Coloring compositions, cured films, light-shielding films, color filters, optical elements, solid-state image sensors, infrared sensors, headlight units

Abstract

The present invention provides: a coloring composition which is capable for forming a cured film that exhibits excellent adhesion to a base material, while having a high color valency; a cured film; a light-blocking film; a color filter; an optical element; a solid-state imaging element; an infrared sensor; and a headlight unit. A coloring composition according to the present invention contains a pigment, a solvent, and a resin that has a constituent unit A having a polymerizable group, a constituent unit B having a phenolic hydroxyl group, and a constituent unit C having an acidic group; and the content of the pigment is 15% by mass or more relative to the total solid content.

Description

[Technical Field]

[0001] The present invention relates to a colored composition, a cured film, a light-shielding film, a color filter, an optical element, a solid-state image sensor, an infrared sensor, and a headlight unit. [Background technology]

[0002] Color filters used in liquid crystal displays are equipped with a colored film called a black matrix, which is used to block light between colored pixels and improve contrast. Furthermore, mobile devices such as mobile phones and PDAs (Personal Digital Assistants) are currently equipped with small, thin imaging units. Solid-state image sensors such as CCD (Charge Coupled Device) image sensors and CMOS (Complementary Metal-Oxide Semiconductor) image sensors are provided with light-shielding films to prevent noise generation and improve image quality.

[0003] For example, Patent Document 1 discloses a radiation-sensitive coloring composition comprising a copolymer consisting of a predetermined monomer, a radiation-sensitive compound, and a pigment. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Application Publication No. 10-254133 [Overview of the project] [Problems that the invention aims to solve]

[0005] The present inventors investigated the coloring composition (radiation-sensitive coloring composition) disclosed in Patent Document 1 and found that it is difficult to achieve both high color value (color intensity) and adhesion to the substrate in the cured film formed using the coloring composition.

[0006] Therefore, the object of the present invention is to provide a coloring composition that can form a cured film with a high color value and excellent adhesion to a substrate. Another object of the present invention is to provide a cured film, a light-shielding film, a color filter, an optical element, a solid-state image sensor, an infrared sensor, and a headlight unit using the above photosensitive composition. [Means for solving the problem]

[0007] As a result of diligent research, the inventors of the present invention have found that the above problems can be solved by the following configuration, and have completed the present invention.

[0008] [1] Pigments and Solvents and, A resin comprising a polymerizable unit A, a phenolic hydroxyl group B, and an acidic group C, A colored composition in which the amount of the above-mentioned pigment is 15% by mass or more relative to the total solid content of the colored composition. [2] The colored composition according to [1], wherein the above-mentioned constituent unit A is a constituent unit represented by formula 1. [ka] In formula 1, R 1 ~R 3 Each of these independently represents either a hydrogen atom or an alkyl group. X 1 represents -COO-, -CONR-, or an arylene group. R represents a hydrogen atom, an alkyl group, or an aryl group. R 4 This represents a linking group with (n+1) valence. X 2 is an oxygen atom or -NR A - represents RA represents a hydrogen atom, an alkyl group, or an aryl group. R 0 represents a hydrogen atom or an alkyl group. n represents an integer of 1 or more. 〔3〕 The coloring composition according to 〔1〕 or 〔2〕, wherein the constitutional unit B is a constitutional unit represented by Formula 2.

Chemical formula

Chemical formula

[10] The colored composition according to any one of [1] to [9], wherein the above resin further comprises a constituent unit D represented by formula D. [ka] In formula D, R D represents a hydrogen atom or an alkyl group. X D is an oxygen atom or -NR C - represents R C represents a hydrogen atom, an alkyl group, or an aryl group. L D This represents a single bond or a divalent linking group. Y 1 and Y 2 Each of these independently represents either an alkylene oxy group or an alkylene carbonyl oxy group. Z 1 This represents an aliphatic hydrocarbon group having 1 to 20 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms. p and q each independently represent non-negative integers. However, the value of p+q must be 1 or greater.

[11] A cured film formed using any of the coloring compositions described in [1] to

[10] .

[12] A light-shielding film comprising the cured film described in

[11] .

[13] A color filter comprising the cured film described in

[11] .

[14] An optical element comprising the cured film described in

[11] .

[15] A solid-state image sensor comprising the cured film described in

[11] .

[16] An infrared sensor comprising the cured film described in

[11] .

[17] A headlight unit for a vehicle, Light source and It has a light-shielding section that blocks at least a portion of the light emitted from the above light source, A headlight unit in which the light-shielding portion includes the hardened film described in

[11] . [Effects of the Invention]

[0009] The present invention provides a coloring composition that can form a cured film with a high color value and excellent adhesion to a substrate. Furthermore, the present invention can also provide a cured film, a light-shielding film, a color filter, an optical element, a solid-state image sensor, an infrared sensor, and a headlight unit using the above coloring composition. [Brief explanation of the drawing]

[0010] [Figure 1] This is a schematic cross-sectional view showing an example of the configuration of a solid-state imaging device. [Figure 2] This is a schematic cross-sectional view showing an enlarged view of the imaging unit of the solid-state imaging device shown in Figure 1. [Figure 3] This is a schematic cross-sectional view showing an example of an infrared sensor configuration. [Figure 4] This is a schematic diagram showing an example of the configuration of a headlight unit. [Figure 5] This is a schematic perspective view showing an example of the configuration of the light-shielding section of a headlight unit. [Figure 6] This is a schematic diagram showing an example of a light distribution pattern created by the light-shielding portion of a headlight unit. [Figure 7] This is a schematic diagram illustrating another example of the light distribution pattern created by the light-shielding portion of the headlight unit. [Modes for carrying out the invention]

[0011] The contents of this specification will be described in detail below. The descriptions of constituent elements described below may be based on representative embodiments of this specification, but this specification is not limited to such embodiments. In this specification, the "~" symbol indicating a numerical range is used to mean that the numbers before and after it are included as the lower and upper limits, respectively. In numerical ranges described stepwise within this specification, the upper or lower limit of one numerical range may be replaced with the upper or lower limit of another numerical range described stepwise. Furthermore, in numerical ranges described within this specification, the upper or lower limit of that range may be replaced with the values ​​shown in the examples. Furthermore, in the notation of groups (atomic groups) in this specification, the notation that does not specify whether they are substituted or unsubstituted includes both those with and without substituents. For example, "alkyl group" includes not only alkyl groups without substituents (unsubstituted alkyl groups) but also alkyl groups with substituents (substituted alkyl groups). In this specification, unless otherwise specified, "Me" represents a methyl group, "Et" represents an ethyl group, "Pr" represents a propyl group, "Bu" represents a butyl group, and "Ph" represents a phenyl group. In this specification, "(meth)acrylic" is a term used to encompass both acrylic and methacrylic, and "(meth)acryloyl" is a term used to encompass both acryloyl and methacryloyl. Furthermore, in this specification, the term "process" includes not only independent processes but also processes that cannot be clearly distinguished from other processes, as long as their intended purpose is achieved. Furthermore, in this specification, a combination of two or more preferred embodiments is a more preferred embodiment. Furthermore, unless otherwise specified, the weight-average molecular weight (Mw) and number-average molecular weight (Mn) in this specification are polystyrene-equivalent values ​​measured under the following conditions. "Equipment: HLC-8220GPC (Tosoh Corporation), Detector: Differential Refractometer (RI detector), Pre-column: TSKGUARDCOLUMN MP(XL) 6mm×40mm (Tosoh Corporation), Sample-side column: Four TSK-GEL Multipore-HXL-M 7.8mm×300mm columns directly connected (all Tosoh Corporation), Reference-side column: Same as sample-side column, Incubator temperature: 40℃, Mobile phase: Tetrahydrofuran, Sample-side mobile phase flow rate: 1.0mL / min, Reference-side mobile phase flow rate: 0.3mL / min, Sample concentration: 0.1% by mass, Sample injection volume: 100μL, Data acquisition time: 16 to 46 minutes after sample injection, Sampling pitch: 300msec"

[0012] Furthermore, in this specification, "active light" or "radiation" means, for example, the emission line spectra of mercury lamps such as g-rays, h-rays, and i-rays, far ultraviolet light represented by excimer lasers, extreme ultraviolet (EUV) light, X-rays, electron beams (EB), etc. Also, in this invention, "light" means active light or radiation. Furthermore, unless otherwise specified, "exposure" in this specification includes not only exposure using far ultraviolet, extreme ultraviolet, X-ray, and EUV light, such as mercury lamps and excimer lasers, but also drawing using particle beams such as electron beams and ion beams. In this specification, "monomer" and "monomer" are synonymous.

[0013] In this specification, "ppm" means "parts per million (10) -6 ) means "ppb" means "parts per billion (10 -9 ) means "ppt" means "parts per trillion (10 -12 It means ")".

[0014] The bonding direction of divalent groups as expressed herein is not limited unless otherwise specified. For example, in a compound represented by the general formula "XYZ", if Y is an ester group (-COO-), the compound may be "XO-CO-Z" or "X-CO-OZ".

[0015] In this specification, "color value" refers to the intensity of a color, and a high color value means that the OD value is high for light across the entire wavelength range of 400 to 1100 nm.

[0016] [Coloring composition (composition)] The colored composition of the present invention (hereinafter also simply referred to as "the composition") comprises a pigment, a solvent, and a resin having a polymerizable unit A, a phenolic hydroxyl group B, and an acidic group C (hereinafter also referred to as "the specific resin"), wherein the content of the pigment is 15% by mass or more with respect to the total solid content of the composition. Furthermore, the "solid content" of a composition refers to the components that form the cured film. If the composition contains a solvent (organic solvent, water, etc.), it refers to all components excluding the solvent. In addition, any liquid components that form the cured film are also considered to be part of the solid content. The mechanism by which the problems of the present invention are solved by a composition having the above configuration is not entirely clear, but the inventors believe it to be as follows. In other words, since the composition of the present invention contains 15% by mass or more of pigment relative to the total solid content of the composition, the color value of the cured film formed is high. Furthermore, the specific resin contained in the composition has a polymerizable unit A and a phenolic hydroxyl group. Since unit A has a polymerizable group, it can polymerize with other specific resins and with polymerizable compounds added as desired, forming a covalent network within the cured film. In addition, the phenolic hydroxyl group of unit B generates hydrogen bonds and stacking interactions between aromatic rings within the cured film. The cured film formed from the composition of the present invention has strong physical properties due to the synergistic contribution of these elements, and it is believed that this strength makes it difficult for the cured film to peel off the substrate on which it is formed, resulting in good adhesion of the cured film. Furthermore, the composition of the present invention also exhibits good suppression of developing residue. Hereinafter, the present invention is said to be more effective if the composition satisfies at least one of the following conditions: the composition can form a cured film with a higher color value; the composition can form a cured film with superior adhesion; and the composition has superior inhibitory properties for developing residue.

[0017] The components of the composition of the present invention will be described below.

[0018] [Resin (Specific Resin)] <Component Unit A> The composition of the present invention comprises a specific resin, the specific resin having constituent unit A. Constituent unit A is a constituent unit that has polymerizable groups. Examples of polymerizable groups include ethylenically unsaturated groups (such as (meth)acryloyl groups, vinyl groups, and styryl groups) and cyclic ether groups (such as epoxy groups and oxetanyl groups). Among these, the polymerizable group is preferably an ethylenically unsaturated group, and more preferably a (meth)acryloyl group. The number of polymerizable groups in constituent unit A is 1 or more, preferably 1 to 6, and more preferably 1. Constituent unit A may use one polymerizable group alone, or two or more polymerizable groups.

[0019] Constituent unit A is preferably the constituent unit represented by formula 1.

[0020] [ka]

[0021] In formula 1, R 1 ~R 3 Each of these independently represents either a hydrogen atom or an alkyl group. The alkyl group described above may be linear or branched, and preferably has 1 to 6 carbon atoms. Among them, R 1 Preferably, it is a hydrogen atom or an alkyl group. R 2 and R 3Preferably, it is a hydrogen atom.

[0022] In formula 1, X 1 This represents -COO-, -CONR-, or an arylene group. The above-mentioned arylene group may be monocyclic or polycyclic, and preferably has 6 to 15 carbon atoms. In -CONR-, R represents a hydrogen atom, an alkyl group, or an aryl group. The alkyl group represented by R in -CONR- may be linear or branched, and preferably has 1 to 6 carbon atoms. The aryl group represented by R in -CONR- may be monocyclic or polycyclic, and preferably has 6 to 15 carbon atoms.

