts of PGMEA were introduced. While flowing nitrogen into the flask, the temperature of the mixture was raised to 75°C. Separately, a solution was prepared by mixing 52.2 parts of a macromonomer B-1 solution with a concentration (solid content) of 50% by mass (26.1 parts of PGMEA, 26.1 parts of macromonomer B-1), 16.95 parts of ω-carboxy-polycaprolactone monoacrylate, 50.9 parts of PGMEA, 0.69 part of dodecyl mercaptan, and 0.484 part of 2,2'-azobis(2-methylpropionic acid methyl) (hereinafter also referred to as "V-601") in a container. This solution was added dropwise to the three-necked flask over 4 hours. After heating the mixture at 75°C for 2 hours, an additional 0.24 part of V-601 was added to the mixture, the temperature was raised to 90°C, and the mixture was stirred for 3 hours. By the above operations, the polymerization reaction was completed. After completion of the reaction, under air, 1.8 parts of dimethyldodecylamine and 0.38 part of 2,2,6,6-tetramethylpiperidine 1-oxyl (TEMPO) were added, and then 5.21 parts of 4-hydroxybutyl acrylate glycidyl ether were added dropwise. After completion of the dropwise addition, the reaction was continued at 90°C for 24 hours under air, and then the completion of the reaction was confirmed by measuring the acid value. A 30% by mass solution of resin PA-24 was obtained by adding 9.3 parts of PGMEA to the resulting mixture. The weight average molecular weight of the obtained resin PA-24 was 16,800, and the acid value was 75 mgKOH / g.

[0174]

Table 2

[0175]

Table 3

[0176]

Table 4

[0177]

Table 5

[0178] The details of the abbreviations described in Tables 2 to 5 other than those described 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 succinic acid, manufactured by Kyoeisha Chemical Co., Ltd.) A-3: Light Ester HOA-HH (2-acryloyloxyethyl hexahydrophthalic acid, manufactured by Kyoeisha Chemical Co., Ltd.) A-4: β-carboxyethyl acrylate (β-CEA, manufactured by Daicel Ornex Co., Ltd.) A-5: Vinyl benzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) A-6: CB-1 (2-methacryloyloxyethyl phthalic acid, 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 (manufactured by 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, the following compound)

[0180]

Chemical Structure

[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]

Chemical Structure

[0184] 200 g of 10-undecen-1-ol (manufactured by Tokyo Chemical Industry Co., Ltd.) and 1,378 g of DMAc: dimethylacetamide were charged into a flask. While cooling the flask with ice, 153.65 g of 3-chloropropionyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise, and the mixture was stirred for 1.5 hours while cooling with ice. 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 3.5 mass% hydrochloric acid aqueous solution and twice with 2,000 mL of 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 the intermediate. Into a flask charged with 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 had 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 the mixture was 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. 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 under ice cooling. 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, and the mixture was washed with 420 g of water and then with 420 g of 5% by mass aqueous sodium bicarbonate solution to obtain 137.9 g of the target product.

[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. 37.26 g of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride was added in portions under ice cooling, and the mixture was stirred for 1 hour. Then, it was washed with 150 mL of 0.1 N hydrochloric acid solution and then with 150 mL of water. 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 curens BEI was confirmed by 1H-NMR, and 50 g of water was added and stirred. The organic layer obtained by liquid separation and discarding the aqueous layer was washed again with 50 g of water. To the washed organic layer, 3 g of magnesium sulfate was added, filtered, and then 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: Brenmer PE-90 (polyethylene glycol monomethacrylate, n≈2, manufactured by NOF Corporation) D-5: Brenmer PP1000 (polypropylene glycol monomethacrylate, n≈4 - 6, manufactured by NOF Corporation) D-6: Placcel 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: Brenmer GLM (glycerin monomethacrylate, manufactured by NOF Corporation)

[0188] E-1: Cyclohexyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) E-2: Brenmer TBCHMA (4-t-butylcyclohexyl methacrylate, manufactured by NOF Corporation) E-3: 2-Ethylhexyl methacrylate (manufactured by 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 (manufactured by Tokyo Chemical Industry Co., Ltd.) E-6: 2-Methoxyethyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0189] F-1: Dimethyldodecylamine F-2: Dimethylbutylamine F-3: Dimethylbenzylamine F-4: Tetrabutylammonium bromide F-5: Triphenylphosphine F-6: Neoester 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> After mixing the raw materials described in Table 6 or Table 7 below, 230 parts by mass of zirconia beads with a diameter of 0.3 mm were added, and dispersion treatment was performed using a paint shaker for 5 hours. The beads were separated by filtration to produce each pigment dispersion.

