Curable composition, light-shielding film, solid-state imaging element, image display device, infrared sensor, and method for producing cured film

Abstract

The first problem of the present invention is to provide a curable composition in which a cured film obtained by curing exhibits excellent adhesion and exhibits excellent low reflectivity to infrared light. A second subject of the present invention is to provide a light-shielding film, a solid-state imaging element, an image display device, and an infrared sensor. This curable composition contains a prescribed resin A, a prescribed resin B, a polymerizable compound, a pigment, and a photopolymerization initiator, the ratio of the content of the resin A to the total content of the resin A and the resin B being 0.30-0.50, and the ratio of the content of the polymerizable compound to the total content of the resin A, the resin B, and the polymerizable compound being 0.30-0.50.

Description

Technical Field

[0001] The present invention relates to a curable composition, a light shielding film, a solid-state imaging element, an image display device, an infrared sensor, and a method for producing a cured film. Background Art

[0002] Image display devices such as liquid crystal display devices, and solid-state imaging devices such as CCD (Charge Coupled Device) image sensors and CMOS (Complementary Metal-Oxide Semiconductor) image sensors often have color filters or light shielding films arranged at specified positions. For example, in liquid crystal display devices, in order to shield the light between the colored pixels to improve the contrast, a light shielding film called a black matrix is ​​sometimes arranged between the colored pixels on the color filter. In addition, in solid-state imaging elements, a light shielding film is sometimes used for the purpose of preventing noise and improving image quality.

[0003] A color filter or a light-shielding film is typically produced by curing a curable composition containing a colorant, an alkali-soluble resin, a monomer, and the like.

[0004] For example, Patent Document 1 discloses a coloring composition containing predetermined components for use in a color filter or the like.

[0005] Previous technical literature

[0006] Patent Literature

[0007] Patent Document 1: Japanese Patent Application Publication No. 2022-029341 Summary of the invention

[0008] Technical issues to be solved by the invention

[0009] The light-shielding film is required to have not only light-shielding properties but also low reflectivity, and in recent years, low reflectivity to infrared light is also desired.

[0010] The present inventors have studied the performance of the cured film of the curable composition described in Patent Document 1 and found that there is room for further reducing the reflectivity of infrared light. In addition, in the process of forming a cured film by using the curable composition, when the exposed film is subjected to a development treatment with an alkaline aqueous solution, it is found that the film in the exposed part is easily peeled off from the support. That is, it is found that there is room for further improving the adhesion of the cured film.

[0011] Therefore, an object of the present invention is to provide a curable composition that exhibits excellent adhesion when a cured film is obtained by curing and that exhibits excellent low reflectivity with respect to infrared light.

[0012] Furthermore, an object of the present invention is to provide a light shielding film, a solid-state imaging element, an image display device, an infrared sensor, and a method for producing a cured film.

[0013] Means for solving technical problems

[0014] The present inventors have conducted intensive studies to solve the above-mentioned problems, and have found that the above-mentioned problems can be solved by the following configuration.

[0015] [1] A curable composition comprising a resin A, a resin B, a polymerizable compound, a pigment and a photopolymerization initiator,

[0016] The resin A comprises a repeating unit having an acid group and a repeating unit having a group selected from a polyoxyalkylene group having an average addition number of 3 or more and a polyoxyalkylene carbonyl group having an average addition number of 3 or more.

[0017] The content of the repeating units having a group selected from the group consisting of polyoxyalkylene groups having an average addition number of 3 or more and polyoxyalkylene carbonyl groups having an average addition number of 3 or more is 35% by mass or more relative to all the repeating units of the resin A.

[0018] The acid value of the resin A is 50 mgKOH / g or more.

[0019] The resin B comprises a repeating unit derived from a monomer selected from an alkyl acrylate and an alkyl methacrylate, a repeating unit having a hydroxyl group, and a repeating unit having a carboxylic acid group.

[0020] The content of the repeating units derived from the monomer selected from the group consisting of alkyl acrylates and alkyl methacrylates is 60% by mass or more relative to all the repeating units of the resin B.

[0021] The ratio of the content of the resin A to the total content of the resin A and the resin B is 0.30 to 0.50,

[0022] The ratio of the content of the polymerizable compound to the total content of the resin A, the resin B, and the polymerizable compound is 0.30 to 0.50.

[0023] [2] The curable composition according to [1], wherein

[0024] The repeating unit having an acid group includes one or more selected from the group consisting of a repeating unit represented by formula (A11) described below, a repeating unit represented by formula (A12) described below, and a repeating unit represented by formula (A13) described below.

[0025] [3] The curable composition according to [1] or [2], wherein:

[0026] The resin A further includes a repeating unit having a benzyl group.

[0027] [4] The curable composition according to any one of [1] to [3], wherein

[0028] In the repeating unit derived from a monomer selected from the group consisting of alkyl acrylates and alkyl methacrylates, the alkyl group linked to the ester bond of the alkyl acrylate and alkyl methacrylate has 4 or more carbon atoms.

[0029] [5] The curable composition according to any one of [1] to [4], wherein

[0030] The content of the repeating unit derived from a monomer selected from the group consisting of alkyl acrylates and alkyl methacrylates is 80% by mass or more based on all the repeating units of the resin B.

[0031] [6] The curable composition according to any one of [1] to [5], wherein

[0032] The acid value of the resin B is 55 mgKOH / g or more.

[0033] [7] The curable composition according to any one of [1] to [6], wherein

[0034] The repeating unit having a hydroxyl group includes a repeating unit derived from a monomer selected from 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate.

[0035] [8] The curable composition according to any one of [1] to [7], wherein

[0036] The above pigment contains titanium oxynitride.

[0037] [9] The curable composition according to any one of [1] to [8], which is a light-shielding film-forming composition.

[0038]

[10] A light-shielding film comprising a cured film formed from the curable composition according to any one of [1] to [9].

[0039]

[11] A solid-state imaging device comprising a cured film formed from the curable composition according to any one of [1] to [9].

[0040]

[12] An image display device comprising a cured film formed from the curable composition according to any one of [1] to [9].

[0041]

[13] An infrared sensor comprising a cured film formed from the curable composition according to any one of [1] to [9].

[0042]

[14] An optical filter comprising a cured film formed from the curable composition according to any one of [1] to [9].

[0043]

[15] A cover glass comprising a cured film formed from the curable composition according to any one of [1] to [9].

[0044]

[16] A method for producing a cured film, comprising:

[0045] a composition layer forming step of forming a composition layer on a support using the curable composition described in any one of [1] to [9];

[0046] an exposure step of irradiating the composition layer with actinic rays or radiation; and

[0047] In the development step, the composition layer after exposure is subjected to development treatment.

[0048] Effects of the Invention

[0049] According to the present invention, it is possible to provide a curable composition in which a cured film obtained by curing exhibits excellent adhesion and excellent low reflectivity with respect to infrared light.

[0050] Furthermore, according to the present invention, a light shielding film, a solid-state imaging element, an image display device, an infrared sensor, and a method for producing a cured film can be provided. DETAILED DESCRIPTION

[0051] Hereinafter, the present invention will be described in detail.

[0052] Although the constituent elements described below are sometimes described based on representative embodiments of the present invention, the present invention is not limited to such embodiments.

[0053] In addition, in this specification, the numerical range expressed using "to" means a range including the numerical values ​​described before and after "to" as the lower limit and the upper limit.

[0054] Furthermore, in the description of groups (atomic groups) in this specification, the descriptions that do not record substitution and unsubstituted include groups without substituents and groups with substituents. For example, "alkyl" includes not only alkyl groups without substituents (unsubstituted alkyl groups) but also alkyl groups with substituents (substituted alkyl groups).

[0055] In addition, "actinic rays" or "radiation" in this specification means, for example, far ultraviolet rays, extreme ultraviolet rays (EUV: Extreme ultraviolet lithography), X-rays, electron beams, etc. In addition, in this specification, light means actinic rays and radiation. Unless otherwise specified, "exposure" in this specification includes not only exposure using far ultraviolet rays, X-rays, EUV light, etc., but also drawing using particle beams such as electron beams and ion beams.

[0056] Furthermore, in this specification, "(meth)acrylate" means acrylate and methacrylate. Furthermore, in this specification, "(meth)acrylic acid" means acrylic acid and methacrylic acid. Furthermore, in this specification, "(meth)acryloyl" means acryloyl and methacryloyl. Furthermore, in this specification, "(meth)acrylamide" means acrylamide and methacrylamide. Furthermore, in this specification, "monomer" has the same meaning as "monomer: monomer".

[0057] In this specification, the weight average molecular weight (Mw) is a polystyrene conversion value based on the GPC (Gel Permeation Chromatography) method.

[0058] In this specification, the GPC method is based on a method using HLC-8020GPC (manufactured by TOSOH Corporation), TSKgel SuperHZM-H, TSKgel SuperHZ4000, TSKgel SuperHZ2000 (manufactured by TOSOH Corporation, 4.6 mmID×15 cm) as a column, and THF (tetrahydrofuran) as an eluent.

[0059] In this specification, the "acid value" can be calculated from the average content of the acid groups in the compound, for example.

[0060] In this specification, the solid content in the composition refers to the composition layer formed using the composition, and when the composition contains a solvent, it refers to all components other than the solvent. In addition, if it is a component that forms the composition layer, the liquid component is also regarded as the solid component.

[0061] [Curable composition]

[0062] A curable composition of the present invention comprises resin A, resin B, a polymerizable compound, a pigment and a photopolymerization initiator, wherein:

[0063] The resin A comprises a repeating unit having an acid group (hereinafter also referred to as "repeating unit A1") and a repeating unit having a group selected from a polyoxyalkylene group having an average addition number of 3 or more and a polyoxyalkylene carbonyl group having an average addition number of 3 or more (hereinafter also referred to as "repeating unit A2"),

[0064] The content of the repeating unit having a group selected from the polyoxyalkylene group and the polyoxyalkylene carbonyl group (repeating unit A2) is 35% by mass or more relative to all the repeating units of the resin A,

[0065] The acid value of the resin A is 50 mgKOH / g or more.

[0066] The resin B comprises a repeating unit derived from a monomer selected from an alkyl acrylate and an alkyl methacrylate (hereinafter also referred to as "repeating unit B1"), a repeating unit having a hydroxyl group (hereinafter also referred to as "repeating unit B2"), and a repeating unit having a carboxylic acid group (hereinafter also referred to as "repeating unit B3"),

[0067] The content of the repeating unit (repeating unit B1) derived from a monomer selected from the above alkyl acrylate and alkyl methacrylate is 60% by mass or more relative to all the repeating units of the above resin B,

[0068] The ratio of the content of the resin A to the total content of the resin A and the resin B (hereinafter also referred to as "content ratio T1") is 0.30 to 0.50,

[0069] The ratio of the content of the polymerizable compound to the total content of the resin A, the resin B, and the polymerizable compound (hereinafter also referred to as "content ratio T2") is 0.30 to 0.50.

[0070] Even when the curable composition of the above structure forms a cured film, the film in the exposed part is not easily peeled off from the support body when the exposed film is subjected to a development treatment based on an alkaline aqueous solution. That is, the cured film obtained by curing the curable composition of the above structure has excellent adhesion. In addition, the cured film obtained by curing the curable composition has excellent low reflectivity to infrared light.

[0071] Hereinafter, the estimated mechanism of action of the configuration and effect of the present invention will be described.

[0072] The cured film obtained by curing the curable composition of the above structure has a phase separation structure (for example, a sea island structure, a co-continuous structure, and a structure in which the sea island structure and the co-continuous structure coexist) due to the difference in compatibility between resin A and resin B, and a fine concavo-convex structure can be generated on the surface of the film. It is speculated that the cured film has excellent light scattering properties, especially for infrared light, due to the above concavo-convex structure, and as a result, it shows excellent low reflectivity to infrared light.

[0073] Furthermore, the resin B included in the curable composition has a highly hydrophobic property because the content of the repeating unit derived from the (meth) alkyl acrylate (repeating unit B1) is 60% by mass or more relative to all the repeating units of the resin B. Therefore, it is presumed that when a cured film is produced by using the curable composition, even when the exposed film is subjected to a development treatment using an alkaline aqueous solution, the alkaline aqueous solution is unlikely to penetrate into the exposed film, and as a result, the film in the exposed portion is unlikely to be peeled off from the support.

[0074] Furthermore, it is considered that even when the content ratio T1 and the content ratio T2 are within the predetermined numerical ranges, this greatly contributes to achieving both excellent adhesion of the cured film and excellent low reflectivity of the cured film with respect to infrared light.

[0075] In addition, as a specific form of the phase separation structure of the above-mentioned cured film, there can be cited an island structure or a co-continuous structure of a domain portion consisting of a pigment and resin A and a resin derived from resin A (for example, a resin formed by polymerizing resin A having a polymerizable group) and a matrix portion consisting of a resin B and a resin derived from resin B (for example, a resin formed by polymerizing resin B having a polymerizable group).

[0076] Hereinafter, when the infrared reflectivity of the cured film obtained by curing the curable composition is better, the adhesion of the cured film is better, and / or the development residue (unexposed portion residue) is less, it is also referred to as "the effect of the present invention is better".

[0077] Hereinafter, various components of the curable composition of the present invention will be described.

[0078] 〔Resin A〕

[0079] The curable composition contains resin A.

[0080] Resin A comprises repeating units having an acid group (repeating unit A1) and repeating units of a group selected from polyoxyalkylene groups having an average addition number of 3 or more and polyoxyalkylene carbonyl groups having an average addition number of 3 or more (repeating unit A2), and has an acid value of 50 mgKOH / g or more. Furthermore, the content of repeating unit A2 is 35% by mass or more relative to all repeating units of resin A.

[0081] In addition, a resin including a repeating unit having a carboxylic acid group (belonging to repeating unit A1 and repeating unit B3 described later), a repeating unit having a group selected from a polyoxyalkylene group having an average addition number of 3 or more and a polyoxyalkylene carbonyl group having an average addition number of 3 or more (repeating unit A2), a repeating unit derived from a monomer selected from an alkyl acrylate and an alkyl methacrylate (belonging to repeating unit B1 described later), and a repeating unit having a hydroxyl group (belonging to repeating unit B2 described later), wherein, for a resin having an acid value of 50 mgKOH / g or more, the content of the repeating unit having a group selected from the polyoxyalkylene group having an average addition number of 3 or more and the polyoxyalkylene carbonyl group having an average addition number of 3 or more (repeating unit A2) is 35% by mass or more relative to all repeating units of the resin, and the content of the repeating unit derived from the monomer selected from the alkyl acrylate and the alkyl methacrylate (repeating unit B1) is 60% by mass or more relative to all repeating units of the resin belongs to resin A.

[0082] In addition, the structure is different from that of the repeating unit A1 and the repeating unit A2.

[0083] Furthermore, the repeating unit A1 may have a group selected from an oxyalkylene group and an oxyalkylenecarbonyl group. When the repeating unit A1 contains a group selected from an oxyalkylene group and an oxyalkylenecarbonyl group, the average number of added oxyalkylene groups and the average number of added oxyalkylenecarbonyl groups are preferably 1-2.

[0084] The repeating unit A2 preferably contains no acid groups.

[0085] It is speculated that the resin A is adsorbed on the surface of the dispersed body such as the pigment through the above structure, and also acts as a resin that can prevent the dispersed body from re-aggregating. Specifically, the repeating unit A1 contained in the resin A becomes an anchor site on the pigment surface, and the re-aggregation of the dispersed body can be prevented by the steric repulsion effect based on the repeating unit A2.

[0086] In addition, as resin A, from the viewpoint that the steric repulsion effect based on the repeating unit A2 is further excellent and the effect of the present invention is more excellent, it is preferably a grafted polymer having a graft chain containing a group selected from polyoxyalkylene groups having an average addition number of 3 or more and polyoxyalkylene carbonyl groups having an average addition number of 3 or more.

[0087] When resin A is a grafted polymer, resin A has affinity with the solvent through the graft chain, so the dispersibility of the pigment and the dispersion stability after time are excellent. In addition, due to the presence of the graft chain, it is easier to produce a difference in compatibility between resin A and resin B, and the effect of the present invention is more likely to be more excellent. In addition, if the graft chain is a specified length, the adsorption force to the dispersed body such as the pigment is increased, thereby tending to improve its dispersibility. Therefore, the number of atoms other than hydrogen atoms in the graft chain is preferably 40 to 10,000, more preferably 50 to 2,000, and further preferably 60 to 500. Here, the graft chain represents the root of the main chain of the copolymer (the atom bonded to the main chain in the group branched from the main chain) to the end of the group branched from the main chain.

[0088] The macromonomer containing such a graft chain (a monomer having a polymer structure and bonding to the main chain of the copolymer to form a graft chain) is not particularly limited, and a macromonomer containing a reactive double-bonding group can be preferably used.

[0089] Hereinafter, the repeating units contained in the resin A will be described.

[0090] <Repeating Unit A1>

[0091] The resin A includes a repeating unit having an acid group (repeating unit A1). In the resin A, the repeating unit A1 not only functions as the above-mentioned pigment adsorption group, but also tends to further improve the developability of the resin A with respect to an alkaline developer.

[0092] Examples of the acid group include a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, and a phenolic hydroxyl group. Among them, a carboxylic acid group is preferred.

[0093] In the repeating unit A1, the number of acid groups may be 1 or more, and for example, 1 to 6 are included.

[0094] The specific structure of the repeating unit A1 is not particularly limited, but a repeating unit represented by the following formula (AX1) is preferred from the viewpoint of easily achieving more excellent effects of the present invention.

[0095] [Chemical formula 1]

[0096]

[0097] In the formula, R A1 It represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.

[0098] As R A1 The number of carbon atoms of the alkyl group represented by is preferably 1 to 3, and more preferably 1.

[0099] L A1 Represents a single bond, -COO- or -CONRA2 -. R A2 With the above R A1 The meanings are the same and the preferred aspects are also the same.

[0100] L A2 represents a single bond or a divalent linking group.

[0101] The type of the divalent linking group is not particularly limited, and examples thereof include divalent aliphatic hydrocarbon groups, divalent aromatic hydrocarbon groups, -O-, -S-, -SO2-, -NR A3 -, -CO-, and a group consisting of two or more of these.