[0023] In formula 1, R 4 This represents a linking group with (n+1) valence. Examples of the above linking groups include ether groups, carbonyl groups, ester groups, thioethers, -SO2-, and -NR. X -(R X This includes a hydrogen atom or substituents such as alkyl groups, alkylene groups (e.g., 1 to 10 carbon atoms), alkenylene groups (e.g., 2 to 12 carbon atoms), alkynylene groups (e.g., 2 to 12 carbon atoms), trivalent groups represented by "-N<", "-CR Y The trivalent group represented by < (R Y Examples include tetravalent groups represented by ">C<", such as a hydrogen atom or a substituent like an alkyl group, aromatic ring groups (e.g., 5 to 15 ring members), alicyclic groups (e.g., 3 to 15 carbon atoms), non-aromatic heterocyclic groups (e.g., 3 to 15 ring members), onium structure-containing groups, and groups that combine these. The above-mentioned onium structure-containing group is a group having an anionic part and a cationic part. The anionic portion preferably has a structure that includes a group from which a proton (for example, 1 to 3 protons) has been dissociated from an acid group. Examples of the acid group include a carboxyl group, a sulfonic acid group, a phosphonic acid group, and a phosphate group. Examples of cation moieties include ammonium cations. When the cation moiety is an ammonium cation, the cation moiety is a cationic nitrogen atom (>N). +It is a substructure that includes <). The cation part is "N + R C The substructure may also be represented as "3-". Each Rc independently represents a hydrogen atom or a substituent, and hydrogen atoms, alkyl groups (e.g., 1 to 20 carbon atoms), or aryl groups (e.g., 6 to 15 carbon atoms) are preferred. R 4 The group is preferably a group with a total number of atoms of 1 to 200, more preferably a group with a total number of atoms of 2 to 100, and even more preferably a group with a total number of atoms of 2 to 60.

[0024] In formula 1, X 2 is an oxygen atom or -NR A - represents R A represents a hydrogen atom, an alkyl group, or an aryl group. The alkyl group described above may be linear or branched, and preferably has 1 to 6 carbon atoms. The above aryl group may be monocyclic or polycyclic, and preferably has 6 to 15 carbon atoms.

[0025] R 0 This represents a hydrogen atom or an alkyl group. The alkyl group described above may be linear or branched, and preferably has 1 to 6 carbon atoms.

[0026] In equation 1, n represents an integer greater than or equal to 1. n is preferably an integer between 1 and 6, and more preferably 1. The value of n explicitly stated in Equation 1 is R 4 This is the same as the value of n in the (n+1) valence linking group represented by . In equation 1, X 2 If there are multiple X 2 These elements are independent of each other and may be identical or different. In equation 1, R 0 If there are multiple instances, then there are multiple R 0 These elements are independent of each other and may be identical or different.

[0027] It is preferable that constituent unit A includes the constituent unit represented by formula 3.

[0028]

Chem.

[0029] In formula 3, R 1 ~R 3 each independently represents a hydrogen atom or an alkyl group. In formula 3, X 1 represents -COO-, -CONR-, or an arylene group, and R represents a hydrogen atom, an alkyl group, or an aryl group. In formula 3, X 2 represents an oxygen atom or -NR A -. R A represents a hydrogen atom, an alkyl group, or an aryl group. In formula 3, n represents an integer of 1 or more. In formula 3, R 0 represents a hydrogen atom or an alkyl group. R in formula 3 1 ~R 3 , X 1 , X 2 , R 0 , and n are the same as R 1 ~R 3 , X 1 , X 2 , R 0 , and n in formula 1, respectively. The value of n specified in formula 3 is the same as the value of n in the (n + 1)-valent linking group represented by R 6 described later. In formula 3, when there are a plurality of X 2 , the plurality of X 2 are each independent and may be the same or different from each other. In formula 3, when there are a plurality of R 0 , the plurality of R 0 are each independent and may be the same or different from each other.

[0030] In formula 3, R 5 represents a divalent linking group. Examples of the above-mentioned divalent linking groups include ether groups, carbonyl groups, ester groups, thioether groups, -SO2-, and -NR. X -(R X Examples include substituents such as hydrogen atoms or alkyl groups, divalent hydrocarbon groups (e.g., alkylene groups (e.g., 1-10 carbon atoms), alkenylene groups (e.g., 2-12 carbon atoms), alkynylene groups (e.g., 2-12 carbon atoms), arylene groups (e.g., 6-15 carbon atoms), and alicyclic groups (e.g., 3-15 carbon atoms)), divalent heterocyclic groups (e.g., 3-15 ring member atoms), heteroarylene groups (e.g., 5-15 ring member atoms), and groups combining these. Also, R 5 For example, R 4 Among the (n+1) valence linking groups represented by , a divalent linking group is an example. Among them, R 5 Preferably, the group is a divalent hydrocarbon group, or a group formed by bonding one or more divalent hydrocarbon groups (e.g., 2 to 10) with a total of one or more groups (e.g., 2 to 10) selected from the group consisting of ether groups, carbonyl groups, and ester groups. Also, R 5 However, it is also preferable to include the group shown below, and it is also preferable to be the group shown below itself. In the group shown below, * indicates the bond position.

[0031] [ka]

[0032] R 5 The group is preferably a group with a total number of atoms of 2 to 60, more preferably a group with a total number of atoms of 2 to 50, and even more preferably a group with a total number of atoms of 2 to 40.

[0033] In formula 3, L 1 This represents a base expressed by formula 4 or formula 5.

[0034] [ka]

[0035] In formula 4, X 3 represents an oxygen atom or -NH-. In equation 4, * indicates a bonding position. In Equation 4, if either the * on the left or the * on the right is R 5 This is the binding position for R, and the other is R 6 This is the binding position for [the element].

[0036] In formula 5, X 4 represents an oxygen atom or -COO-. In the above -COO-, the carbonyl carbon in -COO- is -C(R e1 )(R e2 It is preferable that it be located on the opposite side of )-. In formula 5, R e1 ~R e3 Each of these independently represents either a hydrogen atom or an alkyl group. The alkyl group may be linear or branched, and preferably has 1 to 6 carbon atoms. R e1 ~R e3 At least two of these may be bonded together to form a ring. The ring may be monocyclic or polycyclic, and preferably has 3 to 15 carbon atoms. In equation 5, * indicates a bonding position. In equation 5, if either the * on the left or the * on the right is R 5 This is the binding position for R, and the other is R 6 This is the binding position for [the element].

[0037] In formula 3, R 6 This represents a linking group with (n+1) valence. Examples of the above linking groups include ether groups, carbonyl groups, ester groups, thioethers, -SO2-, and -NR. X -(R X This includes a hydrogen atom or substituents such as alkyl groups, alkylene groups (e.g., 1 to 10 carbon atoms), alkenylene groups (e.g., 2 to 12 carbon atoms), alkynylene groups (e.g., 2 to 12 carbon atoms), trivalent groups represented by "-N<", and "-CR Y The trivalent group represented by < (R YExamples include tetravalent groups represented by ">C<" (where C is a substituent such as a hydrogen atom or an alkyl group), aromatic ring groups (e.g., 5 to 15 ring members), alicyclic groups (e.g., 3 to 15 carbon atoms), non-aromatic heterocyclic groups (e.g., 3 to 15 ring members), and groups combining these. Among them, R 6 It is preferable that the linking group is a divalent linking group, and is preferably an alkylene group, or a group formed by linking one or more alkylenes (e.g., 2 to 10) with a total of one or more groups (e.g., 2 to 10) selected from the group consisting of an ether group, a carbonyl group, and an ester group. R 6 The group is preferably a group with a total number of atoms of 2 to 40, more preferably a group with a total number of atoms of 2 to 30, and even more preferably a group with a total number of atoms of 2 to 20.

[0038] The constituent units represented by Equation 3 are shown below as examples. In the following, m represents an integer greater than or equal to 2 (for example, 2 to 10), and n represents an integer greater than or equal to 1 (for example, 1 to 10).

[0039] [ka]

[0040] [ka]

[0041] Constituent unit A may also preferably include a constituent unit having an onium structure-containing group. For example, it is preferable that constituent unit A includes a constituent unit represented by formula 6.

[0042] [ka]

[0043] In formula 6, R 1 ~R 3 Each of these independently represents either a hydrogen atom or an alkyl group. In formula 6, X 1represents -COO-, -CONR-, or an arylene group, and R represents a hydrogen atom, an alkyl group, or an aryl group. In formula 6, X 2 is an oxygen atom or -NR A - represents R A represents a hydrogen atom, an alkyl group, or an aryl group. In equation 6, n represents an integer greater than or equal to 1. In formula 6, R 0 represents a hydrogen atom or an alkyl group. R in Equation 6 1 ~R 3 , X 1 , X 2 , R 0 , and n is R in Equation 1 1 ~R 3 , X 1 , X 2 , R 0 The same applies to n, respectively. In formula 6, R 6 This represents a linking group with (n+1) valence. R in Equation 6 6 R in Equation 3 is 6 It is similar to that. The value of n explicitly stated in Equation 6 is R 6 This is the same as the value of n in the (n+1) valence linking group represented by . In equation 6, X 2 If there are multiple X 2 These elements are independent of each other and may be identical or different. In equation 6, R 0 If there are multiple instances, then there are multiple R 0 These elements are independent of each other and may be identical or different.

[0044] In formula 6, L 2 This represents the base expressed in Equation 5. In equation 5 above, X 4 represents an oxygen atom or -COO-. In equation 5 above, R e1 ~R e3 Each of these independently represents a hydrogen atom or an alkyl group. e1 ~R e3At least two of these may be joined together to form a ring. L in Equation 6 2 The base represented by formula 5 is L in formula 3. 1 This is similar to the base represented by equation 5, which can be expressed as follows. However, L 2 In equation 5, which is expressed as follows, if one of the * on the left and the * on the right is R 8 This is the binding position for R, and the other is R 6 This is the binding position for [the element].

[0045] In formula 6, R 7 This represents a structure containing a group from which one proton has been dissociated from an acidic group. Examples of the above-mentioned acid groups include carboxyl groups, sulfonic acid groups, phosphonic acid groups, and phosphate groups. A specific example of a group in which one proton has been released from an acid group is, for example, -COO - , -SO3 - -OPO3H - , and -PO3H - The following were mentioned, -COO - It is preferable. Among them, R 7 The preferred group is one that can be represented as "-(divalent linking group)-(a group from which one proton has been released from an acid group)". Examples of the above-mentioned divalent linking groups include ether groups, carbonyl groups, ester groups, thioether groups, -SO2-, and -NR. X -(R X Examples include substituents such as hydrogen atoms or alkyl groups, divalent hydrocarbon groups (e.g., alkylene groups (e.g., 1-10 carbon atoms), alkenylene groups (e.g., 2-12 carbon atoms), alkynylene groups (e.g., 2-12 carbon atoms), arylene groups (e.g., 6-15 carbon atoms), or alicyclic groups (e.g., 3-15 carbon atoms)), divalent heterocyclic groups (e.g., 3-15 ring member atoms), heteroarylene groups (e.g., 5-15 ring member atoms), and groups combining these. The above-mentioned divalent linking group is preferably an alkylene group, or a group formed by bonding one or more alkylenes (e.g., 2 to 10) with a total of one or more groups (e.g., 2 to 10) selected from the group consisting of an ether group, a carbonyl group, and an ester group.

[0046] In formula 6, R 8 This represents a divalent linking group. Examples of the above-mentioned divalent linking groups include ether groups, carbonyl groups, ester groups, thioether groups, -SO2-, and -NR. X -(R X Examples include substituents such as hydrogen atoms or alkyl groups, divalent hydrocarbon groups (e.g., alkylene groups (e.g., 1-10 carbon atoms), alkenylene groups (e.g., 2-12 carbon atoms), alkynylene groups (e.g., 2-12 carbon atoms), arylene groups (e.g., 6-15 carbon atoms), or alicyclic groups (e.g., 3-15 carbon atoms)), divalent heterocyclic groups (e.g., 3-15 ring member atoms), heteroarylene groups (e.g., 5-15 ring member atoms), and groups combining these. Among them, R 8 An alkylene group is preferred.

[0047] In formula 6, R B1 ~R B3 Each of these independently represents a hydrogen atom, an alkyl group, or an aryl group. The alkyl group described above may be linear or branched, and preferably has 1 to 20 carbon atoms. The above aryl group may be monocyclic or polycyclic, and preferably has 6 to 15 carbon atoms.

[0048] The content of constituent unit A having an onium structure-containing group (preferably a constituent unit represented by formula 6) is preferably 0.5 mol% or more, more preferably 10 mol% or more, and even more preferably 20 mol% or more, relative to the total amount of constituent unit A (preferably a constituent unit represented by formula 1) in the specific resin. The upper limit of the above content is 100 mol% or less, preferably 85 mol% or less, and more preferably 70 mol% or less. If the composition contains two or more specific resins, the above content may be the content relative to constituent unit A in all of the two or more specific resins, or it may be the content relative to constituent unit A in one or more of the two or more specific resins (1 to all of them).