[0192]

Table 6

[0193]

Table 7

[0194] The details of the abbreviations described in Table 6 or Table 7 other than those mentioned above are shown below. PR254: C.I.Pigment Red 254 PR264: C.I.Pigment Red 264 PR272: C.I.Pigment Red 272 PY139: C.I.Pigment Yellow 139 PY150: C.I.Pigment Yellow 150 PY185: C.I. Pigment Yellow 185 PB15:6: C.I. Pigment Blue 15:6 PV23: C.I. Pigment Violet 23 PG36: C.I. Pigment Green 36 PG58: C.I. 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]

Chemical Structure

[0196]

Chemical Structure

[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 the curable composition> Each of the components described in Tables 8 to 10 below was mixed in the amounts described in Tables 8 to 10 below to prepare each curable composition, respectively.

[0199] <Evaluation> The evaluation of the curable composition was carried out by the following method. The evaluation results are shown in Tables 8 to 10.

[0200] -Evaluation of pattern adhesion- The curable composition obtained above was applied onto an 8-inch silicon wafer previously sprayed with hexamethyldisilazane using a spin coater so that the film thickness after drying would be the described film thickness (μm), and pre-baked at 100 °C for 120 seconds. Using an i-line stepper exposure apparatus FPA-i5+ (manufactured by Canon Inc.), the coated substrate was irradiated through a mask having an island pattern of 1.1 μm square at a wavelength of 365 nm with an exposure amount of 50 mJ / cm 2 ~1,700 mJ / cm 2 After exposure, development was carried out under the conditions of 25 °C for 40 seconds using an alkaline developer CD-2000 (manufactured by Fujifilm Electronic Materials Co., Ltd.). Then, after rinsing with running water for 30 seconds, spray drying was performed to obtain a colored pattern. Regarding the obtained 1.1-μm square island pattern, observation was carried out from above the pattern using a scanning electron microscope (S-9220 manufactured by Hitachi, Ltd.), and pattern size measurement was performed. Also, evaluation of adhesion was carried out using an optical microscope. The pattern size when all patterns were adhered was evaluated in the following 5 grades. An evaluation of 3 or more is preferable, and evaluations 4 and 5 are evaluated as having excellent performance. 5: Adhesion at 0.9 μm or more and less than 1.0 μm 4: Adhesion at 1.0 μm or more and less than 1.05 μm 3: Adhesion at 1.05 μm or more and less than 1.1 μm 2: Adhesion at 1.1 μm or more and less than 1.2 μm 1: No adhesion unless it is 1.2 μm or more

[0201] -Evaluation of deep curability (evaluation of the edge shape of the cured product)- The edge shape of the patterned cured product formed using each curable composition was evaluated by the following method.

[0202] [Sclerosing Composition Film Formation Process] A sclerosing composition film (composition film) was formed on a silicon wafer so that the film thickness after drying would be 0.9 μm. The sclerosing composition film was formed using spin coating. The rotation speed of the spin coating was adjusted so as to obtain the above-mentioned film thickness. The applied sclerosing 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 sclerosing composition film was exposed under the following conditions. Exposure was performed using an i-line stepper (trade name "FPA-3000iS+", manufactured by Canon Inc.). The sclerosing composition film was irradiated (exposed) through a mask having a linear shape of 20 μm (width 20 μm, length 4 mm) with an exposure dose of 400 mJ / cm 2 (irradiation time 0.5 seconds).

[0204] [Development Process] The sclerosing composition film after curing was developed under the following conditions to obtain a patterned cured film. For the sclerosing composition film after curing, a 0.3 mass% aqueous solution of tetramethylammonium hydroxide (TMAH) was used, and paddle development was repeated 5 times at 23 °C for 60 seconds to obtain a patterned cured product. Thereafter, the patterned cured product was 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 using 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-mentioned 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 Fig. 1, the length T of the notch at the bottom of the pattern edge portion 2 of the patterned cured product formed on the wafer 4 was measured. In Fig. 1, L1 corresponds to the exposed area and L2 corresponds to the unexposed area. The evaluation was performed according to the following criteria. An evaluation of A or higher is preferred, and an evaluation of AA indicates excellent performance. - Evaluation Criteria - AA: The undercut width was more than 0 μm and 0.05 μm or less. A: The undercut width was more than 0.05 μm and 0.15 μm or less. B: The undercut width was more than 0.15 μm and 0.25 μm or less. C: The undercut width was more than 0.25 μm.