[0102] The divalent aliphatic hydrocarbon group may be any of linear, branched, and cyclic, and preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms.

[0103] Examples of the divalent aliphatic hydrocarbon group include an alkylene group, an alkenylene group, and an alkynylene group. Among them, an alkylene group is preferred.

[0104] The divalent aromatic hydrocarbon group preferably has 6 to 10 carbon atoms, and an example thereof is phenylene.

[0105] The divalent aliphatic hydrocarbon group and the divalent aromatic hydrocarbon group may further have a substituent. The substituent is not particularly limited, and may be, for example, a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, or an acid group such as a phenolic hydroxyl group.

[0106] The above R A3 With the above R A1 The meanings are the same and the preferred aspects are also the same.

[0107] Among them, the divalent linking group is preferably a group in which two or more groups selected from the group consisting of an alkylene group which may have a substituent, a phenylene group which may have a substituent, -O-, and -CO- are combined.

[0108] In the above formula (AX1), -L A1 -L A2 The number of atoms other than hydrogen atoms in the portion represented by - is preferably less than 40, for example.

[0109] W A1 Indicates an acid group.

[0110] The acid group is as described above.

[0111] From the viewpoint of achieving more excellent effects of the present invention, the repeating unit A1 preferably contains one or more selected from the group consisting of a repeating unit represented by the following formula (A11), a repeating unit represented by the following formula (A12), and a repeating unit represented by the following formula (A13).

[0112] In formula (A13), n represents the average addition number and is 1 to 2.

[0113] [Chemical formula 2]

[0114]

[0115] The resin A may contain one type of repeating unit A1 alone, or two or more types thereof.

[0116] The content of repeating unit A1 in resin A is preferably 5 to 50% by mass, more preferably 5 to 40% by mass, and further preferably 10 to 40% by mass relative to all repeating units of resin A. When two or more repeating units A1 are used simultaneously, the total content is preferably within the above range.

[0117] <Repeating Unit A2>

[0118] Resin A contains a repeating unit (repeating unit A2) having a group selected from polyoxyalkylene groups having an average addition number of 3 or more and polyoxyalkylene carbonyl groups having an average addition number of 3 or more. As described above, it is presumed that in resin A, the repeating unit A2 not only plays a role in preventing the reagglomeration of the dispersed body such as the pigment, but also contributes to the formation of a phase separation structure when a cured film is formed.

[0119] In addition, an oxyalkylene group represents a group represented by -O-AL-, and an oxyalkylenecarbonyl group represents a group represented by -O-AL-CO-. AL represents an alkylene group.

[0120] Furthermore, the polyoxyalkylene group is represented by -(O-AL) n1 -, polyoxyalkylenecarbonyl is represented by -(O-AL-CO) n2 -represented group.

[0121] In the polyoxyalkylene group and the polyoxyalkylene carbonyl group, a plurality of oxyalkylene groups (—O—AL—) may be the same or different.

[0122] The number of carbon atoms of the alkylene group in the oxyalkylene group and the oxyalkylenecarbonyl group (the number of carbon atoms of AL) is not particularly limited, but is preferably 2-10, more preferably 2-9, and even more preferably 2-7.

[0123] The average addition number (n1) in the polyoxyethylene is 3 or more, preferably 4 or more, more preferably 5 or more, further preferably 6 or more, particularly preferably 10 or more, and most preferably 15 or more. The upper limit is preferably 100 or less, more preferably 70 or less, and further preferably 30 or less.

[0124] The average addition number (n2) in the oxyalkylenecarbonyl group is 3 or more, preferably 4 or more, more preferably 5 or more, and further preferably 6 or more. The upper limit is preferably 100 or less, more preferably 70 or less, and further preferably 30 or less.

[0125] In a polyoxyalkylene group having an average addition number of 3 or more, the carbon number of the alkylene moiety of the plurality of oxyalkylene groups may be the same or different. The case where the carbon number of the alkylene moiety of the plurality of oxyalkylene groups is different means, for example, a structure including an oxyethylene group and an oxypropylene group. Furthermore, in a polyoxyalkylene carbonyl group having an average addition number of 3 or more, the carbon number of the alkylene moiety of the plurality of polyoxyalkylene carbonyl groups may be the same or different. The case where the carbon number of the alkylene moiety of the plurality of oxyalkylene carbonyl groups is different means, specifically, a structure including an oxyethylene carbonyl group and an oxypropylene carbonyl group.

[0126] The repeating unit A2 is preferably a repeating unit represented by any one of the following formulae (1) to (3), and more preferably a repeating unit represented by the following formula (1) or (3).

[0127] [Chemical formula 3]

[0128]

[0129] In formulas (1) to (3), W 1 , W 2 and W 3 Each independently represents an oxygen atom or NH. 1 , W 2 and W 3 , preferably an oxygen atom.

[0130] In formulas (1) to (3), X 1 , X 2 and X 3 Each independently represents a hydrogen atom or a monovalent organic group. 1 , X 2 and X 3 , from the viewpoint of synthetic constraints, each independently preferably is a hydrogen atom or an alkyl group having 1 to 12 carbon atoms (carbon number), more preferably each independently is a hydrogen atom or a methyl group, and still more preferably a methyl group.

[0131] In formulas (1) to (3), Y 1 , Y 2 and Y 3 Each independently represents a divalent linking group. 1 , Y 2 and Y 3The structure of the divalent linking group represented is not particularly limited, and specifically, as an example, the following linking groups (Y-1) to (Y-21) can be cited. In the structures shown below, A and B respectively refer to the bonding sites to the left terminal group and the right terminal group in formulas (1) to (3).

[0132] [Chemical formula 4]

[0133]

[0134] In formulas (1) to (3), Z 1 , Z 2 and Z 3 Each independently represents a hydroxyl group, an amino group or a monovalent organic group. The organic group is not particularly limited, and specific examples thereof include an alkyl group, an alkoxy group, an aryloxy group, a heteroaryloxy group, an alkylthioether group, an arylthioether group, and a heteroarylthioether group.

[0135] As Z 1 , Z 2 and Z 3 The alkyl moiety in the alkyl group, alkoxy group and alkyl thioether group represented by may be linear, branched or cyclic, and the number of carbon atoms is preferably 1 to 30. The methylene group in the alkoxy group may be substituted by -O-.

[0136] As Z 1 , Z 2 and Z 3 The organic group represented by is preferably a group having a steric repulsion effect, particularly from the viewpoint of improving dispersibility, and is more preferably an alkyl group or alkoxy group having 5 to 24 carbon atoms, and further preferably a branched alkyl group having 5 to 24 carbon atoms, a cyclic alkyl group having 5 to 24 carbon atoms, or an alkoxy group having 5 to 24 carbon atoms.

[0137] Furthermore, each of the above groups may have a substituent (for example, an ethylenically unsaturated group such as a hydroxyl group and a (meth)acryloyloxy group).

[0138] In addition, in formula (1), when Z 1 When it is a hydroxyl group, the -COZ 1 The indicated site can be anionized (-COO - ). In this case, as the counter cation, a quaternary ammonium salt can be mentioned.

[0139] In formulas (1) and (2), n and m represent average addition numbers and represent numbers greater than or equal to 3. As the lower limits of n and m, preferably 4 or greater, more preferably 5 or greater, and even more preferably 6 or greater. As the upper limits of n and m, preferably 100 or less, more preferably 70 or less, even more preferably 50 or less, and particularly preferably 30 or less.

[0140] In formula (3), p represents an average addition number and represents a number greater than or equal to 3. As the lower limit value of p, it is preferably greater than or equal to 4, more preferably greater than or equal to 5, further preferably greater than or equal to 6, further preferably greater than or equal to 10, particularly preferably greater than or equal to 15, and most preferably greater than or equal to 20. As the upper limit value of p, it is preferably less than or equal to 100, more preferably less than or equal to 70, further preferably less than or equal to 50, and particularly preferably less than or equal to 30.

[0141] Furthermore, in formulae (1) and (2), j and k each independently represent an integer of 2 to 10. From the viewpoint of achieving better viscosity stability over time and developability of the curable composition, j and k in formulae (1) and (2) are preferably integers of 2 to 9, more preferably integers of 2 to 7, further preferably integers of 4 to 6, and particularly preferably 5.

[0142] And, in formula (3), R 3 represents a branched or linear alkylene group. The number of carbon atoms in the alkylene group is preferably 2 to 10, more preferably 2 to 9, further preferably 2 to 7, and particularly preferably 2 or 3. When p is 2 to 100, there are a plurality of R 3 They can be the same as each other or different.

[0143] From the viewpoint of achieving more excellent effects of the present invention, the repeating unit A2 is preferably a repeating unit having 3 or more polyoxyalkylene carbonyl groups added on average, more preferably a repeating unit represented by the above formula (1) or (2), and still more preferably a repeating unit represented by the above formula (1).

[0144] The resin A may contain one type of repeating unit A2 alone, or two or more types thereof.

[0145] In resin A, the content of repeating unit A2 is 35% by mass or more, preferably 40% by mass or more, more preferably 50% by mass or more, and further preferably 60% by mass or more relative to all repeating units of resin A. In addition, as an upper limit, it is preferably 90% by mass or less, more preferably 80% by mass or less, and further preferably 75% by mass or less. When two or more repeating units A2 are used simultaneously, the total content is preferably within the above range.

[0146] <Other Repeating Units (Repeating Unit A3)>

[0147] The resin A may contain other repeating units (hereinafter also referred to as "repeating units A3") other than the above-mentioned repeating units A1 and A2.

[0148] Examples of other repeating units include other repeating units having various functions other than the above-mentioned repeating units.

[0149] Other repeating units include hydrophobic repeating units (hereinafter also referred to as "repeating units A31"), repeating units having curable groups (hereinafter also referred to as "repeating units A32"), repeating units having functional groups capable of interacting with pigments, etc. (hereinafter also referred to as "repeating units A33"), and repeating units derived from free radical monomers selected from acrylonitriles and methacrylonitris.

[0150] (Repeating unit A31)

[0151] The resin A may contain a hydrophobic repeating unit (repeating unit A31).

[0152] One embodiment of the repeating unit A31 is a repeating unit derived from a compound (monomer) having a ClogP value of 1.2 or more, and among these, a repeating unit derived from a compound having a ClogP value of 1.2 to 8 is preferred.

[0153] In this specification, the ClogP value is a value calculated by the program "CLOGP" that can be obtained from Daylight Chemical Information System, Inc. The program provides the value of "calculated logP" calculated by the fragment method of Hansch, Leo (refer to the following document). The fragment method divides the chemical structure into partial structures (fragments) according to the chemical structure of the compound, and calculates the logP value of the compound by adding up the logP contribution amount assigned to the fragment. The details are described in the following document. In this specification, the ClogP value calculated by the program CLOGP v4.82 is used.

[0154] AJLeo, Comprehensive Medicinal Chemistry, Vol.4, C.Hansch, PGSammnens, JBTaylor and CARamsden, Eds., p.295, Pergamon Press, 1990 C.Hansch&A.J.Leo.SUbstituent Constants For Correlation Analysis in Chemistry and Biology.John Wiley&Sons.AJLeo.Calculating logPoct fromstructure.Chem.Rev., 93, 1281-1306, 1993.

[0155] LogP refers to the common logarithm of the partition coefficient P (Partition Coefficient), and is a physical property value that expresses how a certain organic compound is distributed in the equilibrium of a two-phase system of oil (usually 1-octanol) and water as a quantitative value, and is represented by the following formula.

[0156] logP=log(Coil / Cwater)

[0157] Wherein, Coil represents the molar concentration of the compound in the oil phase, and Cwater represents the molar concentration of the compound in the water phase.

[0158] If the logP value increases positively from 0, the oil solubility increases, and if the absolute value increases negatively, the water solubility increases. It has a negative correlation with the water solubility of organic compounds and is widely used as a parameter for estimating the hydrophilicity / hydrophobicity of organic compounds.

[0159] Furthermore, as another embodiment of the repeating unit A31, a repeating unit represented by the following formula (AX2) can be mentioned.

[0160] [Chemical formula 5]

[0161]

[0162] In the formula, R A4 It represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.

[0163] As R A4 The number of carbon atoms in the alkyl group represented by is preferably 1 or 2, more preferably 1.

[0164] R A5 The term "alkyl group" refers to a linear or branched alkyl group having 1 to 12 carbon atoms or an aralkyl group having 7 to 18 carbon atoms, and is preferably an aralkyl group having 7 to 18 carbon atoms from the viewpoint of further improving the effects of the present invention.

[0165] As R A5 The number of carbon atoms of the alkyl group represented by is preferably 1 to 8, more preferably 1 to 6, and even more preferably 1 to 4. Furthermore, it is preferably a linear alkyl group.

[0166] As R A5 The number of carbon atoms of the aralkyl group represented by is preferably 7-18, more preferably 7-12, and further preferably 7-10.

[0167] And, R A5 The alkyl group and aralkyl group represented by may have a substituent. The substituent is not particularly limited, and an example thereof includes a hydroxyl group.

[0168] From the viewpoint of achieving more excellent effects of the present invention, the repeating unit A31 is preferably a repeating unit having a benzyl group, and more preferably a repeating unit derived from benzyl (meth)acrylate.

[0169] The resin A may contain one type of repeating unit A31 alone, or two or more types thereof.

[0170] In resin A, the content of repeating unit A31 is preferably 5 to 50% by mass, more preferably 5 to 40% by mass, and further preferably 10 to 40% by mass relative to all repeating units of resin A. When two or more repeating units A31 are used simultaneously, the total content is preferably within the above range.

[0171] (Repeating unit A32)

[0172] The resin A may include a repeating unit having a curable group (repeating unit A32).

[0173] As the curable group, for example, ethylenically unsaturated groups (such as (meth) acryloyl, vinyl and styryl groups) and cyclic ether groups (such as epoxy and oxetane groups) can be cited. Among them, as the curable group, ethylenically unsaturated groups are preferred from the viewpoint of being able to control polymerization in a free radical reaction. As the ethylenically unsaturated group, (meth) acryloyl is preferred.

[0174] The specific structure of the repeating unit A32 is not particularly limited, but is preferably a repeating unit represented by the following formula (AX3).

[0175] [Chemical formula 6]

[0176]

[0177] In the formula, R A11 It represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.

[0178] As R A11 The number of carbon atoms of the alkyl group represented by is preferably 1 to 3, and more preferably 1.

[0179] L A11 Represents a single bond, -COO- or -CONR A12 -. R A12 With the above R A11 The meanings are the same and the preferred aspects are also the same.

[0180] L A12 represents a single bond or a divalent linking group.

[0181] The type of the divalent linking group is not particularly limited, and examples thereof include divalent aliphatic hydrocarbon groups, divalent aromatic hydrocarbon groups, -O-, -S-, -SO2-, -NR A13 -, -CO-, and a group consisting of two or more of these.

[0182] The divalent aliphatic hydrocarbon group may be any of linear, branched, and cyclic, and preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms.

[0183] Examples of the divalent aliphatic hydrocarbon group include an alkylene group, an alkenylene group, and an alkynylene group. Among them, an alkylene group is preferred.

[0184] The divalent aromatic hydrocarbon group preferably has 6 to 10 carbon atoms, and an example thereof is phenylene.

[0185] The divalent aliphatic hydrocarbon group and the divalent aromatic hydrocarbon group may further have a substituent. The substituent is not particularly limited, and examples thereof include acid groups such as a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, and a phenolic hydroxyl group, and a hydroxyl group.

[0186] The above R A13 With the above R A11 The meanings are the same and the preferred aspects are also the same.

[0187] Among them, the divalent linking group is preferably a group in which two or more groups selected from the group consisting of an alkylene group which may have a substituent, -O-, and -CO- are combined.

[0188] In the above formula (AX3), as -L A11 -L A12 The number of atoms other than hydrogen atoms in the portion represented by - is preferably less than 40, for example.

[0189] W A11 represents a curable group.

[0190] As W A11 The curable group represented by includes the curable groups already described.

[0191] The resin A may contain one type of repeating unit A32 alone, or two or more types thereof.

[0192] In resin A, the content of repeating unit A32 is preferably 5 to 50% by mass, more preferably 5 to 40% by mass, and further preferably 10 to 40% by mass relative to all repeating units of resin A. When two or more repeating units A32 are used simultaneously, the total content is preferably within the above range.

[0193] (Repeating unit A33)

[0194] The resin A may include a repeating unit (repeating unit A33) having a functional group capable of forming an interaction with a pigment or the like.

[0195] Examples of the functional group capable of interacting with a pigment or the like include a basic group, a ligand, and a reactive functional group.

[0196] Examples of the basic group include a primary amino group, a secondary amino group, a tertiary amino group, a heterocyclic ring containing a N atom, and an amide group. Among them, a tertiary amino group is preferred from the viewpoint of good adsorption to a pigment and high dispersibility.

[0197] The resin A may contain one type of repeating unit containing a basic group alone, or may contain two or more types.

[0198] In resin A, the content of the repeating unit containing a basic group is preferably 0.01 to 50% by mass, and more preferably 0.01 to 30% by mass, relative to all repeating units of resin A, from the viewpoint of suppressing the development inhibition. When two or more repeating units containing a basic group are used simultaneously, the total content is preferably within the above range.

[0199] Examples of the ligand and reactive functional group include acetoacetoxy, trialkoxysilyl, isocyanate, acid anhydride and acid chloride. Among them, acetoacetoxy is preferred from the viewpoint of good adsorption to pigments and high dispersibility of pigments.

[0200] The resin A may contain one type of repeating unit containing a ligand alone, or two or more types thereof.

[0201] In resin A, the content of the repeating unit containing a ligand is preferably 0.01 to 50% by mass, more preferably 0.01 to 30% by mass, based on all repeating units of resin A. When two or more repeating units containing a ligand are used simultaneously, the total content is preferably within the above range.

[0202] The resin A may contain one type of repeating unit containing a reactive functional group alone, or two or more types thereof.

[0203] The content of the reactive functional group in the resin A is preferably 0.01 to 50% by mass, more preferably 0.01 to 30% by mass, based on all repeating units of the resin A. When two or more reactive repeating units are used simultaneously, the total content is preferably within the above range.