[0049] There are no restrictions on the method for introducing constituent unit A into a specific resin; for example, the following methods (1) to (8) can be cited. (1) A method of adding a compound having an epoxy group and an ethylenically unsaturated group to a carboxyl group-containing structural unit in a resin. (2) A method of adding a compound having an epoxy group and an ethylenically unsaturated group to a carboxyl group-containing structural unit in a resin, and further adding a compound having an isocyanate group and an ethylenically unsaturated group to the resulting alcohol moiety. (3) A method of adding a compound having an oxetane group and an ethylenically unsaturated group to a carboxyl group-containing structural unit in a resin. (4) A method of substitution reaction in which a compound having a leaving group (e.g., an alkyl halogenated group) and an ethylenically unsaturated group is added to a carboxyl group-containing structural unit in a resin. (5) A method of condensing a compound having a hydroxyalkyl group and an ethylenically unsaturated group with a carboxyl group-containing structural unit in a resin. (6) A method of adding a compound having an isocyanate group and an ethylenically unsaturated group to a hydroxyl group-containing structural unit in a resin. (7) A method of substitution reaction in which a carboxylic acid chloride is added to a constituent unit having a hydroxyl group in a resin. (8) A method for dehalogenating a structural unit having a halogenated alkyl group in a resin in the presence of a base. Among these, method (1) is preferred for forming the constituent unit A. When the addition reaction of method (1) is carried out in the presence of a tertiary amine catalyst, some or all of the tertiary amine catalyst is incorporated into some or all of the formed constituent unit A in the form of a salt, thereby introducing an onium-containing group. The proportion of the constituent units A into which an onium structure-containing group is introduced among all the constituent units A formed can be appropriately adjusted by changing the type and amount of catalyst, as well as the amount of compound having epoxy groups and ethylenically unsaturated groups added. The above tertiary amine catalyst is N(R A )(R B )(R C A compound represented by ) is preferred. A ~R C Each of these independently represents an alkyl group (preferably having 1 to 20 carbon atoms), an aryl group (preferably having 6 to 20 carbon atoms), or an aralkyl group (preferably having 7 to 20 carbon atoms). Examples of substituents that the alkyl group, aryl group, and aralkyl group may have include hydroxyl groups.

[0050] Constituent unit A may be used alone or in combination of two or more types. The content of constituent unit A (preferably the content of constituent units represented by formula 1, more preferably the total content of constituent units represented by formula 3 and constituent units represented by formula 6) is preferably 1 to 80% by mass, and more preferably 3 to 70% by mass, relative to the total constituent units of the specific resin.

[0051] <Component Unit B> The specific resin has constituent unit B. Constituent unit B is a constituent unit that has a phenolic hydroxyl group. Furthermore, it is preferable not to include polymerizable structural units in structural unit B, even if they have phenolic hydroxyl groups.

[0052] The phenolic hydroxyl group of constituent unit B is a hydroxyl group directly bonded to an aromatic hydrocarbon ring (such as a benzene ring or a naphthalene ring). The aromatic hydrocarbon ring may be monocyclic or polycyclic, and preferably has 6 to 15 carbon atoms. As long as the hydroxyl group in the phenolic hydroxyl group is directly bonded to the aromatic hydrocarbon ring portion, the aromatic hydrocarbon ring may be fused with rings other than the aromatic hydrocarbon ring (such as aromatic heterocyclic rings, non-aromatic heterocyclic rings, or alicyclic rings), or may have substituents other than hydroxyl groups. The number of phenolic hydroxyl groups in constituent unit B is one or more, preferably 1 to 7, more preferably 1 to 5, and even more preferably 1 to 3.

[0053] Examples of constituent unit B include the constituent unit represented by Equation 2-1.

[0054] [ka]

[0055] In formula 2-1, R 11 ~R 13 Each of these independently represents either a hydrogen atom or an alkyl group. The alkyl group described above may be linear or branched, and preferably has 1 to 6 carbon atoms.

[0056] In formula 2-1, L AR This represents a single bond or a divalent linking group. Examples of the above-mentioned divalent linking groups include ether groups, carbonyl groups, ester groups, thioether groups, -SO2-, and -NR. X -(R X Examples include substituents such as hydrogen atoms or alkyl groups, divalent hydrocarbon groups (e.g., alkylene groups (e.g., 1-10 carbon atoms), alkenylene groups (e.g., 2-12 carbon atoms), alkynylene groups (e.g., 2-12 carbon atoms), arylene groups (e.g., 6-15 carbon atoms), or alicyclic groups (e.g., 3-15 carbon atoms)), divalent heterocyclic groups (e.g., 3-15 ring member atoms), heteroarylene groups (e.g., 5-15 ring member atoms), and groups combining these.

[0057] In formula 2-1, Ar represents a (j+1) valent aromatic hydrocarbon ring group. The above aromatic hydrocarbon ring group may be monocyclic or polycyclic, and preferably has 6 to 15 carbon atoms. The aromatic hydrocarbon ring in the above aromatic hydrocarbon ring group may be fused with rings other than aromatic hydrocarbon rings (aromatic heterocycles, non-aromatic heterocycles, alicyclic rings, etc.), or may have substituents other than hydroxyl groups. However, j OH groups are bonded to the aromatic hydrocarbon ring portion of the above aromatic hydrocarbon ring group. Also, L AR It is also preferable that the aromatic hydrocarbon ring portion of the above-mentioned aromatic hydrocarbon ring group is bonded to it. The aromatic hydrocarbon ring group is preferably a benzene ring group or a naphthalene ring group, with a benzene ring group being more preferred.

[0058] In formula 2-1, j represents an integer greater than or equal to 1, preferably an integer between 1 and 7, more preferably an integer between 1 and 5, and even more preferably an integer between 1 and 3.

[0059] The constituent unit B is preferably the constituent unit represented by Equation 2.

[0060] [ka]

[0061] In formula 2, R 11 ~R 13 Each of these independently represents either a hydrogen atom or an alkyl group. The alkyl group described above may be linear or branched, and preferably has 1 to 6 carbon atoms.

[0062] In formula 2, A represents -COO-, -CONR'-, -COO-R”-, -CONR'-R”-, or an arylene group. The above-mentioned arylene group may be monocyclic or polycyclic, and preferably has 6 to 15 carbon atoms. In -CONR'- and -CONR'-R”-, R' represents a hydrogen atom, an alkyl group, or an aryl group. The alkyl group may be linear or branched, and preferably has 1 to 6 carbon atoms. The aryl group may be monocyclic or polycyclic, and preferably has 6 to 15 carbon atoms. In -COO-R”- and -CONR'-R”-, R” represents a divalent linking group. Examples of the above-mentioned divalent linking groups include ether groups, carbonyl groups, ester groups, thioether groups, -SO2-, and -NR. X -(R X Examples include substituents such as hydrogen atoms or alkyl groups, divalent hydrocarbon groups (e.g., alkylene groups (e.g., 1-10 carbon atoms), alkenylene groups (e.g., 2-12 carbon atoms), alkynylene groups (e.g., 2-12 carbon atoms), arylene groups (e.g., 6-15 carbon atoms), or alicyclic groups (e.g., 3-15 carbon atoms)), divalent heterocyclic groups (e.g., 3-15 ring member atoms), heteroarylene groups (e.g., 5-15 ring member atoms), and groups combining these.

[0063] In equation 2, m represents either 0 or 1. In equation 2, l represents an integer from 1 to 5. Preferably, l is an integer from 1 to 3.

[0064] The constituent unit B is more preferably the constituent unit represented by Equation 7.

[0065] [ka]

[0066] In formula 7, R 11 represents a hydrogen atom or an alkyl group. In formula 7, A represents -COO-, -CONR'-, -COO-R”-, -CONR'-R”-, or an arylene group. R' represents a hydrogen atom, an alkyl group, or an aryl group. R” represents a divalent linking group. In equation 7, m represents either 0 or 1. R in Equation 7 11 A and m are R in Equation 2. 11 The same applies to A and m, respectively. In equation 7, k represents an integer between 1 and 3.

[0067] In particular, it is preferable that constituent unit B is one or more selected from the group consisting of constituent units represented by formula 8, constituent units represented by formula 9, and constituent units represented by formula 10.

[0068] [ka]

[0069] Constituent unit B may be used alone or in combination of two or more types. The content of constituent unit B (preferably the content of constituent units represented by formula 2-1, more preferably the content of constituent units represented by formula 2, even more preferably the content of constituent units represented by formula 7, and particularly preferably the total content of constituent units represented by formulas 8 to 10) is preferably 0.1 to 40% by mass, and more preferably 0.5 to 15% by mass, relative to the total constituent units of the specific resin.

[0070] <Constituent Unit C> The specific resin has a constituent unit C. Constituent unit C is a constituent unit that has an acidic group. Note that the acidic groups in the constituent unit C do not include phenolic hydroxyl groups. Furthermore, it is preferable not to include polymerizable structural units in structural unit C, even if they have acidic groups. Similarly, it is preferable not to include structural units in structural unit C, even if they have acidic groups.

[0071] Examples of acidic groups include carboxyl groups, sulfonic acid groups, phosphonic acid groups, and phosphate groups. The number of acidic groups in constituent unit C is 1 or more, preferably 1 to 7, more preferably 1 to 5, and even more preferably 1 to 3.

[0072] The constituent unit C is preferably a repeating unit represented by formula C.

[0073] [ka]

[0074] In formula C, R c represents a hydrogen atom or an alkyl group. The alkyl group described above may be linear or branched, and preferably has 1 to 6 carbon atoms.

[0075] In formula C, X c These are single bonds, -COO-, and -CONR bonds. B - or represents an arylene group. The above-mentioned arylene group may be monocyclic or polycyclic, and preferably has 6 to 15 carbon atoms. -CONR B -R in B represents a hydrogen atom, an alkyl group, or an aryl group. The alkyl group may be linear or branched, and preferably has 1 to 6 carbon atoms. The aryl group may be monocyclic or polycyclic, and preferably has 6 to 15 carbon atoms.

[0076] In formula C, L c This represents a group formed by bonding a total of two or more groups (e.g., 2 to 10) selected from the group consisting of aliphatic hydrocarbon groups having 1 to 20 carbon atoms, arylene groups having 6 to 20 carbon atoms, and aliphatic hydrocarbon groups having 1 to 20 carbon atoms and arylene groups having 6 to 20 carbon atoms, with a total of one or more groups (e.g., 1 to 9) selected from the group consisting of ether groups and ester groups. Examples of the above-mentioned aliphatic hydrocarbon groups include alkylene groups and cycloalkylene groups. Also, X c If L is a single bond or an arylene group, c It may be a single bond.

[0077] In formula C, AC represents an acidic group. Examples of acidic groups include carboxyl groups, sulfonic acid groups, phosphonic acid groups, and phosphate groups.

[0078] The following are examples of constituent units C. In the following, n represents an integer greater than or equal to 1 (for example, 1 to 10).

[0079] [ka]

[0080] The constituent unit C may be used alone or in combination of two or more types. The content of constituent unit C (preferably the content of constituent units represented by formula C) is preferably 1 to 80% by mass, and more preferably 3 to 70% by mass, relative to the total constituent units of the specific resin.

[0081] <Component Unit D> The specific resin preferably has a constituent unit D, which does not fall under any of constituent units A to C. Constituent unit D is a constituent unit represented by equation D. Furthermore, constituent unit D is a group that does not possess any polymerizable group, phenolic hydroxyl group, or acidic group.

[0082] [ka]

[0083] In formula D, R D represents a hydrogen atom or an alkyl group. The alkyl group described above may be linear or branched, and preferably has 1 to 6 carbon atoms.

[0084] In formula D, X D is an oxygen atom or -NR C - represents R C represents a hydrogen atom, an alkyl group, or an aryl group. The alkyl group described above may be linear or branched, and preferably has 1 to 6 carbon atoms. The above aryl group may be monocyclic or polycyclic, and preferably has 6 to 15 carbon atoms.

[0085] In formula D, L D This represents a single bond or a divalent linking group. Examples of the above-mentioned divalent linking groups include ether groups, carbonyl groups, ester groups, thioether groups, -SO2-, and -NR. X -(R XExamples include substituents such as hydrogen atoms or alkyl groups, divalent hydrocarbon groups (e.g., alkylene groups (e.g., 1-10 carbon atoms), alkenylene groups (e.g., 2-12 carbon atoms), alkynylene groups (e.g., 2-12 carbon atoms), arylene groups (e.g., 6-15 carbon atoms), or alicyclic groups (e.g., 3-15 carbon atoms)), divalent heterocyclic groups (e.g., 3-15 ring member atoms), heteroarylene groups (e.g., 5-15 ring member atoms), and groups combining these. L D The group is preferably a group with a total number of atoms of 2 to 30, more preferably a group with a total number of atoms of 3 to 20, and even more preferably a group with a total number of atoms of 4 to 10. Also, L D The group is preferably a group having a urethane group (-O-CO-NH-) or a urea group (-NH-CO-NH-), and more preferably a group in which an alkylene group (e.g., having 1 to 10 carbon atoms) is bonded to a urethane group or a urea group.