[0207] - Evaluation of Storage Stability - 〔1. Exposure Sensitivity (Initial) of the Curable Composition〕 In each example or comparative example, each curable composition immediately after preparation was applied onto a glass substrate using spin coating and dried to form a curable composition film with a film thickness of 1.0 μm. The conditions for spin coating were first 300 rpm (rotation per minute) for 5 seconds, and then 800 rpm for 20 seconds. The drying conditions were 100 °C for 80 seconds. For the coating film obtained as described above, using an i-line stepper exposure apparatus FPA - 3000i5+ (manufactured by Canon Inc.), light with a wavelength of 365 nm was irradiated through a pattern mask having a 1-μm line and space at an exposure dose of 2 ~1,600 mJ / cm 2 The exposed curable composition film was developed using a 60% CD - 2000 (manufactured by Fujifilm Electronic Materials Co., Ltd.) developer at 25 °C for 60 seconds to obtain a patterned cured film. Thereafter, the patterned cured film was rinsed with running water for 20 seconds and then air-dried. In the above exposure process, the minimum exposure dose at which the developed pattern line width in the area irradiated with light 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. Photosensitivity of the curable composition (after aging: after 30 days at 45 °C)] The curable composition immediately after preparation was sealed in a closed container and held in a thermostat (EYELA / LTI-700) with the internal temperature set at 45 °C. It was taken out after 30 days. Using the taken-out curable composition, the same test as that performed using the curable composition immediately after preparation was carried out to determine the photosensitivity. This was defined as the photosensitivity after aging.

[0209] [Evaluation] From the initial photosensitivity and the photosensitivity after aging, the rate of change (%) of the photosensitivity calculated by the following formula was determined. The smaller the value of the above rate of change (%), the better the storage stability of the curable composition. (Formula) Rate of change = [(Photosensitivity after aging - Initial photosensitivity) / Initial photosensitivity] × 100 An evaluation of 3 or more is preferable, and evaluations of 4 and 5 are evaluated as having excellent performance.

[0210] - Evaluation criteria - 5: The rate of change was 0% to 3%. 4: The rate of change exceeded 3% and was 6% or less. 3: The rate of change exceeded 6% and was 10% or less. 2: The rate of change exceeded 10% and was 15% or less. 1: The rate of change exceeded 15%.

[0211] - Evaluation of development residue (unexposed part residue) In the test of [1. Photosensitivity of the curable composition (initial)] above, the cured film obtained at the minimum exposure amount at which the developed pattern line width was 1.0 μm or more 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 part) on the glass substrate that was not irradiated with light in the exposure process was observed with an SEM (Scanning Electron Microscope, magnification: 20,000 times) to evaluate the unexposed part residue. The evaluation was carried out according to the following criteria. In practical terms, an evaluation of 3 or more is preferable, and evaluations of 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 area. 4: A pattern was formed, and 1 to 3 residues were observed in a 1.0 μm square in the unexposed area. 3: A pattern was formed, and 4 to 10 residues were observed in a 1.0 μm square in the unexposed area. 2: A pattern was formed, and 11 or more residues were observed in a 1.0 μm square in 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 described in Tables 8 to 10 other than those described above are shown below. I1: Oxime-based polymerization initiator, IRGACURE OXE-02 (manufactured by BASF) I2: Oxime-based polymerization initiator, IRGACURE OXE-03 (manufactured by BASF) I3: Oxime-based polymerization initiator, IRGACURE OXE-04 (manufactured by BASF) I4: The following compound I5: Oxime-based polymerization initiator, Adeka Arcles NCI-831 (manufactured by ADEKA, containing a nitro group) I6: 2-Benzyl-2-dimethylamino-1-(4-morpholinophenyl)-1-butanone, IRGACURE 369 (manufactured by BASF)

[0217]

Chemical Formula

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

[0219]

Chemical formula

[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]

Chemical formula

[0222] P1: Resin with the following structure, the numerical value in the lower right of the parentheses represents the mass ratio. P2: Resin with the following structure H1: Fluorine-based surfactant, Megafac F-781F (manufactured by DIC Corporation)

[0223]

Chemical formula

[0224]