[0204] The content of the resin A in the curable composition is not particularly limited, but is preferably 2 to 40% by mass, more preferably 5 to 30% by mass, and even more preferably 10 to 25% by mass, based on the total solid content of the curable composition.

[0205] The resin A may be used alone or in combination of two or more. When two or more resins A are used in combination, the total content is preferably within the above range.

[0206] The acid value of resin A is 50 mgKOH / g or more, preferably 55 mgKOH / g or more, and more preferably 60 mgKOH / g or more, from the viewpoint of ensuring the developability to the alkaline developer. As the upper limit, it is preferably 200 mgKOH / g or less, more preferably 150 mgKOH / g or less, further preferably 100 mgKOH / g or less, and particularly preferably 80 mgKOH / g or less. In addition, by changing the content of the repeating unit containing the acid group, which is the constituent component of resin A, a resin having a desired acid value can be obtained.

[0207] The weight average molecular weight of the resin A is preferably 5,000 to 100,000, more preferably 6,000 to 80,000, further preferably 15,000 to 40,000, and most preferably 20,000 to 40,000.

[0208] The glass transition temperature of the resin A is preferably -20 to 100° C., more preferably -20 to 80° C., and further preferably -10 to 60° C. The glass transition temperature can be measured by DSC 3500 Sirius (manufactured by Netzsch).

[0209] 〔Resin B〕

[0210] The curable composition contains resin B.

[0211] In addition, the resin B preferably does not contain a repeating unit having a group selected from a polyoxyalkylene group having an average addition number of 3 or more and a polyoxyalkylene carbonyl group having an average addition number of 3 or more.

[0212] The resin B comprises a repeating unit derived from an alkyl (meth)acrylate (repeating unit B1), a repeating unit having a hydroxyl group (repeating unit B2), and a repeating unit having a carboxylic acid group (repeating unit B3), wherein the content of the repeating unit B1 is 60% by mass or more relative to all the repeating units of the resin B. The resin B having the above structure improves the adhesion of a cured film formed from the curable composition, and can form a phase separation structure due to the difference in compatibility with the resin A.

[0213] Hereinafter, the repeating unit contained in the resin B will be described.

[0214] <Repeating Unit B1>

[0215] Resin B contains a repeating unit derived from an alkyl (meth)acrylate (repeating unit B1).

[0216] The alkyl group linked to the ester bond in the alkyl (meth)acrylate may be linear, branched, or cyclic, but is preferably linear or branched from the viewpoint of achieving more excellent effects of the present invention.

[0217] The number of carbon atoms in the alkyl group is preferably 1 or more, and from the viewpoint of achieving a more excellent effect of the present invention, is preferably 4 or more. The upper limit is preferably 20 or less, more preferably 12 or less, and even more preferably 10 or less.

[0218] The alkyl group may or may not have a substituent, but preferably has no substituent from the viewpoint of more excellent effects of the present invention. In addition, when the alkyl group has a substituent, it is preferably a substituent other than a hydroxyl group and a carboxylic acid group.

[0219] The resin B may contain one type of repeating unit B1 alone, or two or more types thereof.

[0220] In resin B, the content of repeating unit B1 is 60% by mass or more, preferably 61% by mass or more, more preferably 65% ​​by mass or more, further preferably 70% by mass or more, and particularly preferably 80% by mass or more relative to all repeating units of resin B. In addition, there is no particular restriction on the upper limit thereof, but it is preferably 99% by mass or less, more preferably 95% by mass or less. When two or more repeating units B1 are used simultaneously, the total content is preferably within the above range.

[0221] <Repeating Unit B2>

[0222] Resin B contains a repeating unit having a hydroxyl group (repeating unit B2).

[0223] The repeating unit B2 is a repeating unit different from the above-mentioned repeating unit B1.

[0224] The repeating unit B2 preferably has no carboxylic acid group.

[0225] In the repeating unit B2, the number of hydroxyl groups may be 1 or more, and for example, 1 to 6 are included.

[0226] The specific structure of the repeating unit B2 is not particularly limited, but is preferably a repeating unit represented by the following formula (BX1).

[0227] [Chemical formula 7]

[0228]

[0229] R B1 It represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.

[0230] As R B1 The number of carbon atoms of the alkyl group represented by is preferably 1 to 3, and more preferably 1.

[0231] L B1 Represents a single bond, -COO- or -CONR B2 -. R B2 With the above R B1 The meanings are the same and the preferred aspects are also the same.

[0232] L B2 represents a single bond or a divalent linking group.

[0233] The type of the divalent linking group is not particularly limited, and examples thereof include divalent aliphatic hydrocarbon groups, divalent aromatic hydrocarbon groups, -O-, -S-, -SO2-, -NR B3 -, -CO-, and a group consisting of two or more of these.

[0234] The divalent aliphatic hydrocarbon group may be any of linear, branched, and cyclic, and preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms.

[0235] Examples of the divalent aliphatic hydrocarbon group include an alkylene group, an alkenylene group, and an alkynylene group. Among them, an alkylene group is preferred.

[0236] The divalent aromatic hydrocarbon group preferably has 6 to 10 carbon atoms, and an example thereof is phenylene.

[0237] The divalent aliphatic hydrocarbon group and the divalent aromatic hydrocarbon group may further have a substituent. In addition, the substituent is not particularly limited, and examples thereof include a hydroxyl group and the like.

[0238] The above R B3 With the above R B1 The meanings are the same and the preferred aspects are also the same.

[0239] Among them, the divalent linking group is preferably an alkylene group which may have a substituent or an alkylene group which may have a substituent and may contain a group selected from -O- and -CO-.

[0240] In the above formula (BX1), -L B1 -L B2 The number of atoms other than hydrogen atoms in the portion represented by - is preferably less than 40, for example.

[0241] W B1represents a hydroxyl group or a curable group.

[0242] As W B1 The curable group represented by includes the curable groups already described.

[0243] As W B1 , preferably represents a hydroxyl group. In addition, when W B1 When the repeating unit B2 represents a curable group, it is preferred that B1 Among them, L is preferably B2 The divalent linking group represented by and the divalent linking group includes a hydroxyl group.

[0244] As the repeating unit B2, from the viewpoint of achieving more excellent effects of the present invention, a repeating unit derived from 2-ethylhydroxy(meth)acrylate is preferred.

[0245] The resin B may contain one type of repeating unit B2 alone, or two or more types thereof.

[0246] In resin B, as the lower limit of the content of repeating unit B2, relative to all repeating units of resin B, preferably 1% by mass or more, more preferably 2% by mass or more, and further preferably 5% by mass or more. As its upper limit, preferably 50% by mass or less, more preferably 40% by mass or less, and further preferably 20% by mass or less. As one mode of the content of repeating unit B2, relative to all repeating units of resin B, preferably 1 to 50% by mass, more preferably 5 to 50% by mass, further preferably 5 to 40% by mass, particularly preferably 10 to 40% by mass, and most preferably 10 to 20% by mass. When two or more repeating units B2 are used simultaneously, the total content is preferably within the above range.

[0247] <Repeating Unit B3>

[0248] Resin B contains a repeating unit having a carboxylic acid group (repeating unit B3).

[0249] The repeating unit B3 is a repeating unit different from the repeating unit B1 and the repeating unit B2. The repeating unit B3 preferably does not have a hydroxyl group.

[0250] In the repeating unit B3, the number of the carboxylic acid groups may be 1 or more, and may be, for example, 1 to 6.

[0251] Specifically, among the repeating units represented by the formula (AX1) exemplified as the repeating units A1 contained in the resin A, the repeating units B3 may be: A1 The acid group represented by is set as a repeating unit of a carboxylic acid group, and the preferred embodiment is also the same.

[0252] The resin B may contain one type of repeating unit B3 alone, or two or more types thereof.

[0253] In resin B, the content of repeating unit B3 is preferably 5 to 40% by mass, more preferably 5 to 30% by mass, and further preferably 10 to 30% by mass relative to all repeating units of resin B. When two or more repeating units B3 are used simultaneously, the total content is preferably within the above range.

[0254] <Other Repeating Units (Repeating Unit B4)>

[0255] The resin B may contain another repeating unit (hereinafter also referred to as "repeating unit B4") other than the above-mentioned repeating units B1 to B3.

[0256] As other repeating units, other repeating units having various functions other than the above-mentioned repeating units may be contained.

[0257] Examples of other repeating units include a hydrophobic repeating unit (hereinafter, also referred to as "repeating unit B41") and the like.

[0258] Examples of the repeating unit B41 include a repeating unit derived from styrenes (for example, styrene and α-methylstyrene) and the same repeating unit as the repeating unit A31 contained in the resin A.

[0259] The resin B may contain one type of repeating unit B41 alone, or two or more types thereof.

[0260] The content of the repeating unit B41 in the resin B is preferably 1 to 15% by mass, more preferably 5 to 15% by mass, based on all the repeating units of the resin B. When two or more repeating units B41 are used simultaneously, the total content is preferably within the above range.

[0261] The content of the resin B in the curable composition is not particularly limited, but is preferably 2 to 40% by mass, more preferably 5 to 30% by mass, and even more preferably 10 to 25% by mass, based on the total solid content of the curable composition.

[0262] The resin B may be used alone or in combination of two or more. When two or more resins B are used in combination, the total content is preferably within the above range.

[0263] The acid value of resin B is preferably 0 mgKOH / g or more, more preferably 20 mgKOH / g or more, further preferably 40 mgKOH / g or more, and particularly preferably 55 mgKOH / g or more. In addition, as an upper limit, it is preferably 150 mgKOH / g or less, more preferably 100 mgKOH / g or less, and further preferably 90 mgKOH / g or less. In addition, by changing the content of the repeating unit containing the acid group, which is a constituent component of resin B, a resin having a desired acid value can be obtained.

[0264] The weight average molecular weight of the resin B is preferably 5,000 to 100,000, more preferably 8,000 to 80,000, further preferably 15,000 to 40,000, and particularly preferably 18,000 to 25,000.

[0265] The glass transition temperature of the resin B is preferably -20 to 120°C, preferably -20 to 110°C, more preferably -5 to 80°C, and further preferably 0 to 70°C.

[0266] The glass transition temperature can be measured by DSC 3500 Sirius (manufactured by Netzsch).

[0267] 〔Relationship between the contents of resin A and resin B〕

[0268] In the curable composition, the ratio of the content of resin A to the total content of resin A and resin B (content ratio T1. content of resin A / total content of resin A and resin B) is 0.30 to 0.50, preferably 0.33 to 0.47, and more preferably 0.35 to 0.45. When the content ratio T1 is within the above numerical range, the phase separation of resin A and resin B is excellent, and the obtained cured product shows excellent low reflectivity to infrared light.

[0269] 〔Polymerizable compounds〕

[0270] The curable composition contains a polymerizable compound.

[0271] In the present specification, the "polymerizable compound" refers to an organic compound (for example, an organic compound containing an ethylenically unsaturated group) that can be polymerized by the action of a photopolymerization initiator or the like described later.

[0272] When the curable composition contains a solvent, the polymerizable compound is preferably present while being dissolved in the solvent.

[0273] The molecular weight (weight average molecular weight when having a molecular weight distribution) of the polymerizable compound is not particularly limited, but is preferably 2500 or less. The lower limit is preferably 100 or more.

[0274] The polymerizable compound is preferably a compound containing an ethylenically unsaturated group (a group containing an ethylenically unsaturated bond).

[0275] That is, the curable composition preferably contains a low-molecular compound containing an ethylenically unsaturated group as a polymerizable compound.

[0276] As the polymerizable compound, a compound containing one or more ethylenically unsaturated bonds is preferred, a compound containing two or more ethylenically unsaturated bonds is more preferred, a compound containing three or more ethylenically unsaturated bonds is further preferred, and a compound containing four or more ethylenically unsaturated bonds is particularly preferred. The upper limit is, for example, 15 or less. As the ethylenically unsaturated group, for example, vinyl, (meth)allyl and (meth)acryloyl can be cited.

[0277] As the polymerizable compound, for example, the compounds described in paragraph

[0050] of JP-A-2008-260927 and paragraph

[0040] of JP-A-2015-068893 can be cited, and the contents thereof are incorporated into the present specification.

[0278] The polymerizable compound may be in any chemical form such as a monomer, a prepolymer, an oligomer, a mixture thereof, or a multimer thereof.

[0279] The polymerizable compound is preferably a tri- to penta-functional (meth)acrylate compound, and more preferably a tri- to hexa-functional (meth)acrylate compound.

[0280] The polymerizable compound is also preferably a compound having one or more ethylenically unsaturated groups and having a boiling point of 100° C. or higher under normal pressure. For example, compounds described in paragraph

[0227] of JP-A-2013-029760 and paragraphs

[0254] to

[0257] of JP-A-2008-292970 can be cited, and the contents are incorporated into this specification.

[0281] The polymerizable compound is preferably dipentaerythritol triacrylate (commercially available products, for example, KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (commercially available products, for example, KAYARAD D-320; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol penta(meth)acrylate (commercially available products, for example, KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa(meth)acrylate (commercially available products, for example, KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., A-DPH-12E; manufactured by SHIN-NAKAMURACHEMICAL Co., Ltd.), and a structure in which these (meth)acryloyl groups are interrupted by ethylene glycol residues or propylene glycol residues (for example, SR454 and SR499 commercially available from Sartomer Company, Inc.). These oligomer types can also be used. In addition, NK Ester A-TMMT (pentaerythritol tetraacrylate, manufactured by SHIN-NAKAMURA CHEMICAL Co., Ltd.), KAYARAD RP-1040, KAYARAD DPEA-12LT, KAYARAD DPHA LT, KAYARAD RP-3060 and KAYARAD DPEA-12 (all trade names, manufactured by Nippon Kayaku Co., Ltd.) can be used. In addition, as the polymerizable compound, a urethane (meth)acrylate-based compound having both a (meth)acryloyl group and a urethane bond in the compound can be used, and for example, KAYARAD DPHA-40H (trade name, manufactured by Nippon Kayaku Co., Ltd.) can also be used.

[0282] Preferred embodiments of the polymerizable compound are shown below.

[0283] The polymerizable compound may have an acid group such as a carboxylic acid group, a sulfonic acid group, and a phosphoric acid group. The polymerizable compound containing an acid group is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, more preferably a polymerizable compound having an acid group by reacting a non-aromatic carboxylic acid anhydride with an unreacted hydroxyl group of an aliphatic polyhydroxy compound, and further preferably a compound in which the aliphatic polyhydroxy compound in the ester is pentaerythritol and / or dipentaerythritol. Examples of commercially available products include ARONIX TO-2349, M-305, M-510, and M-520 manufactured by TOAGOSEI CO., LTD.

[0284] The acid value of the polymerizable compound containing an acid group is preferably 0.1 to 40 mgKOH / g, and more preferably 5 to 30 mgKOH / g. As long as the acid value of the polymerizable compound is 0.1 mgKOH / g or more, the developing dissolution characteristics are good, and as long as it is 40 mgKOH / g or less, it is advantageous in manufacturing and / or handling. In addition, the photopolymerization performance is good and the curing property is excellent.

[0285] It is also a preferred embodiment that the polymerizable compound contains a caprolactone structure.

[0286] As the compound containing a caprolactone structure, for example, there is no particular limitation as long as the caprolactone structure is contained in the molecule, and examples thereof include ε-caprolactone-modified multifunctional (meth)acrylates obtained by esterifying a polyol such as trimethylolethane, ditrimethylolethane, trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, tripentaerythritol, glycerol, diglycerol, and trimethylolmelamine with (meth)acrylic acid and ε-caprolactone. Among them, a compound containing a caprolactone structure represented by the following formula (Z-1) is preferred.

[0287] [Chemical formula 8]

[0288]

[0289] In formula (Z-1), all six Rs are groups represented by the following formula (Z-2), or one to five of the six Rs are groups represented by the following formula (Z-2), and the rest are groups represented by the following formula (Z-3).

[0290] [Chemical formula 9]

[0291]

[0292] In formula (Z-2), R 1 represents a hydrogen atom or a methyl group, m represents a number of 1 or 2, and * represents a bonding position.

[0293] [Chemical formula 10]

[0294]

[0295] In formula (Z-3), R 1 represents a hydrogen atom or a methyl group, and “*” indicates a bonding position.

[0296] Examples of polymerizable compounds containing a caprolactone structure include DPCA-20 (in the above formulas (Z-1) to (Z-3), m=1, the number of groups represented by the formula (Z-2)=2, R 1All of them are hydrogen atoms), DPCA-30 (in the above formulas (Z-1) to (Z-3), m = 1, the number of groups represented by formula (Z-2) = 3, R 1 All of them are hydrogen atoms), DPCA-60 (in the above formulas (Z-1) to (Z-3), m = 1, the number of groups represented by formula (Z-2) = 6, R 1 All of which are hydrogen atoms) and DPCA-120 (in the above formulas (Z-1) to (Z-3), m = 2, the number of groups represented by formula (Z-2) = 6, R 1 (a compound in which all the atoms are hydrogen atoms). In addition, as a commercially available product of a polymerizable compound containing a caprolactone structure, M-350 (trade name) (trimethylolpropane triacrylate) manufactured by TOAGOSEI CO., LTD. can also be mentioned.

[0297] As the polymerizable compound, a compound represented by the following formula (Z-4) or formula (Z-5) can also be used.

[0298] [Chemical formula 11]

[0299]

[0300] In formula (Z-4) and formula (Z-5), E represents -((CH2) y CH2O)-or-((CH2) y CH(CH3)O)-, y represents an integer of 0 to 10, and X represents a (meth)acryloyl group, a hydrogen atom or a carboxylic acid group.

[0301] In the formula (Z-4), the total number of the (meth)acryloyl groups is 3 or 4, m represents an integer of 0 to 10, and the total number of each m is an integer of 0 to 40.

[0302] In the formula (Z-5), the total number of the (meth)acryloyl groups is 5 or 6, n represents an integer of 0 to 10, and the total number of each n is an integer of 0 to 60.

[0303] In formula (Z-4), m is preferably an integer of 0-6, and more preferably an integer of 0-4.

[0304] Furthermore, the total of each m is preferably an integer of 2-40, more preferably an integer of 2-16, and even more preferably an integer of 4-8.