[0086] In formula D, Y 1 and Y 2 Each of these independently represents either an alkylene oxy group or an alkylene carbonyl oxy group. The number of carbon atoms in the alkylene oxy group is preferably 1 to 30, more preferably 2 to 9, and even more preferably 4 to 7. The number of carbon atoms in the alkylene carbonyloxy group is preferably 2 to 30, more preferably 3 to 10, and even more preferably 5 to 8. The alkylene group portion of the alkylene oxy group and the alkylene carbonyl oxy group may be linear or branched. Y 1 and Y 2 They may be the same or different.

[0087] In formula D, Z 1 This represents an aliphatic hydrocarbon group having 1 to 20 carbon atoms (such as a linear or branched alkyl group), or an aryl group having 6 to 20 carbon atoms. The above aliphatic hydrocarbon group may be linear, branched, or partially or entirely ring-shaped. The above aliphatic hydrocarbon group is preferably an alkyl group. The above alkyl group may be linear or branched. The number of carbon atoms in the above aliphatic hydrocarbon group is 1 to 20, preferably 4 to 20, and more preferably 6 to 20. The above aryl group may be monocyclic or polycyclic, and preferably has 6 to 15 carbon atoms. It is also preferable that the above aryl group further has an aliphatic hydrocarbon group having 1 to 20 carbon atoms as a substituent.

[0088] In equation D, p and q each independently represent a non-negative integer. p is preferably an integer between 1 and 50, preferably an integer between 2 and 30, and preferably an integer between 3 and 20. q is preferably an integer between 0 and 50, preferably an integer between 0 and 30, and preferably an integer between 0 and 20. Note that the value of p+q is 1 or greater (for example, 1 to 100).

[0089] The following is an example of constituent unit D. In the following, n represents an integer greater than or equal to 1 (e.g., 1 to 10). a and b each independently represent an integer greater than or equal to 0 (e.g., 0 to 10), and a+b is an integer greater than or equal to 1 (e.g., 1 to 20). m represents an integer greater than or equal to 1 (e.g., 1 to 20). R represents a hydrogen atom or a methyl group.

[0090] [ka]

[0091] The constituent unit D may be used alone or in combination of two or more types. The content of constituent unit D is preferably 1 to 60% by mass, and more preferably 3 to 30% by mass, relative to the total constituent units of the specific resin.

[0092] <Constituent Unit E> The specific resin may have a constituent unit E. The structural unit E is another structural unit that does not fall under any of the above-mentioned structural units A to D. There are no particular restrictions on the structural unit E, and examples thereof include known structural units. Examples of the structural unit E include, for example, a structural unit represented by formula E.

[0093] [Chemical formula]

[0094] In formula E, it represents a hydrogen atom or an alkyl group. The above alkyl group may be linear or branched, and preferably has 1 to 6 carbon atoms.

[0095] In formula E, X E represents -COO-, -CONR-, or an arylene group. The above arylene group may be monocyclic or polycyclic, and preferably has 6 to 15 carbon atoms. R in -CONR- represents a hydrogen atom, an alkyl group, or an aryl group. The above alkyl group that can be represented by R in -CONR- may be linear or branched, and preferably has 1 to 6 carbon atoms. The above aryl group that can be represented by R in -CONR- may be monocyclic or polycyclic, and preferably has 6 to 15 carbon atoms.

[0096] In formula E, E represents a monovalent organic group having 1 to 42 carbon atoms. The above organic group may be linear, branched, or may form a ring structure in part or in whole. The above organic group is preferably a group composed of an alkyl group, a cycloalkyl group, an aryl group, or a combination thereof (such as an arylalkyl group or an alkylcycloalkyl group, etc.). Further, it is also preferable that these groups have a hydroxyl group other than a phenolic hydroxyl group as a substituent. The above alkyl group may be linear or branched, and preferably has 1 to 6 carbon atoms. The above cycloalkyl group may be monocyclic or polycyclic, and preferably has 3 to 15 carbon atoms. The above aryl group may be monocyclic or polycyclic, and preferably has 6 to 15 carbon atoms.

[0097] Furthermore, the constituent unit represented by formula E does not correspond to any of the constituent units A through D.

[0098] The constituent unit E may be used alone or in combination of two or more types. When a specific resin contains a constituent unit E (preferably a constituent unit represented by formula E), its content is preferably 1 to 80% by mass, and more preferably 3 to 70% by mass, relative to the total constituent units of the specific resin.

[0099] The weight-average molecular weight (Mw) of the specific resin is preferably 1000 or more, more preferably 5000 or more, and even more preferably 10000 or more. The Mw of the specific resin is preferably 200000 or less, more preferably 100000 or less, and even more preferably 50000 or less.

[0100] The ethylenically unsaturated bonding value of the specific resin is preferably 0.01 to 2.5 mmol / g, more preferably 0.1 to 2.2 mmol / g, and even more preferably 0.3 to 2.0 mmol / g. The ethylenically unsaturated bond value of a specific resin represents the molar amount of ethylenically unsaturated groups per gram of solid content of the specific resin. By alkaline treatment, the low molecular weight component (a) of the ethylenically unsaturated group moiety (for example, acrylic acid if the constituent unit represented by formula 1 has an acryloxy group) is extracted from the specific resin, its content is measured by high-performance liquid chromatography (HPLC), and the ethylenically unsaturated bond value can be calculated from the following formula based on the measured value. Specifically, 0.1 g of the sample to be measured is dissolved in a tetrahydrofuran / methanol mixture (50 mL / 15 mL), 10 mL of 4 mol / L sodium hydroxide aqueous solution is added, and the mixture is reacted at 40°C for 2 hours. The reaction solution is neutralized with 10.2 mL of 4 mol / L methanesulfonic acid aqueous solution, and then the mixture of 5 mL of deionized water and 2 mL of methanol is transferred to a 100 mL volumetric flask and the HPLC measurement sample is prepared by making up with methanol, and measured under the following conditions. The content of low molecular weight component (a) is calculated from a calibration curve for low molecular weight component (a) prepared separately, and the ethylenically unsaturated bond value can be calculated using the following formula. -Formula for calculating ethylenically unsaturated bond values- Ethylene-unsaturated bond value [mmol / g] = (Content of low molecular weight component (a) [ppm] / Molecular weight of low molecular weight component (a) [g / mol]) / (Weighing value of prepared polymer solution [g] × (Solid content concentration of polymer solution [%] / 100) × 10) -HPLC measurement conditions- Measuring instrument: Agilent-1200 (manufactured by Agilent Technologies, Inc.) Column: Phenomenex Synergi 4u Polar-RP 80A, 250mm x 4.60mm (inner diameter) + guard column Column temperature: 40℃ Analysis time: 15 minutes Flow rate: 1.0 mL / min (Maximum liquid delivery pressure: 182 bar) Injection volume: 5μL Detection wavelength: 210nm Eluent: Tetrahydrofuran (for HPLC, without stabilizers) / Buffer solution (ion-exchange aqueous solution containing 0.2 vol% phosphoric acid and 0.2 vol% triethylamine) = 55 / 45 (vol%)

[0101] The acid value of the specific resin is preferably 10 to 250 mgKOH / g, more preferably 30 to 200 mgKOH / g, and even more preferably 60 to 150 mgKOH / g. The acid value is determined by neutral titration using an aqueous sodium hydroxide solution. Specifically, a solution in which the specific resin is dissolved in a solvent is titrated with an aqueous sodium hydroxide solution using a potentiometric titration method, the number of millimoles of acid contained in 1 g of the specific solid is calculated, and then the value is obtained by multiplying it by the molecular weight of KOH, 56.1.

[0102] The specific resin may be used alone or in combination of two or more. The content of the specific resin is preferably 2 to 75% by mass, more preferably 5 to 50% by mass, and even more preferably 8 to 25% by mass with respect to the total solid content of the composition.

[0103] 〔Other resins〕 The composition of the present invention may contain other resins that do not correspond to the above-mentioned specific resins. Other resins do not simultaneously have all of the above-mentioned structural units A to C. As long as they do not simultaneously have all of the above-mentioned structural units A to C, other resins may have one or two of the structural units A to C. Other resins are preferably alkali-soluble resins. Examples of the alkali-soluble resin include a polymer in which at least one group that promotes alkali solubility (for example, a carboxy group, a phosphoric acid group, a sulfonic acid group, etc.) is present in a molecule (preferably a molecule having an acrylic copolymer or a styrene copolymer as a main chain). The alkali-soluble resin is preferably soluble in an organic solvent and developable with a weak alkaline aqueous solution. The content of the structural unit having a group that promotes alkali solubility is preferably 1 to 70 mol%, more preferably 5 to 40 mol% with respect to all the structural units of the alkali-soluble resin.

[0104] As alkali-soluble resins, polymers having carboxylic acids in their side chains are preferred. For example, methacrylic acid copolymers, acrylic acid copolymers, itaconic acid copolymers, crotonic acid copolymers, maleic acid copolymers, partially esterified maleic acid copolymers, etc., as described in Japanese Patent Publication No. 59-44615, Japanese Patent Publication No. 54-34327, Japanese Patent Publication No. 58-12577, Japanese Patent Publication No. 54-25957, Japanese Patent Publication No. 59-53836, or Japanese Patent Publication No. 59-71048, are preferred, as are acidic cellulose derivatives having carboxylic acids in their side chains, and polymers having hydroxyl groups to which acid anhydrides have been added. Furthermore, high molecular polymers having (meth)acryloyl groups in their side chains are also preferred.

[0105] Other resins (preferably alkali-soluble resins) are preferably copolymers of (meth)acrylic acid and other monomers copolymerizable therewith. Other monomers copolymerizable with the above-mentioned (meth)acrylic acid include, for example, (meth)acrylic acid esters, crotonic acid esters, vinyl esters, maleic acid diesters, fumaric acid diesters, itaconic acid diesters, (meth)acrylamides, styrenes, vinyl ethers, vinyl ketones, olefins, maleimides, (meth)acrylonitrile, and ether dimers represented by the following formulas ED1 or ED2.

[0106] [ka]

[0107] In formula ED1, R 1 and R 2 Each of these independently represents either a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms. In formula ED2, R represents a hydrogen atom or an organic group having 1 to 30 carbon atoms. For specific examples of formula ED2, refer to the description in Japanese Patent Application Publication No. 2010-168539.

[0108] Other monomers of (meth)acrylic acid that can copolymerize with the above (meth)acrylic acid include, for example, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, amyl (meth)acrylate, n-hexyl (meth)acrylate, cyclohexyl (meth)acrylate, t-butylcyclohexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, t-octyl (meth)acrylate, dodecyl (meth)acrylate, ( Octadecyl meth)acrylate, acetoxyethyl meth)acrylate, phenyl meth)acrylate, 2-hydroxyethyl meth)acrylate, 2-hydroxypropyl meth)acrylate, 3-hydroxypropyl meth)acrylate, 4-hydroxybutyl meth)acrylate, 2-methoxyethyl meth)acrylate, 2-ethoxyethyl meth)acrylate, 2-(2-methoxyethoxy)ethyl meth)acrylate, 3-phenoxy-2-hydroxypropyl meth)acrylate, 2-chloroethyl meth)acrylate, glycidyl meth)acrylate, 3-meth)acrylate4-Epoxycyclohexylmethyl, (meth)acrylate vinyl, (meth)acrylate-2-phenylvinyl, (meth)acrylate-1-propenyl, (meth)acrylate allyl, (meth)acrylate-2-alyloxyethyl, (meth)acrylate propargyl, (meth)acrylate benzyl, (meth)acrylate diethylene glycol monomethyl ether, (meth)acrylate diethylene glycol monoethyl ether, (meth)acrylate triethylene glycol monomethyl ether, (meth)acrylate triethylene glycol monoethyl ether, (meth)acrylate polyethylene glycol monomethyl ether Examples include polyethylene glycol monoethyl ether (meth)acrylate, β-phenoxyethoxyethyl (meth)acrylate, nonylphenoxypolyethylene glycol (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, trifluoroethyl (meth)acrylate, octafluoropentyl (meth)acrylate, perfluorooctylethyl (meth)acrylate, dicyclopentanyl (meth)acrylate, tribromophenyl (meth)acrylate, tribromophenyloxyethyl (meth)acrylate, and γ-butyrolactone (meth)acrylate.

[0109] Furthermore, other resins (preferably alkali-soluble resins) may have constituent units corresponding to the constituent unit A described above. For example, the method described for a specific resin can be used to introduce the constituent unit A into a copolymer of (meth)acrylic acid and another monomer copolymerizable therewith, thereby introducing the constituent unit A into other resins (preferably alkali-soluble resins). If the other resin (preferably an alkali-soluble resin) has constituent unit A, its content is preferably 1 to 70 mol%, and more preferably 5 to 30 mol%, relative to the total constituent units of the other resin (preferably an alkali-soluble resin).

[0110] Furthermore, the other resin (preferably an alkali-soluble resin) may be a cardo resin having a cardo skeleton. An example of a cardo resin is V-259ME (manufactured by Nippon Steel & Sumitomo Metal Corporation).