Chemical formula

[0225] (Examples 101 to 147) So that the colors do not overlap with the above-described curable composition, any one of the Green composition, the Blue composition, and the Red composition was applied by spin coating so that the film thickness after film formation became 1.0 μm. For example, the colors of the curable compositions of Examples 1 to 43 were Red, the color of the curable composition of Example 44 was Blue, and the colors of the curable compositions of Examples 45 to 47 were Green. Next, it was heated at 100 °C for 2 minutes using a hot plate. Next, using an i-line stepper exposure apparatus FPA-3000i5+ (manufactured by Canon Inc.), it was exposed through a mask of a 2-μm square dot pattern at 1,000 mJ / cm 2 Then, paddle development was performed at 23 °C for 60 seconds using a 0.3 mass% aqueous solution of tetramethylammonium hydroxide (TMAH). Thereafter, rinsing was performed with a spin shower, and further washing was performed with pure water. Next, by heating at 200 °C for 5 minutes using a hot plate, the Red composition was patterned on the pattern of the infrared cut filter. Similarly, the remaining one of the Green composition, the Blue composition, and the Red composition was sequentially patterned to form red, green, and blue coloring patterns (Bayer pattern). The Bayer pattern is a pattern in which a 2×2 array of color filter elements having one red (Red) element, two green (Green) elements, and one blue (Blue) element, as disclosed in U.S. Patent No. 3,971,065, is repeated. Regarding the obtained solid-state imaging device, image capture was performed and the image performance was evaluated. In any case where the compositions obtained in Examples 1 to 47 were used, the image could be clearly recognized even in a low-illumination environment.

[0226] The Red composition, the Green composition, the Blue composition, and the 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 with 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 mass Resin 4 (40% by mass PGMEA solution): 0.6 parts by mass Polymerizable compound 4: 0.6 parts by mass Photoinitiator 1: 0.3 parts by mass Surfactant 1: 4.2 parts by mass PGMEA: 42.6 parts by mass

[0228] - Green composition - The following components were mixed and stirred, and then filtered through a nylon filter with 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 Photoinitiator 1: 0.6 parts by mass Surfactant 1: 4.2 parts by mass 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 with 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 Photoinitiator 1: 0.8 parts by mass Surfactant 1: 4.2 parts by mass PGMEA: 45.8 parts by mass

[0230] - Composition for forming an infrared transmission filter - The components in the following composition were mixed and stirred, and then filtered through a nylon filter with 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 liquid 1-1: 46.5 parts by mass Pigment dispersion liquid 1-2: 37.1 parts by mass Polymerizable compound 5: 1.8 parts by mass Resin 4: 1.1 parts by mass Photoinitiator 2: 0.9 parts by mass Surfactant 1: 4.2 parts by mass 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 liquid 2-1: 1,000 parts by mass Polymerizable compound (dipentaerythritol hexaacrylate): 50 parts by mass Resin: 17 parts by mass Photoinitiator (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 concentration 35% by mass)

[0233] <Synthesis example of alkali-soluble polymer F-1> 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 in a reaction vessel, and further 3 parts of 2,2'-azoisobutyronitrile and 5 parts of α-methylstyrene dimer were added. After purging the inside of the reaction vessel with nitrogen, it was heated at 80 °C for 5 hours with stirring and nitrogen bubbling to obtain a solution (solid content concentration: 35% by mass) containing an alkali-soluble polymer F-1. The weight average molecular weight of this polymer in terms of polystyrene was 9,700, the number average molecular weight was 5,700, and Mw / Mn was 1.70.

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

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

[0236] ·Red pigment dispersion liquid A mixed solution consisting of 9.6 parts by mass of C.I.Pigment Red 254, 4.3 parts by mass of C.I.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 using a bead mill (zirconia beads with a diameter of 0.3 mm) for 3 hours to prepare a pigment dispersion liquid. Then, using a high-pressure disperser NANO-3000-10 (manufactured by Nippon BEE International Co., Ltd.) equipped with a decompression mechanism, 2,000 kg / cm 2Under a pressure of, dispersion treatment was carried out at a flow rate of 500 g / min. This dispersion treatment was repeated 10 times to obtain a Red pigment dispersion liquid.

[0237] · Green pigment dispersion liquid A mixed liquid consisting of 6.4 parts by mass of C.I.Pigment Green 36, 5.3 parts by mass of C.I.Pigment 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 with a diameter of 0.3 mm) to prepare a pigment dispersion liquid. Then, using a high-pressure disperser NANO-3000-10 (manufactured by Nippon BEE International Co., Ltd.) with a decompression mechanism, at a pressure of 2,000 kg / cm 2 Under a pressure of, dispersion treatment was carried out at a flow rate of 500 g / min. This dispersion treatment was repeated 10 times to obtain a Green pigment dispersion liquid.