[0305] In formula (Z-5), n is preferably an integer of 0-6, and more preferably an integer of 0-4.

[0306] Furthermore, the total of each n is preferably an integer of 3-60, more preferably an integer of 3-24, and even more preferably an integer of 6-12.

[0307] Furthermore, -((CH2) in formula (Z-4) or formula (Z-5) y CH2O)-or-((CH2) y CH(CH3)O)- is preferably a form in which the terminal on the oxygen atom side is bonded to X.

[0308] The compound represented by formula (Z-4) or formula (Z-5) may be used alone or in combination of two or more. In particular, preferably, in formula (Z-5), all six Xs are acryloyl groups, or in formula (Z-5), a mixture of a compound in which all six Xs are acryloyl groups and a compound in which at least one of the six Xs is a hydrogen atom. Such a structure can further improve the developability.

[0309] Furthermore, the total content of the compound represented by formula (Z-4) or formula (Z-5) in the polymerizable compound is preferably 20% by mass or more, and more preferably 50% by mass or more.

[0310] Among the compounds represented by formula (Z-4) or formula (Z-5), a pentaerythritol derivative and / or a dipentaerythritol derivative is more preferred.

[0311] Furthermore, the polymerizable compound may contain a cardo skeleton.

[0312] The polymerizable compound including a cardo skeleton is preferably a polymerizable compound including a 9,9-bisarylfluorene skeleton.

[0313] Examples of the polymerizable compound containing a cardo skeleton include ONCOAT FX series (manufactured by NAGASE & CO., LTD.) and OGSOL (manufactured by Osaka Gas Chemicals Co., Ltd.).

[0314] The polymerizable compound is also preferably a compound containing an isocyanuric acid skeleton as a central core. Examples of such a polymerizable compound include NK ESTER A-9300 (manufactured by SHIN-NAKAMURA CHEMICAL Co., Ltd.).

[0315] The content of ethylenically unsaturated groups in the polymerizable compound (the value obtained by dividing the number of ethylenically unsaturated groups in the polymerizable compound by the molecular weight (g / mol) of the polymerizable compound) is preferably 5.0 mmol / g or more, and the upper limit is preferably 20.0 mmol / g or less.

[0316] The content of the polymerizable compound in the curable composition is preferably 5% by mass or more, preferably 10% by mass or more, more preferably 15% by mass or more, and further preferably 20% by mass or more relative to the total solid content of the curable composition. Also, as an upper limit, it is preferably 60% by mass or less, more preferably 40% by mass or less, and further preferably 35% by mass or less.

[0317] The polymerizable compound may be used alone or in combination of two or more. When two or more polymerizable compounds are used in combination, the total amount thereof is preferably within the above range.

[0318] [Relationship between the contents of resin A, resin B, and polymerizable compound]

[0319] In the curable composition, the ratio of the content of the polymerizable compound to the total content of resin A, resin B and the polymerizable compound (content ratio T2. Content of polymerizable compound / total content of resin A, resin B and polymerizable compound) is 0.30 to 0.50, preferably 0.33 to 0.47, and more preferably 0.35 to 0.45. When the content ratio T2 is within the above numerical range, the obtained cured film has excellent adhesion and shows excellent low reflectivity to infrared light. When the content ratio T2 is less than 0.30, the obtained cured film has poor adhesion. On the other hand, when the content ratio T2 exceeds 0.50, the obtained cured film has poor low reflectivity to infrared light.

[0320] 〔pigment〕

[0321] The curable composition contains a pigment.

[0322] As the pigment, there is no particular limitation, for example, black pigment, white pigment and color pigment can be mentioned. And as the color pigment, for example, red pigment, green pigment, blue pigment, yellow pigment, purple pigment and orange pigment can be mentioned. As the pigment, among them, preferably black pigment and white pigment, more preferably black pigment.

[0323] Furthermore, the pigment may be any of an inorganic pigment and an organic pigment. Furthermore, as the pigment, a material obtained by substituting a part of the inorganic pigment or the organic-inorganic pigment with an organic chromophore may be used. Substituting the inorganic pigment or the organic-inorganic pigment with an organic chromophore has the advantage of being easy to design the color.

[0324] The curable composition may use one type of pigment alone or two or more types thereof simultaneously.

[0325] For example, when the cured film of the curable composition is used as a light-shielding film, the light-shielding properties of the light-shielding film can be adjusted by using a black pigment and a pigment other than the black pigment at the same time. Furthermore, when the light-shielding film is used as a light attenuation film, it becomes easy to evenly attenuate each wavelength of light containing a wide wavelength component.

[0326] <Black Pigment>

[0327] The curable composition preferably contains a black pigment.

[0328] In the present specification, the black pigment refers to a pigment having absorption over the entire wavelength range of 400 to 700 nm, and is preferably a black pigment that satisfies, for example, the evaluation criterion Z described below.

[0329] First, a composition is prepared, which includes a black pigment, a transparent resin matrix (acrylic resin, etc.) and a solvent, and the content of the black pigment relative to the total solid content is 60% by mass. The obtained composition is applied on a glass substrate until the film thickness of the cured film after drying becomes 1 μm to form a cured film. The light-shielding property of the cured film after drying is evaluated using a spectrophotometer (UV-3600, etc. manufactured by Hitachi, Ltd.). As long as the maximum value of the transmittance of the cured film after drying at a wavelength of 400 to 700 nm is less than 10%, it can be judged that the above-mentioned black pigment is a black pigment suitable for evaluation standard Z. In the evaluation standard Z, the maximum value of the transmittance of the black pigment at a wavelength of 400 to 700 nm of the cured film after drying is more preferably less than 8%, and more preferably less than 5%.

[0330] As the black pigment, a plurality of pigments that cannot be used alone as a black pigment may be combined to adjust the overall color to black.

[0331] For example, a plurality of pigments each having a color other than black when produced independently may be combined and used as a black pigment.

[0332] The average particle size of the black pigment is preferably 250 nm or less, more preferably 200 nm or less, and further preferably 150 nm or less. From the viewpoint of better operability, the average particle size is preferably 1 nm or more, more preferably 5 nm or more, and further preferably 20 nm or more.

[0333] The above average particle size is calculated by the following method.

[0334] The curable composition was diluted with propylene glycol monomethyl ether acetate (PGMEA) to prepare a measurement solution with a solid content concentration of 0.2 mass %. Next, a dynamic light scattering particle size distribution measuring device (LB-500 (trade name) manufactured by HORIBA, Ltd.) in accordance with JIS8826:2005 was used, and a 2 ml measurement quartz cell was used at a temperature of 25°C to read the data of the above measurement solution 50 times, and the obtained number-based particle diameters were arithmetic averaged as the average particle diameter.

[0335] In addition, in the above, the measurement solution is prepared using the curable composition, but the above measurement can be performed using a color material dispersion liquid dispersed with a black pigment. For example, when the curable composition contains particles other than the black pigment, the average particle size of the black pigment can be measured using a color material dispersion liquid dispersed with the black pigment used to prepare the curable composition. In addition, when the curable composition contains particles other than the black pigment, the average particle size of the black pigment can be measured after separating the black pigment from the other particles by any method.

[0336] As the black pigment, a pigment that exhibits black color alone is preferred. Alternatively, a black pigment that exhibits black color alone and absorbs infrared rays may be used.

[0337] Here, the black pigment that absorbs infrared light has absorption in the infrared region (preferably a wavelength of 650 to 1300 nm), and preferably has a maximum absorption wavelength in the wavelength region of 675 to 900 nm.

[0338] As the black pigment, various known black pigments can be used. The black pigment may be an inorganic pigment or an organic pigment.

[0339] From the viewpoint of achieving more excellent effects of the present invention, the black pigment is preferably an inorganic pigment, and more preferably carbon black, metal nitride particles, or metal oxynitride particles.

[0340] (Inorganic Pigments)

[0341] The inorganic pigment that can be used as the black pigment is not particularly limited as long as it has light-shielding properties and is composed of particles of an inorganic compound, and a known inorganic pigment can be used.

[0342] Examples of the inorganic pigment include metal oxides, metal nitrides and metal oxynitrides containing one or more metal elements selected from Group 4 metal elements such as titanium (Ti) and zirconium (Zr), Group 5 metal elements such as vanadium (V) and niobium (Nb), yttrium (Y), aluminum (Al), cobalt (Co), chromium (Cr), copper (Cu), manganese (Mn), ruthenium (Ru), iron (Fe), nickel (Ni), tin (Sn) and silver (Ag).

[0343] Among them, metal oxides, metal nitrides or metal oxynitrides containing one or more metal elements selected from titanium (Ti), zirconium (Zr), vanadium (V), yttrium (Y), aluminum (Al) and iron (Fe) are preferred. That is, the inorganic pigment may contain two or more metal atoms.

[0344] As the metal oxides, metal nitrides and metal oxynitrides, particles mixed with other metal atoms may be used. For example, metal nitride particles containing atoms selected from elements of Groups 13 to 17 of the periodic table (preferably oxygen atoms and / or sulfur atoms) may be used.

[0345] Furthermore, the metal oxides, metal nitrides and metal oxynitrides may be coated with inorganic and / or organic substances.

[0346] Examples of the inorganic substance include metal atoms contained in the inorganic pigment.

[0347] Examples of the organic substance include organic substances having a hydrophobic group, and silane compounds are preferred.

[0348] As the production method of the above-mentioned metal nitride, metal oxide and metal oxynitride, there is no particular limitation as long as a black pigment having desired physical properties can be obtained, and a known production method such as a gas phase reaction method can be used. As the gas phase reaction method, an electric furnace method and a thermal plasma method can be cited, but from the viewpoint of less mixing of impurities, easy uniformity of particle size, and high productivity, the thermal plasma method is preferred.

[0349] The metal nitride, metal oxide and metal oxynitride may be subjected to surface modification. For example, a surface treatment agent having both a silicone group and an alkyl group may be used to perform surface modification. Examples of such inorganic particles include the "KTP-09" series (manufactured by Shin-Ftsu Chemical Co., Ltd.) and the like.

[0350] Among them, from the viewpoint of being able to suppress the occurrence of undercutting when forming a cured film, a nitride or oxynitride of one or more metals selected from titanium, vanadium, zirconium, niobium and iron is more preferred, and a nitride or oxynitride of zirconium or a nitride or oxynitride of titanium (titanium black) is further preferred.

[0351] Titanium black is black particles containing titanium oxynitride.

[0352] The titanium black may be surface-modified as needed to improve dispersibility, suppress agglomeration, etc. Titanium black may be coated with silicon oxide, titanium oxide, germanium oxide, aluminum oxide, magnesium oxide, or zirconium oxide, and may also be treated with a water-repellent substance as described in Japanese Patent Application Laid-Open No. 2007-302836.

[0353] As methods for producing titanium black, there can be cited a method of heating and reducing a mixture of titanium dioxide and metallic titanium under a reducing atmosphere (Japanese Patent Publication No. 49-005432), a method of reducing ultrafine titanium dioxide obtained by high-temperature hydrolysis of titanium tetrachloride in a hydrogen-containing reducing atmosphere (Japanese Patent Publication No. 57-205322), a method of high-temperature reducing titanium dioxide or titanium hydroxide in the presence of ammonium (Japanese Patent Publication No. 60-065069, Japanese Patent Publication No. 61-201610), and a method of attaching a vanadium compound to titanium dioxide or titanium hydroxide and reducing them at high temperature in the presence of ammonium (Japanese Patent Publication No. 61-201610).

[0354] The particle size of titanium black is not particularly limited, but is preferably 10 to 45 nm, more preferably 12 to 20 nm. The specific surface area of ​​titanium black is not particularly limited, but in order to achieve the required water resistance after surface treatment with a water repellent agent, the value measured by the BET (Brunauer, Emmett, Teller) method is preferably 5 to 150 nm. 2 / g, more preferably 20 to 100 m 2 / g.

[0355] Examples of titanium black include titanium black 10S, 12S, 13R, 13M, 13M-C, 13R, 13R-N, and 13M-T (trade names, manufactured by Mitsubishi Materials Corporation), Tilack D (trade name, manufactured by Ako Kasei Co., Ltd.), and MT-150A (trade name, manufactured by TAYCA CORPORATION).

[0356] The curable composition also preferably contains titanium black as a dispersed body containing titanium black and Si atoms. In this embodiment, titanium black is contained as a dispersed body in the curable composition. The content ratio (Si / Ti) of Si atoms to Ti atoms in the dispersed body is preferably 0.05 to 0.5, more preferably 0.07 to 0.4, in terms of mass conversion. Here, the dispersed body includes both a dispersed body in which titanium black is in the state of primary particles and a dispersed body in the state of agglomerates (secondary particles).

[0357] Furthermore, when the Si / Ti ratio of the dispersed body is above a predetermined value, it is difficult for residues to remain in the removed portion when patterning a composition layer using the dispersed body is performed by photolithography or the like, and when the Si / Ti ratio of the dispersed body is below a predetermined value, the light shielding ability is likely to be improved.

[0358] In order to change the Si / Ti of the dispersed body (for example, set it to 0.05 or more), the following method can be used. First, titanium oxide and silicon dioxide particles are dispersed using a disperser to obtain a dispersion, and the mixture is reduced at a high temperature (for example, 850 to 1000° C.), thereby obtaining a dispersed body containing Si and Ti with titanium black particles as the main component. Titanium black with adjusted Si / Ti can be produced, for example, by the method described in paragraphs

[0005] and

[0016] to

[0021] of Japanese Patent Publication No. 2008-266045.

[0359] The content ratio of Si atoms to Ti atoms (Si / Ti) in the dispersed body can be measured by, for example, the method (2-1) or the method (2-3) described in paragraphs

[0054] to

[0056] of International Publication No. 2011 / 049090.

[0360] In the dispersed body containing titanium black and Si atoms, the titanium black can be the above-mentioned titanium black. In addition, in order to adjust the dispersibility, coloring, etc., in the dispersed body, one or more black pigments composed of composite oxides of various metals selected from Cu, Fe, Mn, V and Ni, cobalt oxide, iron oxide, carbon black, and aniline black can be combined with titanium black and used as the dispersed body at the same time. In this case, it is preferred that the dispersed body composed of titanium black accounts for more than 50% by mass in all the dispersed bodies.

[0361] Carbon black can also be mentioned as a black inorganic pigment.

[0362] Examples of carbon black include furnace black, channel black, thermal black, acetylene black, and lamp black.

[0363] As the carbon black, carbon black produced by a known method such as an oil furnace method may be used, or a commercially available product may be used.

[0364] Examples of commercially available carbon black include inorganic pigments such as CI Pigment Black 7.

[0365] As the carbon black, preferably the carbon black is surface treated. The surface state of the carbon black particles can be changed by the surface treatment, and the dispersion stability in the curable composition can be improved. As the surface treatment, there can be cited a coating treatment based on a resin, a surface treatment for introducing an acidic group, and a surface treatment based on a silane coupling agent.

[0366] As carbon black, carbon black coated with resin is preferred. By coating the surface of carbon black particles with insulating resin, the light-shielding and insulating properties of the cured film can be improved. In addition, the reliability of the image display device can be improved by reducing leakage current, etc. Therefore, it is suitable for the case where the cured film is used for applications requiring light-shielding and insulating properties.

[0367] Examples of the coating resin include epoxy resins, polyamides, polyamideimides, novolac resins, phenolic resins, urea resins, melamine resins, polyurethanes, diallyl phthalate resins, alkylbenzene resins, polystyrene, polycarbonates, polybutylene terephthalate, and modified polyphenylene ethers.

[0368] From the viewpoint of obtaining a cured film with better light-shielding properties and insulating properties, the content of the coating resin is preferably 0.1 to 40% by mass, more preferably 0.5 to 30% by mass, based on the total amount of carbon black and the coating resin.

[0369] Examples of inorganic pigments used as black pigments include zirconium described in Japanese Unexamined Patent Application Publication No. 2017-222559, International Publication No. 2019 / 130772, International Publication No. 2019 / 059359, and Japanese Unexamined Patent Application Publication No. 2009-091205, and the contents thereof are incorporated into this specification.

[0370] (Organic Pigments)

[0371] The organic pigment used as the black pigment is not particularly limited as long as it has light-shielding properties and contains particles of an organic compound, and a known organic pigment can be used.

[0372] In the present invention, examples of the organic pigment include bisbenzofuranone compounds, azomethine compounds, perylene compounds, and azo compounds, and bisbenzofuranone compounds or perylene compounds are preferred.

[0373] Examples of the bisbenzofuranone compound include compounds described in JP-A-2010-534726, JP-A-2012-515233, and JP-A-2012-515234. The bisbenzofuranone compound is available as "Irgaphor Black" (trade name) manufactured by BASF.

[0374] Examples of the perylene compound include compounds described in JP-A-62-001753 and JP-B-63-026784. The perylene compound can be obtained as CI Pigment Black 21, 30, 31, 32, 33, and 34.

[0375] The content of the pigment is preferably 10 to 90% by mass, more preferably 25 to 80% by mass, further preferably 30 to 70% by mass, and particularly preferably 30 to 60% by mass relative to the total solid content of the curable composition. The curable composition may contain only one pigment or two or more. When containing two or more, the total amount is preferably within the above range.

[0376] 〔Photopolymerization initiator〕

[0377] The curable composition contains a photopolymerization initiator.

[0378] The photopolymerization initiator is not particularly limited as long as it can initiate polymerization of the polymerizable compound, and a known photopolymerization initiator can be used.

[0379] The photopolymerization initiator is preferably a photopolymerization initiator having photosensitivity from the ultraviolet region to the visible light region, and may be an activator that generates active free radicals by some reaction with a photoexcited sensitizer, or an initiator that initiates cationic polymerization according to the type of polymerizable compound.

[0380] As the photopolymerization initiator, a so-called radical polymerization initiator is preferred.

[0381] Examples of the photopolymerization initiator include halogenated hydrocarbon derivatives (e.g., compounds containing a triazine skeleton, compounds containing an oxadiazole skeleton, etc.), acylphosphine compounds such as acylphosphine oxides, hexaarylbiimidazoles, oxime compounds such as oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, aminoacetophenone compounds, and hydroxyacetophenone.