[0111] The weight-average molecular weight (Mw) of the other resins (preferably alkali-soluble resins) is preferably 5000 or more, and more preferably 10000 to 300000. The number-average molecular weight (Mn) of the other resin (preferably an alkali-soluble resin) is preferably 1000 or more, and more preferably 2000 to 250000. The degree of dispersion (weight-average molecular weight / number-average molecular weight) is preferably 1.1 to 10, and more preferably 1.2 to 5. Other resins (preferably alkali-soluble resins) may be, for example, random polymers, block polymers, and graft polymers.

[0112] Other resins (preferably alkali-soluble resins) include, for example, the compounds described in paragraphs 0162 to 0175 of Japanese Patent Publication No. 2007-277514.

[0113] Other resins (preferably alkali-soluble resins) may be used individually or in combination of two or more types. If the composition contains other resins (preferably alkali-soluble resins), the content thereof is preferably 0.1 to 40% by mass, more preferably 0.5 to 30% by mass, and even more preferably 1 to 10% by mass, relative to the total solid content of the composition.

[0114] [Dispersing agent] The composition may include a dispersing agent. Dispersion aids are components other than the resins mentioned above (specific resins and other resins) that can suppress the aggregation and / or sedimentation of components that exist in a solid state in the composition, such as pigments. Examples of dispersing agents include pigment derivatives. Furthermore, the dispersing aid may also preferably have one or more dialkylamino groups (for example, 1 to 6, preferably 2 to 4). The number of carbon atoms in each alkyl group of the dialkylamino group is preferably 1 to 6. Furthermore, the dispersing aid may also preferably have one or more aromatic rings (for example, 1 to 10, preferably 2 to 8). Each of the aromatic rings may be monocyclic or polycyclic, and may be fused with a non-aromatic ring. The number of member atoms of the aromatic rings is, for example, 5 to 15. The content of the dispersing agent is preferably 0.0001 to 10% by mass, preferably 0.001 to 8% by mass, and more preferably 0.003 to 4% by mass, relative to the total solid content of the composition.

[0115] [Pigments] The composition of the present invention contains a pigment. Examples of pigments include inorganic pigments and organic pigments. The pigment preferably includes one or more selected from the group consisting of, for example, black pigment, white pigment, and chromatic pigment, and more preferably includes at least a black pigment. The black pigment content is preferably 0 to 100% by mass, more preferably 51 to 100% by mass, and even more preferably 90 to 100% by mass, relative to the total mass of the pigment. More specifically, examples of pigments include black pigments such as carbon black, titanium black (titanium nitride, titanium oxynitride, and lower-order titanium oxide, etc.), zirconium nitride, zirconium oxynitride, vanadium nitride, vanadium oxynitride, niobium nitride, and niobium oxynitride; as well as oxides and metal complexes of metals such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, and antimony. In particular, the composition preferably contains one or more pigments selected from the group consisting of carbon black, titanium black, zirconium nitride, and zirconium oxynitride.

[0116] In addition, the following pigments can be cited as organic or inorganic pigments. Color Index (CI) Pigment Yellow: 1, 2, 3, 4, 5, 6, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116 ,117,118,119,120,123,125,126,127,128,129,137,138,139,147,148,150,151,152,153,154,155,156,161,162,164,166,167,168,169,170,171,172,173,174,175,176,177,179,180,181,182,185,187,188,193,194,199,213,214 (all yellow pigments); CI Pigment Orange 2, 5, 13, 16, 17: 1, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 71, 73 (all are orange pigments); CI Pigment Red 1,2,3,4,5,6,7,9,10,14,17,22,23,31,38,41,48:1,48:2,48:3,48:4,49,49:1,49:2,52:1,52:2,53:1,57:1,60:1,63:1,66,67,81:1,81:2,81:3,83,88,90,105,112,119,122,123,144,146, 149, 150, 155, 166, 168, 169, 170, 171, 172, 175, 176, 177, 178, 179, 184, 185, 187, 188, 190, 200, 202, 206, 207, 208, 209, 210, 216, 220, 224, 226, 242, 246, 254, 255, 264, 270, 272, 279 (all of the above are red pigments); CI Pigment Green 7, 10, 36, 37, 58, 59 (all are green pigments); CI Pigment Violet 1, 19, 23, 27, 32, 37, 42, 58, 59 (all purple pigments); CI Pigment Blue 1, 2, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 22, 60, 64, 66, 79, 80 (all blue pigments). CI Pigment White 6, 18, 21 (all are white pigments)

[0117] Furthermore, as a green pigment, zinc halide phthalocyanine pigments can be used, which have an average of 10 to 14 halogen atoms, an average of 8 to 12 bromine atoms, and an average of 2 to 5 chlorine atoms in the molecule. A specific example is the compound described in International Publication No. 2015 / 118720.

[0118] Furthermore, aluminum phthalocyanine compounds containing a phosphorus atom can also be used as a blue pigment. Specific examples include the compounds described in paragraphs 0022-0030 of Japanese Patent Publication No. 2012-247591 and paragraph 0047 of Japanese Patent Publication No. 2011-157478.

[0119] Other examples of white pigments include titanium dioxide, strontium titanate, barium titanate, zinc oxide, magnesium oxide, zirconium oxide, aluminum oxide, barium sulfate, silica, talc, mica, aluminum hydroxide, calcium silicate, aluminum silicate, hollow resin particles, and zinc sulfide.

[0120] Another example of a black pigment is lactam black (such as BASF's Irgaphor Black S 0100 CF).

[0121] In addition, infrared-absorbing pigments can also be used as pigments. The infrared absorbing pigment is not particularly limited, and for example, known infrared absorbing pigments can be used, with diiminium compounds, squarylium compounds, cyanine compounds, phthalocyanine compounds, naphthalocyanine compounds, quaterylene compounds, aminium compounds, iminium compounds, azo compounds, anthraquinone compounds, porphyrin compounds, pyrrolopyrrole compounds, oxonol compounds, crokonium compounds, hexaphyllin compounds, metal dithiol compounds, copper compounds, tungsten compounds, or metal borides being preferred, diiminium compounds, squarylium compounds, cyanine compounds, phthalocyanine compounds, naphthalocyanine compounds, quaterylene compounds, pyrrolopyrrole compounds, metal dithiol compounds, copper compounds, or tungsten compounds being more preferred, squarylium compounds, cyanine compounds, phthalocyanine compounds, or pyrrolopyrrole compounds being even more preferred, and squarylium compounds or pyrrolopyrrole compounds being particularly preferred. Furthermore, examples of infrared absorbing pigments include infrared absorbing agents and other pigments described in Japanese Patent Publication No. 2009-263614, Japanese Patent Publication No. 2011-068731, and International Publication No. 2015 / 166873.

[0122] The infrared absorbing pigment is preferably a compound that has absorption in the wavelength range of 700 to 2000 nm, and more preferably a compound that has a maximum absorption wavelength in the wavelength range of 700 to 2000 nm.

[0123] The volume-average particle size of the pigment is not particularly limited, but is preferably 0.01 to 0.1 μm, and more preferably 0.01 to 0.05 μm.

[0124] Pigments may be used individually or in combination of two or more types. The pigment content is 15% by mass or more, preferably 30% by mass or more, relative to the total solid content of the composition. The above content is preferably 90% by mass or less, and more preferably 60% by mass or less. Furthermore, from the viewpoint of obtaining a cured film with a higher color value, the above content is preferably 48% by mass or more.

[0125] [Photopolymerization initiator] The composition may also contain a photopolymerization initiator. As long as the photopolymerization initiator has the ability to initiate polymerization, there are no particular restrictions, and it can be appropriately selected from known photopolymerization initiators. For example, compounds that are photosensitive to light in the ultraviolet to visible regions are preferred. Alternatively, a compound that interacts with a photoexcited sensitizer to generate an active radical may also be used. From the viewpoint of curability and sensitivity, the photopolymerization initiator is preferably a photoradical polymerization initiator, and more preferably a compound having an oxime structure.

[0126] Examples of photopolymerization initiators include halogenated hydrocarbon derivatives (compounds having a triazine skeleton or compounds having an oxadiazole skeleton, etc.), acylphosphine compounds, hexaarylbiimidazole, oxime compounds, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, α-hydroxyketone compounds, and α-aminoketone compounds. From the viewpoint of exposure sensitivity, the photopolymerization initiator is preferably at least one compound selected from the group consisting of trihalomethyltriazine compounds, benzyldimethylketal compounds, α-hydroxyketone compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, onium compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds, cyclopentadiene-benzene-iron complexes, halomethyloxadiazole compounds, and 3-arylsubstituted coumarin compounds; more preferably at least one compound selected from the group consisting of oxime compounds, α-hydroxyketone compounds, α-aminoketone compounds, and acylphosphine compounds; and even more preferably oxime compounds. With regard to photopolymerization initiators, reference can be made to paragraphs 0065 to 0111 of Japanese Patent Publication No. 2014-130173 and paragraphs 0274 to 0306 of Japanese Patent Publication No. 2013-029760, the contents of which are incorporated herein by reference.

[0127] Examples of commercially available α-hydroxyketone compounds include Omnirad-184, Omnirad-1173, Omnirad-500, Omnirad-2959, and Omnirad-127 (all manufactured by IGM Resins BV). Examples of commercially available α-aminoketone compounds include Omnirad-907, Omnirad-369, Omnirad-379, and Omnirad-379EG (all manufactured by IGM Resins BVF). Examples of commercially available acylphosphine compounds include Omnirad-819 and Omnirad-TPO (both manufactured by BASF).

[0128] Examples of oxime compounds include the compounds described in Japanese Patent Publication No. 2001-233842, Japanese Patent Publication No. 2000-080068, Japanese Patent Publication No. 2006-342166, the compounds described in JCSPerkin II (1979, pp. 1653-1660), the compounds described in JCSPerkin II (1979, pp. 156-162), and the Journal of Photopolymer Science and Examples include compounds described in Technology (1995, pp. 202-232), compounds described in Japanese Patent Publication No. 2000-66385, compounds described in Japanese Patent Publication No. 2000-80068, compounds described in Japanese Patent Publication No. 2004-534797, compounds described in Japanese Patent Publication No. 2006-342166, compounds described in Japanese Patent Publication No. 2017-019766, compounds described in Japanese Patent Publication No. 6065596, compounds described in International Publication No. 2015 / 152153, and compounds described in International Publication No. 2017 / 051680. Specific examples of oxime compounds include, for example, 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropane-1-one, 2-benzoyloxyimino-1-phenylpropane-1-one, 3-(4-toluenesulfonyloxy)iminobutan-2-one, and 2-ethoxycarbonyloxyimino-1-phenylpropane-1-one. Examples of commercially available oxime compounds include IRGACURE-OXE01, IRGACURE-OXE02, IRGACURE-OXE03, IRGACURE-OXE04 (all manufactured by BASF), TRONLY TR-PBG-304, TRONLY TR-PBG-309, TRONLY TR-PBG-305 (manufactured by Changzhou Tronly New Electronic Materials Co., Ltd.), ADEKA Arclus NCI-930, ADEKA Arclus NCI-831, ADEKA Optomer N-1919 (photopolymerization initiator 2 in Japanese Patent Publication No. 2012-14052) (all manufactured by ADEKA), and Omnirad-1312, Omnirad-1313, Omnirad-1314 (all manufactured by IGM Resins BVF).

[0129] Other oxime compounds include, for example, the compound described in Japanese Patent Publication No. 2009-519904, in which an oxime is linked to the N position of the carbazole ring; the compound described in U.S. Patent No. 7,626,957, in which a heterosubstituted group is introduced to the benzophenone moiety; the compound described in Japanese Patent Application Publication No. 2010-015025 and U.S. Patent Application Publication No. 2009-292039, in which a nitro group is introduced to the dye moiety; the ketoxime compound described in International Publication No. 2009 / 131189; the compound described in U.S. Patent No. 7,556,910, which contains a triazine skeleton and an oxime skeleton in the same molecule; and the compound described in Japanese Patent Application Publication No. 2009-221114, which has an absorption maximum at a wavelength of 405 nm and good sensitivity to g-line light sources.

[0130] An oxime compound having a fluorene ring may be used as a photopolymerization initiator. Specific examples of oxime compounds having a fluorene ring include the compounds described in Japanese Patent Application Publication No. 2014-137466. This information is incorporated herein by reference.

[0131] Oxime compounds having a benzofuran skeleton may be used as photopolymerization initiators. Specific examples include compounds OE-01 to OE-75 described in International Publication No. 2015 / 036910.

[0132] As a photopolymerization initiator, an oxime compound having a skeleton in which at least one benzene ring of the carbazole ring is replaced by a naphthalene ring may be used. Examples of such oxime compounds include those described in International Publication No. 2013 / 083505.