[0238] · Blue pigment dispersion liquid A mixed liquid consisting of 9.7 parts by mass of C.I.Pigment Blue 15:6, 2.4 parts by mass of C.I.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 with a diameter of 0.3 mm) to prepare a pigment dispersion liquid. Then, using a high-pressure disperser NANO-3000-10 (manufactured by Nippon BEE International Co., Ltd.) with a decompression mechanism, at a pressure of 2,000 kg / cm 2 Under a pressure of, dispersion treatment was carried out at a flow rate of 500 g / min. This dispersion treatment was repeated 10 times to obtain a Blue pigment dispersion liquid.

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

[0240] · Pigment dispersion liquid 1-2 A mixed liquid with 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 NANO-3000-10 with a decompression mechanism, manufactured by Nippon Bee Inno Co., Ltd.) to prepare pigment dispersion liquid 1-2. · Mixed pigment consisting of a blue pigment (C.I. Pigment Blue 15:6) and a purple pigment (C.I. Pigment Violet 23): 12.6 parts by mass · Resin (Disperbyk-111, manufactured by BYK Chemie): 2.0 parts by mass · Resin A: 3.3 parts by mass · Cyclohexanone: 31.2 parts by mass · PGMEA: 50.9 parts by mass

[0241] Resin A: The following structure (Mw = 14,000, the ratios in each structural unit are molar ratios.)

[0242]

Chemical formula

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

[0244]

Chemical formula

[0245] · Coincidence compound 5: The following structure (a mixture of the left compound and the right compound with a molar ratio of 7:3)

[0246]

Chem.

[0247] · Resin 4: The following structure (acid value: 70 mg KOH / g, Mw = 11,000, and the ratios in each constituent unit are molar ratios.)

[0248]

Chem.

[0249] · Photoinitiator 1: IRGACURE - OXEO1 (1 - [4 - (phenylthio)] - 1,2 - octanedione - 2 - (O - benzoyloxime), manufactured by BASF) · Photoinitiator 2: The following structure

[0250]

Chem.

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

[0252]

Chem.

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

[0254]

Chem.

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

Explanation of Signs

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

Claims

1. A pigment, a resin having at least one of the following structural units, a photopolymerization initiator, and a polymerization inhibitor, wherein the curable composition is 【Chemical 1】 【Chemical Formula 2】 (in each formula, m, n, and p each represent an integer of 1 or more), the resin further has a structural unit represented by the following formula 4, and the polymerization inhibitor has an N - oxyl radical structure, the curable composition. 【Chemical 3】 (In Formula 4, R ６ represents a hydrogen atom or an alkyl group, and X ５ represents -COO-, -CONR Ｂ -, or an arylene group, R Ｂ represents a hydrogen atom, an alkyl group, or an aryl group, L ２ represents an aliphatic hydrocarbon group having 1 to 10 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms, or 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 with one or more structures selected from the group consisting of an ether bond and an ester bond, and furthermore, L ２ may be a single bond when X ５ is an arylene group.)

2. The curable composition according to claim 1, wherein at least one of the said structural units is selected from the following structural units. [Chemical Formula 4] In each formula, n and p each represent an integer of 1 or more.

3. The curable composition according to claim 1 or claim 2, wherein the resin further has a structural unit represented by the following formula 5. [Chemical Formula 5] In Formula 5, R ７ represents a hydrogen atom or an alkyl group, X ６ represents an oxygen atom or -NR Ｃ -, 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 represent an alkyleneoxy group or an alkylene carbonyloxy 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 more, and the value of p + q is 1 or more.

4. The curable composition according to any one of claims 1 to 3, wherein the ethylenically unsaturated bond value of the resin is 0.1 mmol / g to 2.0 mmol / g.

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

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

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

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

9. A step of applying the curable composition according to any one of claims 1 to 6 onto a support to form a composition film, a step of exposing the formed composition film in a pattern, and a step of developing the exposed composition film to form a colored pattern, wherein the method for manufacturing a color filter comprises these steps.

10. A step of applying the curable composition according to any one of claims 1 to 6 onto a support and curing it 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, wherein the method for manufacturing a color filter comprises these steps.

11. A solid - state imaging device having the color filter according to claim 8.

12. An image display device having the color filter according to claim 8.

Images