[0382] As specific examples of the photopolymerization initiator, for example, paragraphs 0265 to 0268 of Japanese Patent Application Laid-Open No. 2013-029760 can be referred to, and the contents are incorporated into the present specification.

[0383] Examples of the photopolymerization initiator include aminoacetophenone-based initiators described in Japanese Patent Application Laid-Open No. 10-291969 and acylphosphine-based initiators described in Japanese Patent No. 4225898.

[0384] Examples of the hydroxyacetophenone compound include Omnirad-184, Omnirad-1173, Omnirad-500, Omnirad-2959, and Omnirad-127 (trade names, all manufactured by IGM RESINS BV).

[0385] As the aminoacetophenone compound, for example, commercially available products Omnirad-907, Omnirad-369 or Omnirad-379EG (trade name: all manufactured by IGM RESINS BV) can be cited. As the aminoacetophenone compound, compounds described in Japanese Patent Application Laid-Open No. 2009-191179 whose absorption wavelength matches a long-wave light source such as a wavelength of 365 nm or a wavelength of 405 nm can also be cited.

[0386] Examples of the acylphosphine compound include commercially available products Omnirad-819 and Omnirad-TPO (trade names, both manufactured by IGM RESINS BV).

[0387] (Oxime Compounds)

[0388] As the photopolymerization initiator, an oxime ester polymerization initiator (oxime compound) is preferred. In particular, an oxime compound is preferred because it has high sensitivity and high polymerization efficiency and can easily increase the content of the pigment in the curable composition.

[0389] Examples of the oxime compound include compounds described in JP-A No. 2001-233842, compounds described in JP-A No. 2000-080068, and compounds described in JP-A No. 2006-342166.

[0390] Examples of the oxime compound include 3-benzoyloxyiminobutane-2-one, 3-acetoxyiminobutane-2-one, 3-propionyloxyiminobutane-2-one, 2-acetoxyiminopentane-3-one, 2-acetoxyimino-1-phenylpropane-1-one, 2-benzoyloxyimino-1-phenylpropane-1-one, 3-(4-toluenesulfonyloxy)iminobutane-2-one and 2-ethoxycarbonyloxyimino-1-phenylpropane-1-one.

[0391] In addition, compounds described in JCS Perkin II (1979) pp. 1653-1660, JCS Perkin II (1979) pp. 156-162, Journal of Photopolymer Science and Technology (1995) pp. 202-232, Japanese Patent Application Publication No. 2000-066385, Japanese Patent Application Publication No. 2000-080068, Japanese National Publication No. 2004-534797 and Japanese Patent Application Publication No. 2006-342166, etc. can also be mentioned.

[0392] Among the commercial products, IRGACURE-OXE01 (manufactured by BASF), IRGACURE-OXE02 (manufactured by BASF), IRGACURE-OXE03 (manufactured by BASF), and IRGACURE-OXE04 (manufactured by BASF) can also be mentioned. In addition, TR-PBG-304 (manufactured by Changzhou Tronly New Electronic Materials CO., LTD.), ADEKA ARKLS NCI-730, ADEKA ARKLS NCI-831, ADEKA ARKLS NCI-930 (manufactured by ADEKA CORPORATION), and N-1919 (a photoinitiator containing a carbazole / oxime ester skeleton (manufactured by ADEKA CORPORATION)) can also be mentioned. In addition, Omnirad1316 (IGM RESINS BV) can also be mentioned.

[0393] In addition, as oxime compounds other than the above, there can be cited compounds described in Japanese Patent Publication No. 2009-519904 in which an oxime is linked to the N-position of carbazole; compounds described in U.S. Patent No. 7626957 in which a hetero substituent is introduced at the benzophenone site; compounds described in Japanese Patent Publication No. 2010-015025 and U.S. Patent Publication No. 2009-292039 in which a nitro group is introduced at the pigment site; ketone oxime compounds described in International Publication No. 2009-131189 and compounds described in U.S. Patent No. 7556910 containing a triazine skeleton and an oxime skeleton in the same molecule; compounds described in Japanese Patent Publication No. 2009-221114 having an absorption maximum at 405 nm and good sensitivity to a g-ray light source, etc.

[0394] For example, paragraphs 0274 to 0275 of Japanese Patent Application Laid-Open No. 2013-029760 can be referred to, and the contents are incorporated into this specification.

[0395] Specifically, the oxime compound is preferably a compound represented by the following formula (OX-1). The NO bond of the oxime compound may be an (E)-form oxime compound, an (Z)-form oxime compound, or a mixture of the (E)-form and the (Z)-form oxime compound.

[0396] [Chemical formula 12]

[0397]

[0398] In the formula (OX-1), R and B each independently represent a monovalent substituent, A represents a divalent organic group, and Ar represents an aryl group.

[0399] In the formula (OX-1), the monovalent substituent represented by R is preferably a monovalent non-metallic atomic group.

[0400] Examples of the monovalent non-metallic atomic group include alkyl, aryl, acyl, alkoxycarbonyl, aryloxycarbonyl, heterocyclic, alkylthiocarbonyl, and arylthiocarbonyl. Furthermore, these groups may have one or more substituents. Furthermore, the above-mentioned substituents may be substituted by other substituents.

[0401] Examples of the substituent include a halogen atom, an aryloxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, an acyl group, an alkyl group, and an aryl group.

[0402] In formula (OX-1), the monovalent substituent represented by B is preferably an aryl group, a heterocyclic group, an arylcarbonyl group or a heterocyclic carbonyl group, and more preferably an aryl group or a heterocyclic group. These groups may also have one or more substituents. As the substituent, the above-mentioned substituents can be exemplified.

[0403] In formula (OX-1), the divalent organic group represented by A is preferably an alkylene group, a cycloalkylene group or an alkynylene group having 1 to 12 carbon atoms. These groups may have one or more substituents. As the substituent, the above-mentioned substituents can be exemplified.

[0404] As the photopolymerization initiator, an oxime compound containing a fluorine atom can also be mentioned. As the oxime compound containing a fluorine atom, for example, the compound described in Japanese Unexamined Patent Publication No. 2010-262028, the compound 24, 36 to 40 described in Japanese Unexamined Patent Publication No. 2014-500852, and the compound (C-3) described in Japanese Unexamined Patent Publication No. 2013-164471 can be mentioned. This content is incorporated into this specification.

[0405] Examples of the polymerization initiator include compounds represented by the following formulae (1) to (4).

[0406] [Chemical formula 13]

[0407]

[0408] [Chemical formula 14]

[0409]

[0410] In formula (1), R 1 and R 2 Each independently represents an alkyl group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group having 4 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an aralkyl group having 7 to 30 carbon atoms. 1 and R 2When the phenyl group is a phenyl group, the phenyl groups may be bonded to each other to form a fluorenyl group. 3 and R 4 Each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 4 to 20 carbon atoms, and X represents a direct bond or a carbonyl group.

[0411] In formula (2), R 1 , R 2 , R 3 and R 4 With R in formula (1) 1 , R 2 , R 3 and R 4 has the same meaning, R 5 Indicates -R 6 、-OR 6 、-SR 6 、-COR 6 、-CONR 6 R 6 、-NR 6 COR 6 、-OCOR 6 、-COOR 6 ,-SCOR 6 、-OCSR 6 ,-COSR 6 ,-CSOR 6 , -CN, halogen atom or hydroxyl group, R 6 represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 4 to 20 carbon atoms, X represents a direct bond or a carbonyl group, and a represents an integer of 0 to 4.

[0412] In formula (3), R 1 represents an alkyl group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group having 4 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an arylalkyl group having 7 to 30 carbon atoms, and R 3 and R 4 Each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 4 to 20 carbon atoms, and X represents a direct bond or a carbonyl group.

[0413] In formula (4), R 1 , R 3 and R 4 The meaning of is the same as R in formula (3) 1 , R 3 and R 4 has the same meaning, R 5Indicates -R 6 、-OR 6 、-SR 6 、-COR 6 、-CONR 6 R 6 、-NR 6 COR 6 、-OCOR 6 、-COOR 6 ,-SCOR 6 、-OCSR 6 ,-COSR 6 ,-CSOR 6 , -CN, halogen atom or hydroxyl group, R 6 represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 4 to 20 carbon atoms, X represents a direct bond or a carbonyl group, and a represents an integer of 0 to 4.

[0414] Examples of the compounds represented by formula (1) and formula (2) include compounds described in paragraphs 0076 to 0079 of JP-A-2014-137466, which are incorporated herein.

[0415] Furthermore, as the photopolymerization initiator, a compound represented by the following formula (1) is also preferred.

[0416] [Chemical formula 15]

[0417]

[0418] In formula (1), R represents a group represented by the following formula (1a),

[0419] [Chemical formula 16]

[0420]

[0421] In formula (1a), n represents an integer of 1 to 5. m represents an integer of 1 to 6. * represents a bonding position.

[0422] m is preferably 3 or 4.

[0423] The compound represented by the formula (1) can be synthesized by the synthesis method described in, for example, JP-A-2012-519191.

[0424] Specific examples of the oxime compound preferably used in the curable composition are shown below.

[0425] Furthermore, as the oxime compound, there can be mentioned compounds described in Table 1 of International Publication No. 2015-036910, and the above contents are incorporated into the present specification.

[0426] [Chemical formula 17]

[0427]

[0428] [Chemical formula 18]

[0429]

[0430] [Chemical formula 19]

[0431]

[0432] The oxime compound preferably has a maximum absorption wavelength in the wavelength region of 350 to 500 nm, more preferably has a maximum absorption wavelength in the wavelength region of 360 to 480 nm, and further preferably has high absorbance at wavelengths of 365 nm and 405 nm.

[0433] From the viewpoint of sensitivity, the molar absorption coefficient of the oxime compound at 365 nm or 405 nm is preferably 1,000 to 300,000, more preferably 2,000 to 300,000, and even more preferably 5,000 to 200,000.

[0434] The molar absorption coefficient of the compound can be measured using a known method, for example, preferably using an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian) using ethyl acetate at a concentration of 0.01 g / L.

[0435] The photopolymerization initiators may be used in combination of two or more types as necessary.

[0436] Furthermore, as the photopolymerization initiator, compounds described in paragraph 0052 of JP-A-2008-260927, paragraphs 0033 to 0037 of JP-A-2010-097210, and paragraph 0044 of JP-A-2015-068893 can also be used, and the contents thereof are incorporated into the present specification.

[0437] As the photopolymerization initiator, an oxime ester-based polymerization initiator is preferred from the viewpoint of achieving more excellent effects of the present invention.

[0438] The content of the photopolymerization initiator in the curable composition is preferably 0.5 to 20% by mass, more preferably 1.0 to 10% by mass, and even more preferably 1.5 to 8% by mass, relative to the total solid content of the curable composition.

[0439] The photopolymerization initiator may be used alone or in combination of two or more. When two or more photopolymerization initiators are used in combination, the total amount thereof is preferably within the above range.

[0440] 〔Surfactant〕

[0441] The curable composition may contain a surfactant. The surfactant helps to improve the coating properties of the curable composition.

[0442] Examples of the surfactant include silicone-based surfactants, fluorine-based surfactants, nonionic surfactants, cationic surfactants, and anionic surfactants.

[0443] Among them, silicone-based surfactants are preferred from the viewpoint of more excellent effects of the present invention.

[0444] Examples of the silicone-based surfactant include linear polymers composed of siloxane bonds and modified siloxane polymers having an organic group introduced into a side chain and / or a terminal.

[0445] Examples of the silicone surfactant include DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH30PA, and SH8400 of the DOWSIL (registered trademark) series (all manufactured by Dow Corning Toray Co., Ltd.); X-22-4952, X-22-4272, X-22-6266, KF-351A, K354L, KF-355A, KF-945, KF-640, KF-642, KF-643, X-22-6191, X-22-4515, KF-6000, KF-6004, KP-323, KP-341, KF-6001, and KF-6002 (all manufactured by Shin-Etsu Silicone Co., Ltd.); F-4440, TSF-4300, TSF-4445, TSF-4460 and TSF-4452 (all manufactured by Momentive performance Materials Inc.); BYK307, BYK323 and BYK330 (all manufactured by BYK Co., LTD.).

[0446] As a preferred embodiment of the silicone surfactant, from the viewpoint of more excellent effects of the present invention, an aromatic group-modified silicone surfactant (a silicone surfactant having an aromatic group) is preferred, and a phenyl-modified silicone surfactant (a silicone surfactant having a phenyl group) is more preferred.

[0447] Examples of the fluorine-based surfactant include MEGAFACE F171, MEGAFACE F172, MEGAFACE F173, MEGAFACE F176, MEGAFACE F177, MEGAFACE F141, MEGAFACE F142, MEGAFACE F143, MEGAFACE F144, MEGAFACE R30, MEGAFACE F437, MEGAFACE F475, MEGAFACE F479, MEGAFACE F482, MEGAFACE F554, and MEGAFACE F780 (all manufactured by DIC CORPORATION); Fluorad FC430, Fluorad FC431, and Fluorad FC171 (all manufactured by Sumitomo 3M Limited); Surflon S-382, Surflon SC-101, Surflon SC-103, Surflon SC-104, Surflon SC-105, Surflon SC1068, Surflon SC-381, Surflon SC-383, Surflon S393 and Surflon KH-40 (all manufactured by Asahi Glass Co., Ltd.); and PF636, PF656, PF6320, PF6520 and PF7002 (manufactured by OMNOVA Solutions Inc.), etc.

[0448] As the fluorine-based surfactant, a block polymer can also be used, and examples thereof include compounds described in JP-A-2011-089090.

[0449] When the curable composition contains a surfactant, the content of the surfactant in the curable composition is not particularly limited. From the viewpoint of achieving a more excellent effect of the present invention, the content of the surfactant is preferably 0.001 to 2.0% by mass, more preferably 0.005 to 0.5% by mass, and further preferably 0.01 to 0.1% by mass, relative to the total solid content of the curable composition.

[0450] The surfactant may be used alone or in combination of two or more. When two or more surfactants are used in combination, the total amount is preferably within the above range.

[0451] 〔Solvent〕

[0452] The curable composition may contain a solvent.

[0453] The solvent is not particularly limited, and a known solvent can be used, and examples thereof include organic solvents and water.

[0454] In the curable composition, the content of the solid component is preferably 10 to 90% by mass, more preferably 10 to 50% by mass, and further preferably 15 to 50% by mass relative to the total mass of the curable composition. That is, the content of the solvent in the curable composition is not particularly limited, but is preferably adjusted so that the solid content of the curable composition becomes the above content.

[0455] The solvent may be used alone or in combination of two or more. When two or more solvents are used in combination, the solvents are preferably adjusted so that the total solid content of the curable composition is within the above range.

[0456] Examples of the organic solvent include acetone, methyl ethyl ketone, cyclohexane, ethyl acetate, ethylene dichloride, tetrahydrofuran, toluene, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, acetylacetone, cyclohexanone, cyclopentanone, diacetone alcohol, ethylene glycol monomethyl ether acetate, ethylene glycol ethyl ether acetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether acetate, 3-methoxypropanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether. , diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxypropyl acetate, N,N-dimethylformamide, dimethyl sulfoxide, γ-butyrolactone, ethyl acetate, butyl acetate, methyl lactate, N-methyl-2-pyrrolidone and ethyl lactate, 3-methoxybutanol, 1,3-butanediol, 2,3-butanediol, propylene glycol, ethylene glycol, dimethyl sulfoxide and γ-valerolactone, etc., but are not limited to these.

[0457] [Epoxy-containing compounds (sealing agents)]

[0458] The curable composition may contain an epoxy group-containing compound.

[0459] The epoxy group-containing compound may include compounds having one or more epoxy groups, preferably compounds having two or more epoxy groups. The number of epoxy groups is preferably 1 to 100. The upper limit may be, for example, 10 or less, or 5 or less. The lower limit is preferably 2 or more.

[0460] In addition, the epoxy group-containing compound refers to a component different from the above-mentioned dispersant, alkali-soluble resin and polymerizable compound.

[0461] The epoxy equivalent of the epoxy-containing compound (=molecular weight of the epoxy-containing compound / number of epoxy groups) is preferably 500 g / equivalent or less, more preferably 100 to 400 g / equivalent or less, and further preferably 100 to 300 g / equivalent or less.

[0462] The compound containing an epoxy group may be a low molecular weight compound (e.g., a molecular weight of less than 2000) or a macromolecule (e.g., a molecular weight of 2000 or more, and in the case of a polymer, a weight average molecular weight of 2000 or more). The weight average molecular weight of the compound containing an epoxy group is preferably 200 to 100000, more preferably 500 to 50000. The upper limit of the weight average molecular weight is more preferably 10000 or less, further preferably 5000 or less, and particularly preferably 3000 or less.

[0463] Commercially available products can be used as the epoxy group-containing compound, and examples thereof include EHPE3150 (manufactured by Daicel Corporation), EOCN-1020 (manufactured by Nippon Kayaku Co., Ltd.), EPICLON N-695 (manufactured by DIC), and CELLOXIDE 2021P (manufactured by Daicel Corporation).

[0464] Examples of the epoxy group-containing compound include compounds described in paragraphs 0034 to 0036 of JP-A-2013-011869, paragraphs 0147 to 0156 of JP-A-2014-043556, and paragraphs 0085 to 0092 of JP-A-2014-089408. These contents are incorporated into the present specification.

[0465] When the curable composition contains an epoxy group-containing compound, the content of the epoxy group-containing compound in the curable composition is preferably 0.001 to 10 mass %, more preferably 0.01 to 8 mass %, and even more preferably 0.01 to 6 mass % relative to the total solid content in the curable composition.

[0466] The epoxy group-containing compound may be used alone or in combination of two or more. When the curable composition contains two or more epoxy group-containing compounds, the total content thereof is preferably within the above range.

[0467] 〔Silane coupling agent (sealing agent)〕

[0468] The curable composition may contain a silane coupling agent.

[0469] When a cured film is formed on a substrate, the silane coupling agent functions as an adhesion agent that improves adhesion between the substrate and the cured film.

[0470] The silane coupling agent refers to a compound containing a hydrolyzable group and other functional groups in the molecule. In addition, a hydrolyzable group such as an alkoxy group is bonded to a silicon atom.