[0133] An oxime compound containing a fluorine atom may be used as a photopolymerization initiator. Examples of oxime compounds containing a fluorine atom include the compound described in Japanese Patent Publication No. 2010-262028, compounds 24, 36-40 described in Japanese Patent Publication No. 2014-500852, and compound (C-3) described in Japanese Patent Publication No. 2013-164471. This information is incorporated herein by reference.

[0134] As a photopolymerization initiator, an oxime compound having a nitro group can be used. The oxime compound having a nitro group can also be used in dimer form. Examples of oxime compounds having a nitro group include the compounds described in paragraphs 0031 to 0047 of Japanese Patent Publication No. 2013-114249, paragraphs 0008 to 0012 and 0070 to 0079 of Japanese Patent Publication No. 2014-137466, the compounds described in paragraphs 0007 to 0025 of Japanese Patent No. 4223071, and ADEKA Arclus NCI-831 (manufactured by ADEKA).

[0135] Specific examples of oxime compounds are shown below.

[0136] [ka]

[0137] [ka]

[0138] The oxime compound is preferably one that has a maximum absorption wavelength in the 350-500 nm wavelength range, and more preferably one that has a maximum absorption wavelength in the 360-480 nm wavelength range. Furthermore, the oxime compound is preferably one that has high absorbance at wavelengths of 365 nm and 405 nm.

[0139] The molar extinction coefficient of oxime compounds at wavelengths of 365 nm or 405 nm should be between 1,000 and 300,000 mol, from the viewpoint of sensitivity. -1 L cm -1 Preferably, 2,000 to 300,000 moles -1 L cm -1 More preferably, 5,000 to 200,000 moles -1 L cm -1 This is even more preferable. The molar extinction coefficient of the compound can be measured using known methods. For example, it can be measured using an ultraviolet-visible spectrophotometer (Varian Cary-5 spectrophotometer) with ethyl acetate solvent at a concentration of 0.01 g / L.

[0140] As photopolymerization initiators, bifunctional or trifunctional or more photopolymerization initiators may be used. Specific examples of such photopolymerization initiators include, for example, the dimers of oxime compounds described in JP 2010-527339, JP 2011-524436, International Publication No. 2015 / 004565, paragraphs 0417-0412 of JP 2016-532675, and paragraphs 0039-0055 of International Publication No. 2017 / 033680, as well as compounds (E) and (G) described in JP 2013-522445, and Cmpd1-7 described in International Publication No. 2016 / 034963.

[0141] The photopolymerization initiator may be used alone or in combination of two or more types. If the composition contains a photopolymerization initiator, its content is preferably 0.1 to 50% by mass, more preferably 0.5 to 30% by mass, and even more preferably 1 to 20% by mass, based on the total solids content of the composition.

[0142] [Polymerization inhibitors] The composition may contain polymerization inhibitors from the viewpoint of storage stability. Examples of polymerization inhibitors include 2,2,6,6-tetramethylpiperidine-1-oxyl, 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl, hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, tert-butylcatechol, benzoquinone, 4,4'-thiobis(3-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-methyl-6-tert-butylphenol), and N-nitrosophenylhydroxyamine salts (ammonium salts, cerium salts, etc.). From the viewpoint of storage stability, compounds having an N-oxyl radical structure are also preferred. Furthermore, the polymerization inhibitor may be a compound that does not have an aromatic ring, from the viewpoint of curability and pattern shape. Furthermore, polymerization inhibitors can sometimes function as antioxidants. From the viewpoint of curability and pattern shape, the molecular weight of the polymerization inhibitor is preferably 200 or less, more preferably 180 or less, even more preferably 160 or less, and particularly preferably 120 to 160.

[0143] Polymerization inhibitors may be used individually or in combination of two or more types. If the composition contains a polymerization inhibitor, its content is preferably 0.00001 to 1% by mass, more preferably 0.0001 to 0.5% by mass, and even more preferably 0.001 to 0.1% by mass, relative to the total solid content of the composition.

[0144] [Polymerizable compound] The composition may contain polymerizable compounds. Polymerizable compounds are compounds that are different from specific resins. The polymerizable compounds that can be used in this specification are preferably ethylenically unsaturated compounds (compounds having ethylenically unsaturated groups such as (meth)acryloyl groups, vinyl groups, and / or styryl groups), and more preferably compounds having terminal ethylenically unsaturated groups ((meth)acryloyl groups, vinyl groups, and styryl groups). The polymerizable compound preferably has one or more ethylenically unsaturated groups, more preferably 2 to 10, and even more preferably 3 to 6. Such a group of compounds can include any known compounds without any particular limitations. Polymerizable compounds may include, for example, monomers, prepolymers (dimers, trimers, or oligomers, etc.), or mixtures or copolymers thereof. Examples of monomers and copolymers thereof include unsaturated carboxylic acids (e.g., acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), as well as their esters and amides. Among these, polymerizable compounds that are esters of unsaturated carboxylic acids and aliphatic polyhydric alcohol compounds, or amides of unsaturated carboxylic acids and aliphatic polyhydric amine compounds are preferred. Furthermore, polymerizable compounds include, for example, addition reaction products of unsaturated carboxylic acid esters or amides having nucleophilic substituents such as hydroxyl groups, amino groups, or mercapto groups with monofunctional or polyfunctional isocyanates or epoxys; and dehydration condensation reaction products of unsaturated carboxylic acid esters or amides having nucleophilic substituents such as hydroxyl groups, amino groups, or mercapto groups with monofunctional or polyfunctional carboxylic acids. Furthermore, polymerizable compounds include, for example, addition reaction products of unsaturated carboxylic acid esters or amides having electrophilic substituents such as isocyanate groups or epoxy groups with monofunctional or polyfunctional alcohols, amines, or thiols; and substitution reaction products of unsaturated carboxylic acid esters or amides having leaving substituents such as halogen groups or tosyloxy groups with monofunctional or polyfunctional alcohols, amines, or thiols. Furthermore, as polymerizable compounds, for example, compounds obtained by replacing the above-mentioned unsaturated carboxylic acid with unsaturated phosphonic acid, styrene, or vinyl ether may be used.

[0145] Examples of esters of aliphatic polyhydric alcohol compounds with unsaturated carboxylic acids include ethylene glycol diacrylate, triethylene glycol diacrylate, 1,3-butanediol diacrylate, tetramethylene glycol diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane tri(acryloyloxypropyl) ether, trimethylolethane triacrylate, hexanediol diacrylate, 1,4-cyclohexanediol diacrylate, tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, and sorbitol hexaacrylate. Examples include tri(acryloyloxyethyl) isocyanurate, polyester acrylate oligomer, isocyanurate EO-modified triacrylate, tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, ethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, hexanediol dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol dimethacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexamethacrylate, sorbitol trimethacrylate, sorbitol tetramethacrylate, bis[p-(3-methacryloxy-2-hydroxypropoxy)phenyl]dimethylmethane, and bis-[p-(methacryloxyethoxy)phenyl]dimethylmethane.

[0146] Furthermore, as polymerizable compounds, for example, urethane-based addition polymerizable compounds produced by the addition reaction of isocyanates and hydroxyl groups can also be used. Specifically, examples include vinyl urethane compounds having two or more polymerizable vinyl groups per molecule, obtained by adding a vinyl monomer having a hydroxyl group represented by the following formula (I) to a polyisocyanate compound having two or more isocyanate groups per molecule as described in Japanese Patent Publication No. 48-41708.

[0147] CH2=C(R)COOCH2CH(R')OH (I) (However, R and R' represent H or CH3.)

[0148] Furthermore, polymerizable compounds can also be used, for example, urethane acrylates as described in Japanese Patent Publication No. 51-37193, Japanese Patent Publication No. 2-32293, and Japanese Patent Publication No. 2-16765; urethane compounds having an ethylene oxide-based skeleton as described in Japanese Patent Publication No. 58-49860, Japanese Patent Publication No. 56-17654, Japanese Patent Publication No. 62-39417, and Japanese Patent Publication No. 62-39418; and addition polymerizable compounds having an amino structure or sulfide structure in the molecule as described in Japanese Patent Publication No. 63-277653, Japanese Patent Publication No. 63-260909, and Japanese Patent Publication No. 1-105238.

[0149] Examples of polymerizable compounds include those described in paragraphs 0178 to 0190 of Japanese Patent Publication No. 2007-277514.

[0150] Among these, polymerizable compounds are those represented by the following formula (Z-6).

[0151] [ka]

[0152] In equation (Z-6), E is independently -(CH2) y -CH2-O-, -(CH2) y-CH(CH3)-O-, -(CH2) y -CH2-CO-O-, -(CH2) y -CH(CH3)-CO-O-, -CO-(CH2) y -CH2-O-, -CO-(CH2) y -CH(CH3)-O-, -CO-(CH2) y -CH2-CO-O-, or -CO-(CH2) y This represents -CH(CH3)-CO-O-. It is preferable that the bond position on the right side of these groups is the bond position on the X side. Each 'y' independently represents an integer between 1 and 10. Each X independently represents either a (meth)acryloyl group or a hydrogen atom. Each 'p' independently represents an integer between 0 and 10. q represents an integer between 0 and 3.

[0153] In formula (Z-6), it is preferable that the total number of (meth)acryloyl groups is (3+2q) or (4+2q). p is preferably an integer between 0 and 6, and more preferably an integer between 0 and 4. The sum of each p is preferably 0 to (40 + 20 q), more preferably 0 to (16 + 8 q), and even more preferably 0 to (12 + 6 q).

[0154] Other polymerizable compounds include those in formula (Z-6) where q is 0 and there are four "-O-(E) p A compound in which one of the groups represented by "-X" is replaced with a methyl group may also be used.

[0155] The molecular weight of the polymerizable compound (or weight-average molecular weight if it has a molecular weight distribution) is preferably 80 or more and less than 1000.

[0156] If the composition contains polymerizable compounds, their content is preferably 1 to 90% by mass, more preferably 5 to 50% by mass, and even more preferably 15 to 35% by mass, based on the total solid content of the composition.

[0157] [Surfactants] The composition may contain a surfactant. Surfactants contribute to improving the applicability of the composition.

[0158] Examples of surfactants include fluorine-based surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and silicone-based surfactants.

[0159] Examples of fluorine-based surfactants include Megafac F171, F172, F173, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780, and F781F (all manufactured by DIC Corporation); Florard FC430, FC431, and FC171 ( Examples include: Sumitomo 3M Co., Ltd.'s Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC1068, SC-381, SC-383, S393, and KH-40 (all manufactured by Asahi Glass Co., Ltd.); and PF636, PF656, PF6320, PF6520, and PF7002 (manufactured by OMNOVA). Block polymers can also be used as fluorine-based surfactants, and a specific example is the compound described in Japanese Patent Publication No. 2011-89090. Examples of silicone-based surfactants include KF-6001 (manufactured by Shin-Etsu Chemical Co., Ltd.) and BYK-333 (manufactured by BIC Chemie Japan Co., Ltd.).

[0160] Surfactants may be used individually or in combination of two or more types. If the composition contains a surfactant, its content is preferably 0.001 to 20% by mass, more preferably 0.003 to 15% by mass, and even more preferably 0.005 to 10% by mass, relative to the total solid content of the composition.

[0161] 〔solvent〕 The composition contains a solvent. Examples of solvents include water and organic solvents. Examples of organic solvents 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, methoxymethoxyethanol, 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, butyl acetate, methyl lactate, N-methyl-2-pyrrolidone, and ethyl lactate.

[0162] The solvent may be used alone or in combination of two or more types. The solvent content is preferably such that the total solid content of the composition is 10 to 90% by mass, more preferably 15 to 80% by mass, and even more preferably 20 to 50% by mass. The solvent content is preferably 10 to 90% by mass, more preferably 20 to 85% by mass, and even more preferably 50 to 80% by mass, based on the total mass of the composition.

[0163] [Other ingredients] The composition may also contain other components not mentioned above. Other components include, for example, dyes, sensitizers, cosensitizers, fluorine-based organic compounds, fillers other than pigments, adhesion promoters, antioxidants, UV absorbers, and anti-aggregation agents.

[0164] [Method for manufacturing the composition] The method for preparing the composition is not particularly limited, and can be obtained, for example, by mixing each component contained in the composition in a known manner. For example, the composition may be obtained as a pigment dispersion liquid by mixing a pigment, a specific resin, a solvent, a dispersing aid added as desired, and a polymerization inhibitor added as desired. Furthermore, if the composition contains additional components in addition to those contained in the pigment dispersion, the additional components may be added to and mixed with the pigment dispersion to form the composition. As these additional components, pigments, specific resins, solvents, dispersion aids, and / or polymerization inhibitors, different from those contained in the pigment dispersion, may be added. Furthermore, for purposes such as removing foreign matter or reducing defects, the composition or components used in preparing the composition may be filtered. Any filter that has been conventionally used for filtration purposes is not particularly limited and can be used.

[0165] [Manufacturing of hardened films] A composition layer formed using the composition of the present invention can be cured to obtain a cured film (including a patterned cured film). The method for manufacturing the cured film is not particularly limited, but it is preferable to have the following steps. ·Composition layer formation process • Exposure process ·Development process The following describes each step.

[0166] [Composition layer forming process] In the composition layer formation process, prior to exposure, the composition is applied to a support or the like to form a layer of the composition (composition layer). As the support, for example, a substrate (for example, a silicon substrate or a glass substrate containing Si atoms) and a solid-state image sensor substrate on which an image sensor (photodetector) such as a CCD or CMOS is provided can be used. In addition, if necessary, an undercoat layer may be provided on the support to improve adhesion with the upper layer, prevent diffusion of the material, and flatten the substrate surface.

[0167] Various coating methods can be applied to the support, such as slit coating, inkjet coating, rotary coating, casting coating, roll coating, and screen printing. The film thickness of the composition layer in the dry state is preferably 0.1 to 10 μm, more preferably 0.2 to 5 μm, and even more preferably 0.2 to 3 μm. Drying (pre-baking) of the composition layer applied to the support can be done at a temperature of 50 to 140°C for 10 to 300 seconds using a hot plate or oven.

[0168] [Exposure process] In the exposure process, the composition layer (dried film) formed in the composition layer formation process is exposed by irradiating it with active light or radiation, and the light-irradiated composition layer is cured. The preferred method of light irradiation is to irradiate the subject with light through a photomask having a patterned opening. Exposure is preferably performed by radiation. The radiation that can be used for exposure is preferably ultraviolet light such as g-rays, h-rays, or i-rays, and the light source is preferably a high-pressure mercury lamp. The irradiation intensity is 5 to 1500 mJ / cm². 2 Preferably, 10 to 1000 mJ / cm² 2 This is preferable. If the composition contains a thermal polymerization initiator, the composition layer may be heated during the exposure step described above. The heating temperature is not particularly limited, but 80 to 250°C is preferred. The heating time is preferably 30 to 300 seconds. Furthermore, if the composition layer is heated during the exposure process, this process may also serve as the post-heating process described later. In other words, if the composition layer is heated during the exposure process, the method for manufacturing the cured film does not need to include a post-heating process.

[0169] [Development process] The developing process involves developing the above-mentioned composition layer after exposure to form a cured film. In this process, the un-irradiated portions of the composition layer during the exposure process are dissolved, leaving only the photo-cured portions, thus obtaining a patterned cured film. While there are no particular restrictions on the type of developer used in the development process, an alkaline developer is preferable as it will not damage the underlying image sensor and circuitry. The development temperature is, for example, 20-30°C. The development time is typically 20 to 90 seconds. In recent years, development has sometimes been extended to 120 to 180 seconds to better remove residue. Furthermore, to further improve residue removal, the developer solution may be shook out every 60 seconds, and the process of supplying fresh developer solution may be repeated several times.

[0170] The alkaline 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). Examples of alkaline compounds 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 (of which organic bases are preferred). When used as an alkaline developer, the film is generally washed with water after development.

[0171] [Post-bake] It is also preferable to perform a heat treatment (post-bake) after the exposure process. Post-bake is a heat treatment after development to ensure complete curing. The heating temperature is preferably 240°C or lower, and more preferably 220°C or lower. There is no particular lower limit, but considering efficient and effective processing, 50°C or higher is preferable, and 100°C or higher is more preferable. Post-baking can be carried out continuously or in batches using heating means such as a hot plate, convection oven (hot air circulation dryer), or high-frequency heater.

[0172] The above post-bake process may also be carried out under a low oxygen concentration atmosphere. The oxygen concentration is preferably 19% by volume or less, more preferably 15% by volume or less, even more preferably 10% by volume or less, particularly preferably 7% by volume or less, and most preferably 3% by volume or less. There is no lower limit, but 10 ppm by volume or more is practical.

[0173] Alternatively, instead of post-baking by heating as described above, curing may be completed by UV (ultraviolet) irradiation. In this case, the above-mentioned composition preferably further contains a UV curing agent. The UV curing agent is preferably one that can cure at a wavelength shorter than 365 nm, which is the exposure wavelength of the polymerization initiator added for the lithography process using normal i-line exposure. An example of a UV curing agent is Omnirad 2959 manufactured by IGM Resins BV. When UV irradiation is performed, it is preferable that the composition layer is made of a material that cures at a wavelength of 340 nm or less. There is no particular lower limit for the wavelength, but 220 nm or higher is common. The exposure dose for UV irradiation is 100 to 5000 mJ / cm². 2 Preferably, 300-4000 mJ / cm² 2 More preferably, 800-3500 mJ / cm² 2 This is even more preferable. Performing this UV curing step after the exposure step is preferable for more effective low-temperature curing. It is preferable to use an ozone-free mercury lamp as the exposure light source.

[0174] [Physical properties of the cured film, and applications of the cured film] [Physical properties of the cured film] The cured film formed using the composition of the present invention preferably has an optical density (OD) of 2.0 or higher, and more preferably 3.0 or higher, per 1.5 μm of film thickness in the wavelength range of 400 to 1100 nm. There is no particular upper limit, but generally, 10 or less is preferred. If the optical density is 2.0 or higher, the cured film formed using the composition can be said to have a high color value. In this specification, an optical density of 2.0 or higher per 1.5 μm of film thickness in the wavelength range of 400 to 1100 nm means that the optical density of 2.0 or higher per 1.5 μm of film thickness is present throughout the entire wavelength range of 400 to 1200 nm. Furthermore, the cured film (light-shielding film) preferably also has good light-shielding properties in the infrared region, and the optical density per 1.5 μm of film thickness at a wavelength of 940 nm is preferably greater than 2.0, and more preferably greater than 3.0. There is no particular upper limit, but it is generally preferable to be 10 or less. Furthermore, the film thickness and optical density of the composition layer (dried film) after coating and drying the composition usually do not change significantly compared to the state of the cured film after subsequent exposure and curing. In such cases, the optical density of the composition layer (dried film) may be measured using the above measurement method, and the obtained value may be used as the optical density of the cured film. The thickness of the cured film is preferably 0.1 to 4.0 μm, and more preferably 1.0 to 2.5 μm. The cured film may also be thinner or thicker than this range, depending on the application.

[0175] The reflectivity of the cured film is preferably less than 8%, more preferably less than 6%, and even more preferably less than 4%. The lower limit is 0% or more. The reflectance referred to here is determined from the reflectance spectrum obtained by incident light with a wavelength of 400 to 1100 nm at an incident angle of 5° using the VAR unit of the V7200 spectrometer (product name) manufactured by JASCO Corporation. Specifically, the reflectance of the light at the wavelength that shows the maximum reflectance in the range of 400 to 1100 nm is taken as the reflectance of the cured film.

[0176] Furthermore, the above-mentioned cured film is suitable for light-shielding members and light-shielding films, as well as anti-reflective members and anti-reflective films, used in optical filters and modules such as portable devices including personal computers, tablets, mobile phones, smartphones, and digital cameras; OA (Office Automation) equipment such as printers and scanners; industrial equipment such as surveillance cameras, barcode readers, automated teller machines (ATMs), high-speed cameras, and devices with personal authentication functions using facial image recognition or biometric authentication; in-vehicle camera equipment; medical camera equipment such as endoscopes, capsule endoscopes, and catheters; and space equipment such as biosensors, biosensors, military reconnaissance cameras, 3D map cameras, weather and ocean observation cameras, land resource exploration cameras, and space exploration cameras for astronomy and deep space targets.

[0177] The above-mentioned cured film can also be used in applications such as micro-LEDs (Light Emitting Diodes) and micro-OLEDs (Organic Light Emitting Diodes). The above-mentioned cured film is suitable for optical filters and optical films used in micro-LEDs and micro-OLEDs, as well as for components that provide light-shielding or anti-reflective functions. Examples of micro-LEDs and micro-OLEDs include those described in Japanese Patent Publication No. 2015-500562 and Japanese Patent Publication No. 2014-533890.

[0178] The above-mentioned cured film is also suitable as an optical and optical film used in quantum dot sensors and quantum dot solid-state image sensors. It is also suitable as a component that provides light-shielding and anti-reflective functions. Examples of quantum dot sensors and quantum dot solid-state image sensors are described in U.S. Patent Application Publication No. 2012 / 37789 and International Publication No. 2008 / 131313.

[0179] [Light-shielding film, optical element, and solid-state image sensor and solid-state imaging device] The cured film of the present invention is also preferably used as a so-called light-shielding film. Such a light-shielding film is also preferably used in solid-state image sensors. As described above, the cured film formed using the light-shielding composition of the present invention exhibits excellent light-shielding properties and low reflectivity. Furthermore, a light-shielding film is one of the preferred uses of the cured film of the present invention, and the production of the light-shielding film of the present invention can be carried out in the same manner as described above as a method for producing a cured film. Specifically, a light-shielding film can be produced by coating a substrate with the composition to form a composition layer, exposing it to light, and developing it.

[0180] The present invention also includes the invention of an optical element. The optical element of the present invention is an optical element having the above-mentioned cured film (light-shielding film). Examples of optical elements include optical elements used in optical instruments such as cameras, binoculars, microscopes, and semiconductor exposure equipment. Among these, solid-state image sensors mounted in cameras and the like are preferred as the optical elements.

[0181] Furthermore, the solid-state image sensor of the present invention is a solid-state image sensor that includes the cured film (light-shielding film) of the present invention described above. One example of a solid-state image sensor of the present invention that includes a cured film (light-shielding film) is a configuration in which a substrate has a plurality of photodiodes and a light-receiving element made of polysilicon or the like that constitute the light-receiving area of ​​a solid-state image sensor (CCD image sensor, CMOS image sensor, etc.), and the cured film is present on the side of the support where the light-receiving element is formed (for example, the part other than the light-receiving portion and / or the color adjustment pixels, etc.) or on the opposite side of the formation surface. The solid-state imaging device comprises the above-mentioned solid-state image sensor.

[0182] Examples of the configuration of a solid-state imaging device and a solid-state image sensor will be explained with reference to Figures 1 and 2. Note that in Figures 1 and 2, the relative thickness and / or width ratios of each part are ignored and some parts are exaggerated in order to clarify their appearance. Figure 1 is a schematic cross-sectional view showing an example of the configuration of a solid-state imaging device including the solid-state image sensor of the present invention. As shown in Figure 1, the solid-state imaging device 100 comprises a rectangular solid-state image sensor 101 and a transparent cover glass 103 held above the solid-state image sensor 101 and sealing the solid-state image sensor 101. Furthermore, a lens layer 111 is superimposed on the cover glass 103 via a spacer 104. The lens layer 111 is composed of a support 113 and a lens material 112. The lens layer 111 may also be configured in which the support 113 and the lens material 112 are integrally molded. When stray light is incident on the peripheral region of the lens layer 111, the light diffusion weakens the light-gathering effect of the lens material 112, reducing the amount of light reaching the imaging unit 102. In addition, noise due to stray light occurs. For this reason, the peripheral region of the lens layer 111 is shielded from light by a light-shielding film 114. The cured film of the present invention can also be used as the light-shielding film 114.

[0183] The solid-state image sensor 101 converts the optical image formed on its light-receiving surface, the imaging unit 102, into an image signal. This solid-state image sensor 101 includes a laminated substrate 105 made of two stacked substrates. The laminated substrate 105 consists of a rectangular chip substrate 106 and a circuit board 107 of the same size, with the circuit board 107 stacked on the back surface of the chip substrate 106.

[0184] For example, known materials can be used as the material for the substrate used as the chip substrate 106.

[0185] An imaging unit 102 is provided in the center of the surface of the chip substrate 106. A light-shielding film 115 is provided in the peripheral region of the imaging unit 102. By blocking stray light incident on this peripheral region with the light-shielding film 115, the generation of dark current (noise) from the circuit in this peripheral region can be prevented. The cured film of the present invention is preferably used as the light-shielding film 115.

[0186] Multiple electrode pads 108 are provided on the surface edge of the chip substrate 106. The electrode pads 108 are electrically connected to the imaging unit 102 via signal lines (bonding wires may also be used) provided on the surface of the chip substrate 106.

[0187] On the back surface of the circuit board 107, external connection terminals 109 are provided approximately below each electrode pad 108. Each external connection terminal 109 is connected to the electrode pad 108 via a through-electrode 110 that penetrates the laminated substrate 105 vertically. Furthermore, each external connection terminal 109 is connected via wiring (not shown) to a control circuit that controls the driving of the solid-state image sensor 101, and to an image processing circuit that performs image processing on the imaging signal output from the solid-state image sensor 101.

[0188] Figure 2 shows a schematic cross-sectional view of the imaging unit 102. As shown in Figure 2, the imaging unit 102 is composed of various parts provided on a substrate 204, such as a light-receiving element 201, a color filter 202, and a microlens 203. The color filter 202 has blue pixels 205b, red pixels 205r, green pixels 205g, and a black matrix 205bm. The cured film of the present invention may be used as the black matrix 205bm.