[0471] The hydrolyzable group refers to a substituent that is directly bonded to the silicon atom and can generate a siloxane bond by a hydrolysis reaction and / or a condensation reaction. As the hydrolyzable group, for example, a halogen atom, an alkoxy group, an acyloxy group and an alkenyloxy group can be cited. When the hydrolyzable group contains carbon atoms, the number of carbon atoms is preferably 6 or less, more preferably 4 or less. In particular, an alkoxy group having 4 or less carbon atoms or an alkenyloxy group having 4 or less carbon atoms is preferably preferred.

[0472] Furthermore, when a cured film is formed on a substrate, in order to improve the adhesion between the substrate and the cured film, the silane coupling agent preferably does not contain fluorine atoms and silicon atoms (except for silicon atoms bonded to hydrolyzable groups), and preferably does not contain fluorine atoms, silicon atoms (except for silicon atoms bonded to hydrolyzable groups), alkylene groups substituted with silicon atoms, linear alkyl groups with 8 or more carbon atoms, and branched alkyl groups with 3 or more carbon atoms.

[0473] The silane coupling agent may contain an ethylenically unsaturated group such as a (meth)acryloyl group. When containing an ethylenically unsaturated group, the number thereof is preferably 1 to 10, more preferably 4 to 8. In addition, a silane coupling agent containing an ethylenically unsaturated group (e.g., a compound having a molecular weight of 2000 or less containing a hydrolyzable group and an ethylenically unsaturated group) does not belong to the above-mentioned polymerizable compound.

[0474] Examples of the silane coupling agent include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, vinyltrimethoxysilane, and vinyltriethoxysilane.

[0475] When the curable composition contains a silane coupling agent, the content of the silane coupling agent in the curable composition is preferably 0.1 to 10 mass %, more preferably 0.5 to 8 mass %, and further preferably 1.0 to 6 mass % relative to the total solid content in the curable composition.

[0476] The silane coupling agent may be contained alone or in combination of two or more. When the curable composition contains two or more silane coupling agents, the total amount thereof may be within the above range.

[0477] 〔Ultraviolet light absorber〕

[0478] The curable composition may contain an ultraviolet absorber. This can make the pattern shape of the cured film formed by exposure to light more excellent (fine).

[0479] As ultraviolet absorbers, salicylate-based, benzophenone-based, benzotriazole-based, substituted acrylonitrile-based and triazine-based ultraviolet absorbers can be cited. In addition, compounds described in paragraphs 0137 to 0142 of Japanese Patent Application Publication No. 2012-068418 (corresponding to paragraphs 0251 to 0254 of US2012 / 0068292) can also be cited, and these contents can be cited and incorporated into this specification.

[0480] In addition, a diethylamino-phenylsulfonyl ultraviolet absorber (manufactured by DAITO CHEMICAL CO., LTD., trade name: UV-503) and the like can also be mentioned.

[0481] Examples of the ultraviolet absorber include the compounds exemplified in paragraphs 0134 to 0148 of JP-A-2012-032556.

[0482] When the curable composition contains a UV absorber, the content of the UV absorber is preferably 0.001 to 15% by mass, more preferably 0.01 to 10% by mass, and even more preferably 0.1 to 5% by mass, based on the total solid content of the curable composition.

[0483] 〔dye〕

[0484] The curable composition may contain a dye.

[0485] As the dye, a known dye can be used, and examples thereof include black dyes and color dyes. Examples of the color dye include red dyes, green dyes, blue dyes, yellow dyes, violet dyes, and orange dyes.

[0486] Among the dyes, black dyes are preferred.

[0487] As a black dye, for example, a dye that exhibits black alone can be used, such as pyrazole azo compounds, pyrromethene compounds, aniline azo compounds, triphenylmethane compounds, anthraquinone compounds, benzal compounds, oxonol compounds, pyrazolotriazole azo compounds, pyridone azo compounds, cyanine compounds, phenothiazine compounds and pyrrolopyrazole azomethine compounds.

[0488] Furthermore, as black dyes, for example, reference can be made to compounds described in Japanese Patent Application Publication No. 64-90403, Japanese Patent Application Publication No. 64-91102, Japanese Patent Application Publication No. 01-94301, Japanese Patent Application Publication No. 06-11614, Japanese Patent No. 2592207, U.S. Patent No. 4808501, U.S. Patent No. 5667920, U.S. Patent No. 505950, U.S. Patent No. 5667920, Japanese Patent Application Publication No. 05-333207, Japanese Patent Application Publication No. 06-35183, Japanese Patent Application Publication No. 06-51115, and Japanese Patent Application Publication No. 06-194828, and the like, and these contents are incorporated into this specification.

[0489] Examples of these black dyes include dyes specified in the color index (CI) of Solvent Black 27 to 47, and dyes specified in the CI of Solvent Black 27, 29, or 34 are preferred.

[0490] In addition, as commercial products of these black dyes, for example, Spilon Black MH, Black BH (above, manufactured by Hodogaya Chemical Co., Ltd.), VALIFAST Black 3804, 3810, 3820, 3830 (above, manufactured by ORIENT CHEMICAL INDUSTRIES CO., LTD.), Sayinyl Black RLSN (above, manufactured by Clariant Chemicals), KAYASET Black KR, K-BL (above, manufactured by Nippon Kayaku CO., LTD.) and the like can be cited. In addition, polymerizable dyes having polymerizability in the molecule can also be used, and as commercial products, for example, RDW series manufactured by Wako Pure Chemical Industries, LTD. can be cited.

[0491] Furthermore, a pigment multimer may be used as the black dye. Examples of the pigment multimer include compounds described in Japanese Patent Application Laid-Open Nos. 2011-213925 and 2013-041097.

[0492] In addition, as described above, a plurality of dyes having colors other than black may be combined to be used as black dyes. As such coloring dyes, for example, in addition to color dyes (color dyes) such as R (red), G (green), and B (blue), dyes described in paragraphs 0027 to 0200 of Japanese Patent Application Laid-Open No. 2014-42375 may be used.

[0493] 〔Infrared absorber〕

[0494] The curable composition may further contain an infrared absorber.

[0495] The infrared absorber is a compound having absorption in the infrared region (preferably a wavelength of 650 to 1300 nm). The infrared absorber is preferably a compound having a maximum absorption wavelength in the wavelength region of 675 to 900 nm.

[0496] Examples of colorants having such spectral characteristics include pyrrolopyrrole compounds, copper compounds, cyanine compounds, phthalocyanine compounds, imine compounds, thiol complex compounds, transition metal oxide compounds, squarylium compounds, naphthalocyanine compounds, quaterrylene compounds, dithiol metal complex compounds, and crotonium compounds.

[0497] Phthalocyanine compounds, naphthalocyanine compounds, imine compounds, cyanine compounds, squaryl compounds and crotonium compounds can use compounds disclosed in paragraphs 0010 to 0081 of Japanese Patent Application Publication No. 2010-111750, and the contents are incorporated into this specification. For cyanine compounds, for example, reference can be made to "Functional Pigments, Okawara Nobuyuki / Matsuoka Ken / Kitao Teijiro / Hirashima Tsuneaki, Kodansha Ltd.", and the contents are incorporated into this specification.

[0498] As a colorant having the above-mentioned spectral characteristics, the compounds disclosed in paragraphs 0004 to 0016 of Japanese Patent Application Laid-Open No. 07-164729 and / or the compounds disclosed in paragraphs 0027 to 0062 of Japanese Patent Application Laid-Open No. 2002-146254, and the near-infrared absorbing particles disclosed in paragraphs 0034 to 0067 of Japanese Patent Application Laid-Open No. 2011-164583, which are composed of microcrystals of Cu and / or P oxides and have a number average aggregated particle size of 5 to 200 nm, can also be used.

[0499] The compound having a maximum absorption wavelength in the wavelength region of 675 to 900 nm is preferably at least one selected from the group consisting of cyanine compounds, pyrrolopyrrole compounds, squarylium compounds, phthalocyanine compounds, and naphthalocyanine compounds.

[0500] The infrared absorber is preferably a compound that dissolves 1% by mass or more in water at 25° C., more preferably a compound that dissolves 10% by mass or more in water at 25° C. By using such a compound, solvent resistance is improved.

[0501] For pyrrolopyrrole compounds, reference may be made to paragraphs 0049 to 0062 of Japanese Patent Application Publication No. 2010-222557, and the contents are incorporated into the present specification. For cyanine compounds and squaric acid compounds, reference may be made to paragraphs 0022 to 0063 of International Publication No. 2014 / 088063, paragraphs 0053 to 0118 of International Publication No. 2014 / 030628, paragraphs 0028 to 0074 of Japanese Patent Application Publication No. 2014-59550, paragraphs 0013 to 0091 of International Publication No. 2012 / 169447, and paragraphs 0017 to 0018 of Japanese Patent Application Publication No. 2014-59550. 15-176046, paragraphs 0019 to 0033, Japanese Patent Application Publication No. 2014-63144, paragraphs 0053 to 0099, Japanese Patent Application Publication No. 2014-52431, paragraphs 0085 to 0150, Japanese Patent Application Publication No. 2014-44301, paragraphs 0076 to 0124, Japanese Patent Application Publication No. 2012-8532, paragraphs 0045 to 0078, Japanese Patent Application Publication No. 2014-52431, paragraphs 0085 to 0150, Japanese Patent Application Publication No. 2014-52431, paragraphs 0076 to 0124 ... Paragraphs 0027 to 0067 of Japanese Patent Application Publication No. 2015-172102, paragraphs 0029 to 0067 of Japanese Patent Application Publication No. 2015-172004, paragraphs 0029 to 0085 of Japanese Patent Application Publication No. 2015-40895, paragraphs 0022 to 0036 of Japanese Patent Application Publication No. 2014-126642, paragraphs 001 1 to 0017, paragraphs 0010 to 0025 of Japanese Patent Application Publication No. 2015-157893, paragraphs 0013 to 0026 of Japanese Patent Application Publication No. 2014-095007, paragraphs 0013 to 0047 of Japanese Patent Application Publication No. 2014-80487, and paragraphs 0007 to 0028 of Japanese Patent Application Publication No. 2013-227403, and the like, and the contents are incorporated into this specification.

[0502] 〔Other optional ingredients〕

[0503] The curable composition may further include any other components other than the above components. For example, polymerization inhibitors, sensitizers, co-sensitizers, crosslinking agents, curing accelerators, fillers, thermosetting accelerators, plasticizers, diluents, and lipid-sensitizing agents may be cited. In addition, adhesion promoters and other auxiliary agents (for example, conductive particles, fillers, defoamers, flame retardants, leveling agents, peeling accelerators, antioxidants, fragrances, surface tension modifiers, and chain transfer agents) to the substrate surface may be added as needed.

[0504] For example, these components can be referred to in paragraphs 0183 to 0228 of Japanese Patent Application Publication No. 2012-003225 (paragraphs 0237 to 0309 of the corresponding U.S. Patent Application Publication No. 2013 / 0034812), paragraphs 0101 to 0102, 0103 to 0104, and 0107 to 0109 of Japanese Patent Application Publication No. 2008-250074, and paragraphs 0159 to 0184 of Japanese Patent Application Publication No. 2013-195480, and the like, and these contents are incorporated into the present specification.

[0505] [Method for producing curable composition]

[0506] Regarding the curable composition, it is preferred that a dispersion composition in which a pigment is dispersed is first prepared, and the obtained dispersion composition is further mixed with other components to prepare a composition.

[0507] The dispersion composition is preferably prepared by mixing a pigment, a resin A, and a solvent. Furthermore, it is also preferred to introduce a polymerization inhibitor into the dispersion composition.

[0508] The above-mentioned dispersion composition can be prepared by mixing the above-mentioned components by a known mixing method (for example, a mixing method using a stirrer, a homogenizer, a high-pressure emulsifier, a wet pulverizer, a wet disperser, or the like).

[0509] After the dispersion composition is prepared, the dispersion composition, the resin B, the polymerizable compound, the photopolymerization initiator, and the solvent can be mixed to prepare the dispersion composition.

[0510] When preparing the curable composition, the components may be mixed at once or successively after being dissolved or dispersed in a solvent. The order of addition and the working conditions during mixing are not particularly limited.

[0511] In order to remove foreign matter and reduce defects, the curable composition is preferably filtered with a filter. As a filter, for example, as long as it is a filter used for filtering purposes, it can be used without particular restrictions. For example, filters based on polyamide resins such as fluororesins such as PTFE (polytetrafluoroethylene), nylon, and polyolefin resins such as polyethylene and polypropylene (PP) (including high density, ultra-high molecular weight) can be cited. Among them, preferably polypropylene (including high-density polypropylene) or nylon.

[0512] The pore size of the filter is preferably 0.1 to 7.0 μm, more preferably 0.2 to 2.5 μm, further preferably 0.2 to 1.5 μm, and particularly preferably 0.3 to 0.7 μm. Within this range, clogging of the filter of the pigment (including black pigment) can be suppressed, and fine foreign matter such as impurities and aggregates contained in the pigment can be reliably removed.

[0513] The curable composition preferably does not contain impurities such as metals, halogen-containing metal salts, acids, and bases. The content of impurities contained in these materials is preferably 1 mass ppm or less, more preferably 1 mass ppb or less, further preferably 100 mass ppt or less, particularly preferably 10 mass ppt or less, and most preferably substantially free (below the detection limit of the measuring device).

[0514] The impurities described above can be measured using an inductively coupled plasma mass spectrometer (manufactured by Yokogawa Flectric Corporation, Agilent 7500cs model).

[0515] [Method for producing cured film]

[0516] In the present specification, the term “cured film” refers to a film formed by subjecting a composition layer formed using a curable composition to a curing treatment such as an exposure treatment.

[0517] Hereinafter, the method for producing the cured film will be described.

[0518] The method for producing a cured film preferably includes the following steps. Through the above steps, for example, a patterned cured film can be formed. In addition, when the cured film is not set to a patterned shape, the development step may not be performed.

[0519] Hereinafter, each step will be described.

[0520] [Composition layer forming step]

[0521] In the composition layer forming step, a layer (composition layer) of a curable composition is formed on a support or the like by imparting a curable composition before exposure. As a support, for example, a solid-state imaging element substrate can be used in which an imaging element (light-receiving element) such as a CCD (Charge Coupled Device) or a CMOS (Complementary Metal-Oxide Semiconductor) is provided on a substrate (for example, a silicon substrate). In addition, as required, a primer layer for improving adhesion with an upper layer, preventing diffusion of a substance, and flattening the surface of the substrate can be provided on the support.

[0522] As a method for applying the curable composition on the support, various coating methods such as slit coating, inkjet, spin coating, cast coating, roll coating and screen printing can be cited. The film thickness of the composition layer is preferably 0.1 to 10 μm, more preferably 0.2 to 5 μm, and further preferably 0.2 to 3 μm. The drying (prebaking) of the composition layer coated on the support can be performed using a hot plate and an oven at a temperature of 50 to 140° C. for 10 to 300 seconds.

[0523] [Exposure process]

[0524] The exposure step is a step of irradiating the composition layer formed in the composition layer forming step with actinic rays or radiation to expose the composition layer formed in the composition layer forming step. Specifically, the exposure step is a step of irradiating the composition layer formed in the composition layer forming step with actinic rays or radiation to expose the composition layer and cure the light irradiated region of the composition layer.

[0525] The method of light irradiation is not particularly limited, but light irradiation is preferably performed through a photomask having patterned openings.

[0526] The exposure is preferably performed by irradiation with radiation. In particular, ultraviolet rays such as g-rays, h-rays and i-rays are preferred as the radiation that can be used for exposure. A high-pressure mercury lamp is preferred as the light source. The irradiation intensity is preferably 5 to 1500 mJ / cm 2 , more preferably 10 to 1000 mJ / cm 2 .

[0527] In addition, when the composition layer is heated in the exposure step, it can also serve as a post-heating step described later. In other words, when the composition layer is heated in the exposure step, the method for producing a cured film does not need to include a post-heating step.

[0528] 〔Development process〕

[0529] The development step is a step of performing a development treatment on the composition layer after exposure. Through this step, the composition layer in the light-exposed area in the exposure step is dissolved, and only the photocured portion remains. For example, in the exposure step, when light irradiation is performed through a photomask having a patterned opening, a patterned cured film can be obtained.

[0530] The type of developer used in the development step is not particularly limited, but an alkaline developer that does not damage the underlying imaging element, circuit, etc. is preferably used.

[0531] The development temperature is, for example, 20 to 30°C.

[0532] The developing time is, for example, 20 to 90 seconds. In recent years, in order to further remove the residue, it is sometimes implemented for 120 to 180 seconds. In addition, in order to further improve the residue removal performance, the following process is sometimes repeated multiple times: the developer is dried every 60 seconds and a new developer is supplied.

[0533] The alkali developer is preferably an alkaline aqueous solution prepared by dissolving an alkaline compound in water to a concentration of 0.001 to 10% by mass (preferably 0.01 to 5% by mass).

[0534] Examples of the alkaline compound include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide, choline, pyrrole, piperidine and 1,8-diazabicyclo[5.4.0]-7-undecene (among which, an organic base is preferred).

[0535] When used as an alkaline developer, washing treatment with water is usually performed after development.

[0536] 〔Post-baking〕

[0537] After the exposure process, a heat treatment (post-baking) is preferably performed. Post-baking is a heat treatment after development for complete curing. The heating temperature is preferably 240°C or less, more preferably 220°C or less. The lower limit is not particularly limited, but if efficient and effective processing is considered, it is preferably 50°C or more, more preferably 100°C or more.

[0538] Post-drying can be performed continuously or intermittently using a heating mechanism such as a hot plate, a convection oven (hot air circulation dryer), or a high-frequency heater.

[0539] The post-drying is preferably carried out in an atmosphere of low oxygen concentration. The oxygen concentration is preferably 19% by volume or less, more preferably 15% by volume or less, further preferably 10% by volume or less, particularly preferably 7% by volume or less, and most preferably 3% by volume or less. The lower limit is not particularly limited, but is actually 10 ppm by volume or more.

[0540] Furthermore, the post-baking by heating described above may be changed to complete curing by UV (ultraviolet) irradiation.

[0541] At this time, the curable composition preferably further comprises a UV curing agent. The UV curing agent is preferably a UV curing agent that can be cured at a wavelength shorter than 365nm, and the wavelength shorter than 365nm is the exposure wavelength of the polymerization initiator added for the photolithography process through the usual i-ray exposure. As a UV curing agent, for example, CibaIRGACURE 2959 (trade name) can be cited. When UV irradiation is performed, the composition layer is preferably a material that is cured at a wavelength of less than 340nm. The lower limit of the wavelength is not particularly limited, and is usually more than 220nm. In addition, the exposure amount of UV irradiation is preferably 100 to 5000mJ, more preferably 300 to 4000mJ, and further preferably 800 to 3500mJ. In order to perform low-temperature curing more effectively, the UV curing process is preferably performed after the photolithography process. The exposure light source preferably uses an ozone-free mercury lamp.

[0542] [Physical properties of cured film and uses of cured film]

[0543] The cured film obtained by curing the curable composition of the present invention is preferably used as a light-shielding film. Hereinafter, preferred physical properties and uses of the cured film obtained by curing the curable composition of the present invention when used as a light-shielding film will be described.

[0544] [Physical properties of light-shielding films and uses of light-shielding films]

[0545] From the viewpoint of excellent light-shielding property, the light-shielding film preferably has an optical density (OD: Optical Density) per 5.0 μm film thickness in the wavelength range of 400 to 1100 nm of 3.0 or more, more preferably 3.5 or more. The upper limit is not particularly limited, but is usually preferably 10 or less.

[0546] In addition, in this specification, the optical density of 3.0 or more per 5.0 μm film thickness in the wavelength region of 400 to 1100 nm means that the optical density of 3.0 or more per 5.0 μm film thickness in the entire wavelength region of 400 to 1100 nm. As a method for measuring the optical density of the light-shielding film, first, a light-shielding film is formed on a glass substrate and measured using a spectrophotometer (e.g., U-4100 manufactured by Hitachi High-Tech Corporation, etc.).

[0547] The thickness of the light-shielding film is, for example, preferably 0.1 to 6.0 μm, more preferably 1.0 to 5.0 μm, and further preferably 1.0 to 2.5 μm. Depending on the application, the light-shielding film may be thin or thicker than this range.

[0548] Furthermore, from the viewpoint of having excellent low reflectivity, the maximum reflectivity (incident angle 5°) of the light-shielding film per 5.0 μm film thickness in the wavelength region of 350 to 1200 nm is preferably less than 5%, more preferably less than 3%, and further preferably less than 1%. In addition, the lower limit is not particularly limited and is usually above 0%. As a method for measuring the maximum reflectivity of the light-shielding film, first, a light-shielding film is formed on a glass substrate, and a spectrometer (e.g., a VAR unit of a spectrometer V7200 manufactured by JASCO Corporation, etc.) is used to obtain a reflectivity spectrum relative to an incident angle of 5°, and the reflectivity of light of a wavelength showing a maximum reflectivity in the wavelength region of 350 to 1200 nm is obtained.

[0549] Furthermore, from the viewpoint of having excellent low reflectivity, the reflectivity of the light-shielding film per 5.0 μm film thickness in the wavelength region of 350 to 1200 nm (reflectivity under light with an incident angle of 5° and a wavelength of 940 nm) is preferably less than 5%, more preferably less than 3%, and further preferably less than 1%. In addition, the lower limit is not particularly limited and is usually above 0%. As a method for measuring the reflectivity of the light-shielding film, first, a light-shielding film is formed on a glass substrate, and a spectrometer (for example, a VAR unit of a spectrometer V7200 manufactured by JASCO Corporation, etc.) is used to obtain a reflectivity spectrum relative to an incident angle of 5°, and the reflectivity under light with a wavelength of 940 nm is obtained.

[0550] In addition, the shading film is suitable for portable devices such as personal computers, tablets, mobile phones, smart phones and digital cameras; OA (Office Automation) equipment such as multi-function printers and scanners; industrial equipment such as surveillance cameras, barcode readers and automatic teller machines (ATMs), high-speed cameras and equipment with personal identification functions using face recognition; vehicle-mounted camera equipment; medical camera equipment such as endoscopes, capsule endoscopes and catheters; and aerospace equipment such as living sensors, biosensors (Biosensors), military reconnaissance cameras, stereo map cameras, meteorological and ocean observation cameras, land resource reconnaissance cameras, and astronomical and deep space target exploration cameras in the universe; and shading components and shading films of filters and modules used in the shading films, and are therefore suitable for anti-reflection components and anti-reflection films.

[0551] The light-shielding film can also be used for micro LED (Light Emitting Diode) and micro OLED (Organic Light Emitting Diode) etc. In addition to filters and optical films used in micro LED and micro OLED, the light-shielding film is also suitable for components that provide light-shielding function or anti-reflection function.

[0552] Examples of micro LEDs and micro OLEDs include those described in Japanese Unexamined Patent Application Publication No. 2015-500562 and Japanese Unexamined Patent Application Publication No. 2014-533890.

[0553] The light-shielding film is suitable as an optical film used in quantum dot sensors and quantum dot solid-state imaging elements. In addition, it is suitable as a component that imparts light-shielding function and anti-reflection function. Examples of quantum dot sensors and quantum dot solid-state imaging elements include those described in U.S. Patent Application Publication No. 2012 / 37789 and International Publication No. 2008 / 131313.

[0554] <Solid-state imaging element and solid-state imaging device>

[0555] The light shielding film is also preferably used for a solid-state imaging element.

[0556] In other words, the solid-state imaging element of the present invention is a solid-state imaging element having the light-shielding film of the present invention.

[0557] There is no particular limitation on the manner in which a solid-state imaging element includes a light-shielding film, and for example, the following manner can be cited: a light-receiving element composed of a plurality of photodiodes and polycrystalline silicon that constitute a light-receiving area of ​​a solid-state imaging element (CCD image sensor, CMOS image sensor, etc.) is provided on a substrate, and a light-shielding film is provided on the light-receiving element forming surface side of the supporting body (for example, a portion other than the light-receiving portion and / or pixels for color adjustment, etc.) or on the side opposite to the forming surface.

[0558] Furthermore, when the light shielding film is used as the light attenuation film, for example, the dynamic range of the solid-state imaging element can be improved as long as the light attenuation film is arranged so that a part of light enters the light receiving element after passing through the light attenuation film.

[0559] A solid-state imaging device includes the above-mentioned solid-state imaging element.

[0560] <Image Display Device>

[0561] The light-shielding film is also preferably used in an image display device.

[0562] In other words, the image display device of the present invention is an image display device having the light-shielding film of the present invention.

[0563] As a mode in which the image display device has a light-shielding film, for example, there is a mode in which a color filter including a black matrix including a light-shielding film is applied to the image display device.

[0564] Next, a black matrix and a color filter including the black matrix will be described, and further, a liquid crystal display device including such a color filter will be described as a specific example of an image display device.

[0565] (Black Matrix)

[0566] The light-shielding film is also preferably included in the black matrix. The black matrix may be included in an image display device such as a color filter, a solid-state imaging element, and a liquid crystal display device.

[0567] Examples of the black matrix include the black matrix described above; a black edge provided at the periphery of an image display device such as a liquid crystal display device; a grid-shaped and / or linear black portion between red, blue, and green pixels; a dot-shaped and / or linear black pattern used for TFT (thin film transistor) light shielding; etc. The definition of the black matrix is ​​described, for example, in Taihei Kanno, "Dictionary of Terms for Liquid Crystal Display Manufacturing Equipment", 2nd edition, NIKKANKOGYO SHIMBUN, LTD., 1996, p. 64.

[0568] In order to improve display contrast and prevent image quality degradation caused by light current leakage in the case of an active matrix driven liquid crystal display device using a thin film transistor (TFT), the black matrix preferably has a high light shielding property (optical density OD of 3 or more).

[0569] The method for manufacturing the black matrix is ​​not particularly limited, and can be manufactured by the same method as the method for manufacturing the above-mentioned light-shielding film. Specifically, a curable composition can be applied to a substrate to form a composition layer, and a patterned light-shielding film (black matrix) is manufactured by exposure and development. In addition, the film thickness of the light-shielding film (black matrix) is preferably 0.1 to 4.0 μm.

[0570] The substrate is not particularly limited, but preferably has a transmittance of 80% or more to visible light (wavelength 400 to 800 nm). Examples of the material of the substrate include glasses such as soda-lime glass, alkali-free glass, quartz glass, and borosilicate glass; plastics such as polyester resins and polyolefin resins; and the like. From the viewpoint of chemical resistance and heat resistance, alkali-free glass or quartz glass is preferred.

[0571] (Color Filter)

[0572] It is also preferable that a light-shielding film is included in the color filter.

[0573] There is no particular limitation on the method of including a light-shielding film in a color filter, and examples thereof include a color filter having a substrate and the above-mentioned black matrix. That is, examples thereof include a color filter having red, green, and blue colored pixels formed in the openings of the above-mentioned black matrix formed on the substrate.

[0574] A color filter including a black matrix can be manufactured by the following method, for example.

[0575] First, a coating film (composition layer) of a curable composition containing a pigment corresponding to each color pixel of the color filter is formed in the opening of the patterned black matrix formed on the substrate. In addition, there is no particular limitation on the composition for each color, and a known composition can be used. Among the compositions described in this specification, a composition in which the black pigment is replaced with a colorant corresponding to each pixel is preferably used.

[0576] Next, the composition layer is exposed via a photomask having a pattern corresponding to the opening of the black matrix. Then, after the unexposed portion can be removed by development, baking is performed to form colored pixels at the opening of the black matrix. For example, as long as a series of operations are performed using each color composition containing red, green and blue pigments, a color filter having red, green and blue pixels can be manufactured.

[0577] (Liquid Crystal Display Device)

[0578] The light-shielding film is also preferably included in the liquid crystal display device. The embodiment in which the liquid crystal display device includes the light-shielding film is not particularly limited, and an embodiment including a color filter including the black matrix (light-shielding film) described above can be given.

[0579] As a liquid crystal display device, for example, there can be mentioned a mode including a pair of substrates arranged to face each other and a liquid crystal compound sealed between these substrates. As the above-mentioned substrate, a substrate for a black matrix has been described.

[0580] As a specific form of the above-mentioned liquid crystal display device, for example, a stacked body including polarizer / substrate / color filter / transparent electrode layer / orientation film / liquid crystal layer / orientation film / transparent electrode layer / TFT (Thin Film Transistor) element / substrate / polarizer / backlight unit in order from the user side can be cited.

[0581] In addition, the liquid crystal display device is not limited to the above, and for example, the liquid crystal display device described in "Electronic Display Device (written by Akio Sasaki, Kogyo Chosakai Publishing Co., Ltd., published in 1990)", "Display Device (written by Junsho Ibuki, Sangyotosyo Inc., published in 1989)", etc., can be cited. In addition, for example, the liquid crystal display device described in "Next Generation Liquid Crystal Display Technology (edited by Tatsuo Uchida, Kogyo Chosakai Publishing Co., Ltd., published in 1994)" can be cited.

[0582] <Infrared sensor>

[0583] It is also preferable that a light shielding film is included in the infrared sensor.

[0584] Next, a solid-state imaging device to which the above-mentioned infrared sensor is applied will be described.

[0585] The solid-state imaging device includes a lens optical system, a solid-state imaging element, an infrared light emitting diode, etc. For each structure of the solid-state imaging device, reference can be made to paragraphs 0032 to 0036 of Japanese Patent Application Laid-Open No. 2011-233983, the contents of which are incorporated into this specification.

[0586] <Cover glass, filter>

[0587] The light shielding film is also preferably used for the optical filter and cover glass assembled in the solid-state imaging device. As the optical filter, for example, an IR cut filter can be cited. By forming the light shielding film on the periphery of the optical filter and the cover glass, the generation of flare and ghosting can be suppressed.

[0588] Regarding the various structures of the above-mentioned filter with a light-shielding film and the solid-state imaging device, regarding paragraphs 0009 to 0012 of Japanese Patent Gazette No. 2014-132333, and the various structures of the cover glass with a light-shielding film and the solid-state imaging device, reference can be made to paragraphs 0017 to 0020, 0037 and 0040 of Japanese Patent Gazette No. 2021-092605, and the contents are incorporated into this specification.

[0589] Example

[0590] Below, the present invention is further described in detail based on embodiment. The material, usage, ratio, processing content and processing step etc. shown in the following embodiment can be appropriately changed as long as they do not depart from the gist of the present invention. Therefore, the scope of the present invention should not be interpreted restrictively by the following embodiment.

[0591] [[Preparation and evaluation of curable composition (1)]]

[0592] [Various components used in preparation of curable composition]

[0593] Hereinafter, the components for preparing the curable composition will be described in detail.

[0594] 〔Resin A〕

[0595] Table 1 shows the structures of the resins A (resins A-1 to A-15 and RA-1) shown in Table 3.

[0596] As resins A-1 to A-15 and RA-1, synthetic resins were used. The synthesis example of resin A-1 is shown below as an example. In addition, resins A-2 to A-15 and RA-1 were synthesized in the same steps as the synthesis example of resin A-1 except that the types and proportions of the raw material monomers were changed.

[0597] <Synthesis of Resin A-1>

[0598] 20.0 g of methacrylic acid (manufactured by FUJIFILM Wako Pure Chemical Corporation), 130.0 g of PME-1000 (manufactured by NOF CORPORATION), and 50.0 g of benzyl methacrylate (manufactured by FUJIFILM Wako Pure Chemical Corporation) were added to propylene glycol monomethyl ether acetate at 233% by mass relative to the total mass of the raw material monomers, and heated to 80° C. under a nitrogen stream. Next, 2 mol% of dodecanethiol and 0.5% by mass of a thermal polymerization initiator (V-601 manufactured by FUJIFILM Wako Pure Chemical Corporation) were added relative to the total mass of the raw material monomers, and stirred for 2 hours. Next, 0.5% by mass of a thermal polymerization initiator (V-601 manufactured by FUJIFILM Wako Pure Chemical Corporation) was added relative to the total mass of the raw material monomers, and stirred for further 2 hours. Then, 0.5% by mass of a thermal polymerization initiator (V-601 manufactured by FUJIFILM Wako Pure Chemical Corporation) was added based on the total mass of the raw material monomers, and the mixture was heated to 90° C. and stirred for 2 hours to synthesize resin A-1.

[0599] In addition, the weight average molecular weight of resins A-1 to A-15 is in the range of 15,000 to 39,000.

[0600] Table 1 is shown below.

[0601] [Table 1]

[0602]

[0603] [Table 2]

[0604]

[0605] 〔Resin B〕

[0606] Table 2 shows the structures of the resins B (resins B-1 to B-15 and RB-1 to RB-3) shown in Table 4.

[0607] As resins B-1 to B-15 and RB-1 to RB-3, synthesized resins were used. The synthesis example of resin B-1 is shown below as an example. In addition, resins B-2 to B-15 and RB-1 to RB-3 were synthesized in the same steps as the synthesis example of resin B-1, except that the types and proportions of raw material monomers were changed.

[0608] <Synthesis of Resin B-1>

[0609] A raw material monomer solution was prepared by mixing 172.0 g of methyl methacrylate (manufactured by FUJIFILM Wako Pure Chemical Corporation), 20.0 g of methacrylic acid (manufactured by FUJIFILM Wako Pure Chemical Corporation), and 8.0 g of 2-hydroxyethyl methacrylate (manufactured by FUJIFILM Wako Pure Chemical Corporation). In addition, a mixed solution A was prepared, which was mixed with 2 mol% of a thermal polymerization initiator (V-601 manufactured by FUJIFILM Wako Pure Chemical Corporation) and 111% by mass of 1-methoxy-2-propanol relative to the total mass of the raw material monomers. Next, a mixed solution B of the raw material monomer mixed solution and 74% by mass of 1-methoxy-2-propanol relative to the total mass of the raw material monomers was prepared and heated to 80° C., and then the mixed solution A was dripped into the mixed solution B over 2 hours (drop polymerization), and after the dripping, it was heated at 80° C. for 2 hours, and further heated at 90° C. for 3 hours, thereby synthesizing resin B-1.

[0610] In addition, the weight average molecular weight of resins B-1 to B-15 is within the range of 12,000 to 30,000.

[0611] Table 2 is shown below.

[0612] [Table 3]

[0613]

[0614] [Table 4]

[0615]

[0616] [Table 5]

[0617]

[0618] 〔Polymerizable compounds〕

[0619] The polymerizable compounds (C-1 to C-3) shown in Table 4 are shown below.

[0620] C-1: NK Ester A-TMMT (manufactured by SHIN-NAKAMURA CHEMICAL Co., Ltd., pentaerythritol tetraacrylate)

[0621] C-2: KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd., a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate)

[0622] C-3: NK Ester A-DPH-12E (manufactured by SHIN-NAKAMURA CHEMICAL Co., Ltd., ethoxylated dipentaerythritol polyacrylate)

[0623] 〔pigment〕

[0624] The pigments (D-1 to D-4) shown in Table 3 are shown below.

[0625] D-1: TiON (titanium oxynitride)

[0626] D-2: TiN (titanium nitride)

[0627] D-3: TiO2 (titanium oxide)

[0628] D-4: CB (carbon black)

[0629] 〔Photopolymerization initiator〕

[0630] The photopolymerization initiators (E-1 to E-3) shown in Table 4 are shown below.

[0631] · E-1: IRGACURE OXE02 (manufactured by BASF, oxime ester polymerization initiator)

[0632] ·E-2: ADEKA ARKLS NCI-831E (manufactured by ADEKA CORPORATION, oxime ester polymerization initiator)

[0633] ·E-3: Compound having the following structure (oxime ester polymerization initiator)

[0634] [Chemical formula 20]

[0635]

[0636] [Thermal cross-linking compound]

[0637] The thermally crosslinkable compounds (F-1 to F-3) shown in Table 4 are shown below.

[0638] F-1: CELLOXIDE 2021P (manufactured by DAICEL CHEMICAL INDUSTRIES, LTD.)

[0639] ·F-2: EOCN-1020 (manufactured by Nippon Kayaku Co., Ltd.)

[0640] ·F-3: EHPE-3150 (manufactured by DAICEL CHEMICAL INDUSTRIES, LTD.)

[0641] 〔Surfactant〕

[0642] The surfactants (W-1) shown in Table 4 are shown below.

[0643] W-1: KF6001 (manufactured by Shin-Etsu Chemical Co., Ltd.)

[0644] 〔Solvent〕

[0645] The solvents shown in Table 3 and Table 4 are shown below.

[0646] PGMEA: Propylene glycol monomethyl ether acetate

[0647] PGME: 1-methoxy-2-propanol

[0648] Butyl acetate

[0649] 〔Preparation of pigment dispersion〕

[0650] After mixing the components shown in Table 3 in the amounts (parts by mass) shown in Table 3, 230 parts by mass of zirconia beads having a diameter of 0.3 mm were added, and dispersion treatment was performed for 5 hours using a paint shaker, and the beads were separated by filtration to produce each pigment dispersion (pigment dispersion 1 to 16). The parts by mass of resin A are recorded as parts by mass of the resin solid component excluding the solvent described in <Synthesis Example of Resin A-1>.

[0651] Table 3 is shown below.

[0652] [Table 6]

[0653]

[0654] [Preparation of curable composition]

[0655] The curable compositions of Examples and Comparative Examples were prepared by mixing the components shown in Table 4 in the amounts (parts by mass) shown in Table 4. The parts by mass of the pigment dispersion are the amount of the entire solution including the solvent, and the parts by mass of the resin B are the parts by mass of the resin solid content excluding the solvent described in <Synthesis Example of Resin B-1>.

[0656] Table 4 is shown below.

[0657] In addition, "content ratio T1" in Table 4 represents the ratio of the content of resin A to the total content of resin A and resin B [A / (A+B) (A: content of resin A, B: content of resin B].

[0658] In addition, "content ratio T2" in Table 4 represents the ratio of the content of the polymerizable compound to the total content of resin A, resin B and the polymerizable compound [C / (A+B+C). A: content of resin A, B: content of resin B, C: content of polymerizable compound].

[0659]

[0660]

[0661] [evaluate]

[0662] The curable composition was evaluated by the following method. The results are shown in Table 5.

[0663] 〔Evaluation of reflectivity〕

[0664] Each curable composition of the embodiment and the comparative example was applied on a glass substrate by spin coating to prepare a coating film having a thickness of 5.0 μm after exposure. After pre-baking at 90° C. for 120 seconds, the coating film was heated by a high-pressure mercury lamp (lamp power of 50 mW / cm 2 ), 1000mJ / cm 2 The entire surface of the substrate was exposed with an exposure amount of . The exposed substrate was post-baked at 220° C. for 300 seconds to obtain a substrate with a cured film.

[0665] For the substrate with a cured film produced, a spectrometer V7200 (trade name) VAR unit manufactured by JASCO Corporation was used to inject light of a wavelength of 350 to 1200 nm at an incident angle of 5°, and the reflectivity spectrum of the obtained reflection angle of 5° was evaluated. Specifically, the reflectivity of light with a wavelength of 940 nm was used as an evaluation standard and evaluated according to the following classification. In addition, in practical application, an evaluation of "3" or more is preferred, and an evaluation of "4" or more is more preferred.

[0666] (Evaluation Criteria)

[0667] "5": reflectivity less than 1%

[0668] "4": Reflectivity is 1% or more and less than 3%

[0669] "3": Reflectivity is 3% or more and less than 5%

[0670] "2": Reflectivity is 5% or more and less than 7%

[0671] "1": Reflectivity is 7% or more

[0672] [Evaluation of pattern adhesion]

[0673] Using a spin coater, each curable composition of the example and the comparative example was applied to an 8-inch silicon wafer pre-sprayed with hexamethyldisilazane to produce a coating film having a thickness of 5.0 μm after exposure. Then, the obtained coating film was pre-baked at 100° C. for 120 seconds to produce a substrate with a film.

[0674] Then, an i-ray stepper FPA-i5+ (manufactured by Canon Inc.) was used to expose the film at a wavelength of 365 nm at a temperature of 50 to 1,700 mJ / cm through a mask having an island pattern of 50 μm square (a mask having 25 openings of 50 μm square). 2 The film in the produced film-bearing substrate was irradiated with an exposure amount of . After exposure, it was developed using an alkaline developer CD-2000 (manufactured by FUJIFILM Flectronic Materials Co., Ltd.) at 25° C. and for 40 seconds. Then, after rinsing under running water for 30 seconds, it was spray-dried to obtain a substrate with a cured film.

[0675] The obtained 50 μm square island pattern was observed from above using a scanning electron microscope (S-9220 manufactured by Hitachi, Ltd.), and the number of patterns obtained was measured. The minimum exposure required when all the 50 μm square island patterns are closely fitted was determined, and the close fit was evaluated according to the following classification. If the evaluation is "3" or above, it is judged that there is no problem in practical application. In addition, in practical application, an evaluation of "3" or above is preferred, and an evaluation of "4" or above is more preferred.

[0676] (Evaluation Criteria)

[0677] "5": minimum exposure is 400mJ / cm 2 the following.

[0678] "4": minimum exposure exceeds 400mJ / cm 2 And 900mJ / cm 2 the following.

[0679] "3": minimum exposure exceeds 900mJ / cm 2 And 1700mJ / cm 2 the following.

[0680] "2": 50~1700mJ / cm 2 The exposure amount can form at least one 50μm square island pattern, but cannot form all patterns.

[0681] "1": 50~1700mJ / cm 2 The exposure amount was not enough to form an island pattern of 50 μm square.

[0682] [Evaluation of Development Residue (Residue in Unexposed Area)]

[0683] Using a spin coater, each curable composition of the example and the comparative example was applied to an 8-inch silicon wafer pre-sprayed with hexamethyldisilazane to produce a coating film having a thickness of 5.0 μm after exposure. Then, the obtained coating film was pre-baked at 100° C. for 120 seconds to produce a substrate with a film.

[0684] Then, an i-ray stepper FPA-3000i5+ (manufactured by Canon Inc.) was used to expose the film at a rate of 50 to 1,700 mJ / cm 2 The film in the produced film-bearing substrate was irradiated with light of a wavelength of 365 nm at an exposure amount of . Next, the exposed film (cured film) was developed at 25° C. for 60 seconds using a 60% CD-2000 (manufactured by FUJIFILM Flectronic Materials Co., Ltd.) developer to obtain a patterned cured film. The patterned cured film was then rinsed with running water for 20 seconds and then air-dried.

[0685] In the exposure step, the minimum exposure amount at which the pattern line width after development in the region irradiated with light becomes 50 μm or more is set as exposure sensitivity, and this exposure sensitivity is set as initial exposure sensitivity.

[0686] The cured film obtained by the minimum exposure amount at which the pattern line width after development becomes 50 μm or more was heated in an oven at 220°C for 1 hour per substrate. After the cured film was heated, the number of residues present in the area (unexposed part) not irradiated with light was observed by SEM (Scanning Electron Microscope: Scanning Electron Microscope: Scanning Electron Microscope, magnification: 20000 times) in the exposure process on the substrate, and the development residue (unexposed part residue) was evaluated according to the following classification. In addition, in practical application, the evaluation of "3" or more is preferred, and the evaluation of "4" or more is more preferred.

[0687] "5": No pattern was formed, and no residue was observed in the unexposed portion.

[0688] "4": Patterning was not formed, and 1 to 3 residues were observed in a 1.0 μm square area in the unexposed portion.

[0689] "3": Patterning was not formed, and 4 to 10 residues were observed in a 1.0 μm square area in the unexposed portion.

[0690] "2": Patterning was not formed, and 11 or more residues were observed in a 1.0 μm square area in the unexposed portion.

[0691] "1": Development is poor and no pattern is formed.

[0692] Table 5 is shown below.

[0693] [Table 9]

[0694]

[0695] From the results shown in Table 5, it was found that the cured film obtained by curing the curable composition of the example was excellent in low reflectivity to infrared light if it was excellent in adhesiveness.

[0696] Furthermore, it was confirmed that when the following requirement A1 or the following requirement A2 is satisfied (preferably, when the following requirement B1 or the following requirement B2 is satisfied), the cured film obtained by curing the curable composition has more excellent low reflectivity to infrared light.

[0697] Requirement A1: The repeating unit A2 in the resin A contains a repeating unit having a polyoxyalkylene carbonyl group with an average addition number of 3 or more.

[0698] Requirement A2: Resin A contains repeating units having a polyoxyalkylene group with an average addition number of 10 or more, and Resin A contains repeating units having a benzyl group (preferably repeating units derived from benzyl (meth)acrylate).

[0699] Requirement B1: Repeating unit A2 in resin A contains repeating units having a polyoxyalkylene carbonyl group with an average addition number of 3 or more, and the number of carbon atoms of the alkyl group bonded to the ester bond in repeating unit B1 in resin B is 4 or more.

[0700] Requirement B2: Resin A contains repeating units having a polyoxyalkylene group with an average addition number of 10 or more and repeating units having a benzyl group (preferably a repeating unit derived from benzyl (meth)acrylate), and the number of carbon atoms of the alkyl group bonded to the ester bond in repeating unit B1 in resin B is 4 or more.

[0701] Furthermore, it was confirmed that when the curable composition contains a thermally crosslinkable compound, there is a tendency for the adhesion of the cured film to be further improved.

[0702] Furthermore, it was confirmed that when the resin A in the curable composition contains a repeating unit represented by formula (A11), formula (A12) or formula (A13) (especially, a repeating unit represented by formula (A12)) as a repeating unit having an acid group, there is a tendency to further reduce the development residue.

[0703] [[Preparation and evaluation of curable composition (2)]]

[0704] [Preparation of curable composition]

[0705] Compositions 24 to 36 were prepared in the same manner as in Example 20 except that the solvent (mixed solvent of PGMEA and PGME (PGMEA: 12.60 parts by mass, PGME: 12.52 parts by mass)) in Example 20 was changed to the solvent shown in Table 6 below (mixed solvent in which solvents 1 to 4 were mixed in the combination described in Table 6). The results of these were evaluated by the same evaluation method as in Example 20, and the same evaluation results as in Example 20 were obtained.

[0706] [Table 10]

[0707]

[0708] 〔Solvent〕

[0709] In addition, the abbreviations of the solvents shown in Table 6 represent the following solvents.

[0710] PGMEA: Propylene glycol monomethyl ether acetate

[0711] PGME: 1-methoxy-2-propanol

[0712] CyP: Cyclopentanone

[0713] CyH: Cyclohexanone

[0714] MB: 3-methoxybutanol

[0715] 1,3-BG: 1,3-Butanediol

[0716] 2,3-BG: 2,3-Butanediol

[0717] PG: Propylene glycol

[0718] EG: Ethylene glycol

[0719] DMSO: dimethyl sulfoxide

[0720] GVL: gamma-valerolactone

[0721] DAA: diacetone alcohol

[0722] [[Preparation and evaluation of curable composition (3)]]

[0723] [Various components used in preparation of curable composition]

[0724] Hereinafter, the components for preparing the curable composition will be described in detail.

[0725] 〔Pigment dispersion〕

[0726] The pigment dispersions 11 and 13 shown in Table 8 are the same as the pigment dispersions 11 and 13 used in Table 4.

[0727] 〔Resin B〕

[0728] The resins B (resin B-8, resins B-16 to B-19) shown in Table 8 are shown below.

[0729] Resin B-8: The same as the resin B-8 used in Table 4.

[0730] Resins B-16 to B-19: The structures of resins B-16 to B-19 are shown in Table 7. In addition, as resins B-16 to B-19, synthesized resins were used. In addition, resins B-16 to B-19 were synthesized by the same procedure as the synthesis example of resin B-1 except that the types and proportions of raw material monomers were changed.

[0731] In addition, the weight average molecular weight of resins B-16 to B-19 is in the range of 18,000 to 39,000.

[0732] Table 7 is shown below.

[0733] [Table 11]

[0734]

[0735] 〔Polymerizable compounds〕

[0736] The polymerizable compounds (C-2, C-4 to C-6) shown in Table 8 are shown below.

[0737] C-2: The same as the polymerizable compound C-2 used in Table 4.

[0738] C-4: KAYARAD RP-1040 (manufactured by Nippon Kayaku Co., Ltd., ethoxylated pentaerythritol tetraacrylate)

[0739] C-5: KAYARAD DCPA-20 (manufactured by Nippon Kayaku Co., Ltd., a polymerizable compound containing a caprolactone structure)

[0740] C-6: OGSOLEA-0300 (manufactured by Osaka Gas Chemicals Co., Ltd., a polymerizable compound having a 9,9-bisarylfluorene skeleton)

[0741] 〔Photopolymerization initiator〕

[0742] The photopolymerization initiators (E-2, E-4 to E-6) shown in Table 8 are shown below.

[0743] E-2: The same as the photopolymerization initiator E-2 used in Table 4.

[0744] · E-4: IRGACURE OXE01 (manufactured by BASF, oxime ester polymerization initiator)

[0745] ·E-5: Omnirad 1316 (manufactured by TGM RESINS BV, oxime ester polymerization initiator)

[0746] · E-6: Omnirad-2959 (manufactured by IGM RESINS BV, hydroxyacetophenone compound-based polymerization initiator)

[0747] [Thermal cross-linking compound]

[0748] The heat-crosslinkable compound F-3 shown in Table 8 is the same as the heat-crosslinkable compound F-3 used in Table 4.

[0749] 〔Solvent〕

[0750] PGME: 1-methoxy-2-propanol

[0751] CyP: Cyclopentanone

[0752] 〔Surfactant〕

[0753] The surfactant W-1 shown in Table 8 is the same as the surfactant W-1 used in Table 4.

[0754] [Preparation of curable composition]

[0755] The components shown in the following Table 8 were mixed in the amounts (parts by mass) shown in Table 8 to prepare the curable compositions of Examples and Comparative Examples. The parts by mass of the pigment dispersion are the amount of the entire solution including the solvent, and the parts by mass of the resin B are the parts by mass of the resin solid content excluding the solvent described in <Synthesis Example of Resin B-1>.

[0756] The above-mentioned various evaluations were carried out in the same manner using the obtained curable composition. The evaluation results are shown in Table 8.

[0757] Table 8 is shown below.

[0758] In addition, "content ratio T1" in Table 8 represents the ratio of the content of resin A to the total content of resin A and resin B [A / (A+B) (A: content of resin A, B: content of resin B].

[0759] In addition, "content ratio T2" in Table 8 represents the ratio of the content of the polymerizable compound to the total content of resin A, resin B and the polymerizable compound [C / (A+B+C). A: content of resin A, B: content of resin B, C: content of polymerizable compound].

[0760]

[0761] [Table 13]

[0762]

[0763] From the results shown in Table 9, it was found that the cured film obtained by curing the curable composition of the example was excellent in low reflectivity to infrared light if it was excellent in adhesiveness.

[0764] Furthermore, from the comparison of Examples, it was confirmed that when the acid value of the resin B contained in the curable composition was 100 mgKOH / g or less, there was a tendency that the adhesion of the cured film was further improved.

Claims

1. A curable composition comprising a resin A, a resin B, a polymerizable compound, a pigment and a photopolymerization initiator, The resin A comprises a repeating unit having an acid group and a repeating unit having a group selected from a polyoxyalkylene group having an average addition number of 3 or more and a polyoxyalkylene carbonyl group having an average addition number of 3 or more, The content of the repeating unit having a group selected from the group consisting of polyoxyalkylene groups having an average addition number of 3 or more and polyoxyalkylene carbonyl groups having an average addition number of 3 or more is 35% by mass or more relative to all the repeating units of the resin A, The acid value of the resin A is above 50 mgKOH / g, The resin B comprises a repeating unit derived from a monomer selected from an alkyl acrylate and an alkyl methacrylate, a repeating unit having a hydroxyl group, and a repeating unit having a carboxylic acid group, The content of the repeating unit derived from the monomer selected from alkyl acrylate and alkyl methacrylate is 60% by mass or more relative to all the repeating units of the resin B, The content of the resin A is in the range of 0.30 to 0.50 relative to the total content of the resin A and the resin B. The ratio of the content of the polymerizable compound to the total content of the resin A, the resin B, and the polymerizable compound is 0.30 to 0.

50.

2. The curable composition according to claim 1, wherein The repeating unit having an acid group includes one or more selected from the group consisting of a repeating unit represented by the following formula (A11), a repeating unit represented by the following formula (A12), and a repeating unit represented by the following formula (A13), In formula (A13), n represents the average addition number, which is 1 to 2.

3. The curable composition according to claim 1 or 2, wherein The resin A further includes a repeating unit having a benzyl group.

4. The curable composition according to claim 1 or 2, wherein In the repeating unit derived from a monomer selected from an alkyl acrylate and an alkyl methacrylate, the alkyl group linked to the ester bond of the alkyl acrylate and the alkyl methacrylate has 4 or more carbon atoms.

5. The curable composition according to claim 1 or 2, wherein The content of the repeating unit derived from a monomer selected from the group consisting of alkyl acrylates and alkyl methacrylates is 80% by mass or more based on all the repeating units of the resin B.

6. The curable composition according to claim 1 or 2, wherein The acid value of the resin B is 55 mgKOH / g or more.

7. The curable composition according to claim 1 or 2, wherein The repeating unit having a hydroxyl group includes a repeating unit derived from a monomer selected from 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate.

8. The curable composition according to claim 1 or 2, wherein The pigment comprises titanium oxynitride. 9 . The curable composition according to claim 1 , which is a composition for forming a light-shielding film. 10 . A light-shielding film comprising a cured film formed from the curable composition according to claim 1 or 2. 11 . A solid-state imaging element comprising a cured film formed from the curable composition according to claim 1 or 2. 12 . An image display device comprising a cured film formed from the curable composition according to claim 1 . 13 . An infrared sensor comprising a cured film formed from the curable composition according to claim 1 or 2 . 14 . An optical filter comprising a cured film formed from the curable composition according to claim 1 or 2. 15 . A cover glass comprising a cured film formed from the curable composition according to claim 1 or 2 .

16. A method for producing a cured film, comprising: A composition layer forming step, forming a composition layer on a support using the curable composition according to claim 1 or 2; an exposure step of exposing the composition layer by irradiating actinic rays or radiation; and The development step is to perform a development treatment on the composition layer after exposure.

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