[0189] For the substrate 204, for example, the same material as the aforementioned chip substrate 106 can be used. A p-well layer 206 is formed on the surface of the substrate 204. Within this p-well layer 206, photodetectors 201, which consist of n-type layers and generate and store signal charges by photoelectric conversion, are arranged in a square grid.

[0190] On one side of the photodetector 201, a vertical transfer path 208 made of an n-type layer is formed via a read gate portion 207 on the surface of a p-well layer 206. On the other side of the photodetector 201, a vertical transfer path 208 belonging to an adjacent pixel is formed via an element isolation region 209 made of a p-type layer. The read gate portion 207 is a channel region for reading the signal charge accumulated in the photodetector 201 into the vertical transfer path 208.

[0191] A gate insulating film 210 made of an ONO (Oxide-Nitride-Oxide) film is formed on the surface of the substrate 204. A vertical transfer electrode 211 made of polysilicon or amorphous silicon is formed on this gate insulating film 210 so as to cover approximately directly above the vertical transfer path 208, the read gate section 207, and the element isolation region 209. The vertical transfer electrode 211 functions as a drive electrode that drives the vertical transfer path 208 to perform charge transfer, and as a read electrode that drives the read gate section 207 to perform signal charge readout. The signal charge is sequentially transferred from the vertical transfer path 208 to a horizontal transfer path (not shown) and an output section (floating diffusion amplifier), and then output as a voltage signal.

[0192] A light-shielding film 212 is formed on the vertical transfer electrode 211 so as to cover its surface. The light-shielding film 212 has an opening directly above the light-receiving element 201, and shields the other areas from light. The cured film of the present invention may be used as the light-shielding film 212. A transparent intermediate layer is provided on the light-shielding film 212, consisting of an insulating film 213 made of BPSG (borophosphosilite glass), an insulating film (passivation film) 214 made of P-SiN, and a planarization film 215 made of a transparent resin or the like. The color filter 202 is formed on the intermediate layer.

[0193] [Image display device] The image display device of the present invention comprises the cured film of the present invention. One example of an image display device having a cured film is a configuration in which the cured film is used as a black matrix, and a color filter containing such a black matrix is ​​used in the image display device.

[0194] <Black Matrix> The cured film of the present invention may also preferably be included in a black matrix. The black matrix may be included in a color filter, a solid-state image sensor, and an image display device such as a liquid crystal display device. Examples of black matrices include those already described above; the black borders provided around the edges of image display devices such as liquid crystal displays; grid-like and / or striped black areas between red, blue, and green pixels; and dot-like and / or linear black patterns for light shielding of TFTs (thin film transistors). For a definition of this black matrix, see, for example, Taihei Sugano, "Dictionary of Liquid Crystal Display Manufacturing Equipment Terms," ​​2nd edition, Nikkan Kogyo Shimbun, 1996, p. 64. The black matrix preferably has high light-shielding properties (optical density OD of 3 or higher) in order to improve display contrast and, in the case of liquid crystal display devices using an active matrix drive system with thin-film transistors (TFTs), to prevent image quality degradation due to light current leakage.

[0195] The black matrix can be manufactured, for example, by the same method as the method for manufacturing the cured film described above. Specifically, the composition can be applied to a substrate to form a composition layer, which is then exposed to light and developed to produce a patterned cured film (black matrix). The thickness of the cured film used as the black matrix is ​​preferably 0.1 to 4.0 μm.

[0196] The substrate material described above preferably has a transmittance of 80% or more for visible light (wavelength 400-800 nm). Examples of such materials include soda-lime glass, alkali-free glass, quartz glass, and borosilicate glass; plastics such as polyester resins and polyolefin resins; and from the viewpoint of chemical resistance and heat resistance, alkali-free glass or quartz glass is preferred.

[0197] <Color Filter> The cured film of the present invention may also be included in a color filter. Examples of color filters that include a cured film include a color filter comprising a substrate and the black matrix described above. Specifically, a color filter comprising red, green, and blue colored pixels formed in the openings of the black matrix formed on the substrate can be given as an example.

[0198] Color filters containing a black matrix (cured film) can be manufactured, for example, by the following method. First, a coating film (composition layer) of a composition containing a pigment corresponding to each colored pixel of the color filter is formed at the openings of a patterned black matrix formed on the substrate. For each color, for example, known compositions can be used. It is also preferable to use compositions that contain a coloring agent (pigment, etc.) corresponding to each pixel, as described herein, as each color composition. Next, the composition layer is exposed through a photomask having a pattern corresponding to the openings of the black matrix. Then, after removing the unexposed areas by a development process, it can be baked to form colored pixels at the openings of the black matrix. By performing this series of operations using, for example, color compositions containing red, green, and blue pigments, a color filter having red, green, and blue pixels can be manufactured.

[0199] Another form of the color filter including the cured film is, for example, a color filter comprising a substrate, a black matrix, and red, green, and blue colored pixels formed in the openings of the black matrix, wherein at least a portion of the colored pixels is the cured film of the present invention. In this case, the black matrix may be other than the cured film of the present invention.

[0200] <Liquid crystal display device> The cured film of the present invention may also be included in a liquid crystal display device. An example of a liquid crystal display device that includes the cured film is one that includes a color filter as described above.

[0201] An example of a liquid crystal display device according to this embodiment is a configuration comprising a pair of substrates arranged opposite each other and a liquid crystal compound sealed between the substrates. As for the substrates, for example, the substrate for the black matrix has already been described.

[0202] A specific form of the above-mentioned liquid crystal display device is, for example, a laminate having, from the user's side, a polarizing plate / substrate / color filter / transparent electrode layer / alignment film / liquid crystal layer / alignment film / transparent electrode layer / TFT (Thin Film Transistor) element / substrate / polarizing plate / backlight unit in this order.

[0203] Examples of liquid crystal display devices include those described in "Electronic Display Devices" (by Akio Sasaki, published by Kogyo Chosakai Co., Ltd. in 1990) and "Display Devices" (by Yoshiaki Ibuki, published by Sangyo Tosho Co., Ltd. in 1989). Additionally, examples of liquid crystal display devices include those described in "Next-Generation Liquid Crystal Display Technology" (edited by Tatsuo Uchida, published by Kogyo Chosakai Co., Ltd. in 1994).

[0204] [Infrared Sensor] The cured film of the present invention may also be included in an infrared sensor. The infrared sensor according to the above embodiment will be described with reference to Figure 3. Figure 3 is a schematic cross-sectional view showing an example of the configuration of an infrared sensor equipped with the cured film of the present invention. The infrared sensor 300 shown in Figure 3 includes a solid-state image sensor 310. The imaging area provided on the solid-state image sensor 310 is configured by combining an infrared absorption filter 311 and a color filter 312 according to an embodiment of the present invention. The infrared absorption filter 311 is a film that transmits light in the visible light region (for example, light with a wavelength of 400 to 700 nm) and shields light in the infrared region (for example, light with a wavelength of 800 to 1300 nm, preferably light with a wavelength of 900 to 1200 nm, more preferably light with a wavelength of 900 to 1000 nm), and a cured film containing an infrared absorbent (the form of the infrared absorbent is as already described) can be used as the pigment. The color filter 312 is a color filter in which pixels that transmit and absorb light of specific wavelengths in the visible light region are formed. For example, a color filter in which red (R), green (G), and blue (B) pixels are formed is used, and its form is as already described. Between the infrared transmission filter 313 and the solid-state image sensor 310, a resin film 314 (for example, a transparent resin film) capable of transmitting light of wavelengths that have passed through the infrared transmission filter 313 is placed. The infrared transmission filter 313 is a filter that has visible light shielding properties and transmits infrared rays of a specific wavelength, and can use a cured film of the present invention which contains a coloring agent that absorbs light in the visible light region (e.g., perylene compounds and / or bisbenzofuranone compounds, etc.) and an infrared absorbing agent (e.g., pyrrolopyrrole compounds, phthalocyanine compounds, naphthalocyanine compounds and polymethine compounds, etc.). Preferably, the infrared transmission filter 313 shields light with wavelengths of 400 to 830 nm and transmits light with wavelengths of 900 to 1300 nm. A microlens 315 is positioned on the incident light hν side of the color filter 312 and the infrared transmission filter 313. A planarization film 316 is formed to cover the microlens 315. In the configuration shown in Figure 3, a resin film 314 is arranged, but an infrared transmission filter 313 may be formed instead of the resin film 314. That is, an infrared transmission filter 313 may be formed on the solid-state image sensor 310. Furthermore, in the configuration shown in Figure 3, the film thickness of the color filter 312 and the infrared transmission filter 313 are the same, but their film thicknesses may be different. Furthermore, in the configuration shown in Figure 3, the color filter 312 is positioned on the incident light hν side of the infrared absorption filter 311. However, the order of the infrared absorption filter 311 and the color filter 312 may be reversed, so that the infrared absorption filter 311 is positioned on the incident light hν side of the color filter 312. Furthermore, in the configuration shown in Figure 3, the infrared absorption filter 311 and the color filter 312 are stacked adjacent to each other, but the two filters do not necessarily have to be adjacent, and other layers may be provided in between. The cured film of the present invention can be used as a light-shielding film on the edges and / or sides of the surface of the infrared absorption filter 311, and if used on the inner wall of an infrared sensor device, it can prevent internal reflection and / or the incidence of unintended light on the light-receiving part, thereby improving sensitivity. This infrared sensor can simultaneously capture image information, enabling motion sensing and other applications that recognize moving objects. Furthermore, because it can acquire distance information, it can capture images containing 3D data. In addition, this infrared sensor can also be used as a biometric authentication sensor.

[0205] Next, a solid-state imaging device using the above-mentioned infrared sensor will be described. The above-described solid-state imaging device comprises a lens optical system, a solid-state image sensor, an infrared light-emitting diode, etc. For details regarding the configuration of the solid-state imaging device, please refer to paragraphs 0032 to 0036 of Japanese Patent Application Publication No. 2011-233983, which are incorporated into this specification.

[0206] [Headlight Unit] The cured film of the present invention is also preferably included in a headlight unit for a vehicle such as an automobile as a light-shielding film. The cured film of the present invention included in a headlight unit as a light-shielding film is preferably formed in a pattern so as to block at least a portion of the light emitted from the light source. The headlight unit according to the above embodiment will be described with reference to Figures 4 and 5. Figure 4 is a schematic diagram showing an example of the configuration of the headlight unit, and Figure 5 is a schematic perspective view showing an example of the configuration of the light-shielding part of the headlight unit. As shown in Figure 4, the headlight unit 10 has a light source 12, a light shield 14, and a lens 16, and the light source 12, light shield 14, and lens 16 are arranged in that order. As shown in Figure 5, the light-shielding portion 14 has a base 20 and a light-shielding film 22. The light-shielding film 22 has patterned openings 23 formed therein to illuminate the light emitted from the light source 12 in a specific shape. The shape of the openings 23 in the light-shielding film 22 determines the light distribution pattern illuminated by the lens 16. The lens 16 projects the light L from the light source 12 that has passed through the light-shielding portion 14. The lens 16 is not necessarily required if a specific light distribution pattern can be illuminated from the light source 12. The lens 16 is appropriately determined according to the illumination distance and illumination range of the light L. Furthermore, the substrate 20 is not particularly limited in its composition as long as it can hold the light-shielding film 22, but it is preferable that it does not deform due to the heat of the light source 12, and is made of, for example, glass. Figure 5 shows an example of a light distribution pattern, but it is not limited to this example. Furthermore, the light source 12 is not limited to one; for example, it may be arranged in a row or in a matrix. When multiple light sources are provided, for example, one light-shielding section 14 may be provided for each light source 12. In this case, the light-shielding films 22 of each of the multiple light-shielding sections 14 may all have the same pattern, or they may each have different patterns.

[0207] The light distribution pattern based on the pattern of the light-shielding film 22 will be explained. Figure 6 is a schematic diagram showing an example of a light distribution pattern by a headlight unit, and Figure 7 is a schematic diagram showing another example of a light distribution pattern by a headlight unit. Note that both the light distribution pattern 30 shown in Figure 6 and the light distribution pattern 32 shown in Figure 7 indicate the areas to which light is irradiated. Furthermore, both the area 31 shown in Figure 6 and the area 31 shown in Figure 7 indicate the illumination area illuminated by the light source 12 (see Figure 4) when the light-shielding film 22 is not provided. Due to the pattern of the light-shielding film 22, the light intensity decreases sharply at the edge 30a, for example, as shown in the light distribution pattern 30 in Figure 6. The light distribution pattern 30 shown in Figure 6 is a pattern that does not shine light on oncoming vehicles, for example, when driving on the left side of the road. Furthermore, as shown in Figure 7, the light distribution pattern 32 can be created by cutting out a portion of the light distribution pattern 30 shown in Figure 6. In this case as well, similar to the light distribution pattern 30 shown in Figure 6, the light intensity drops sharply at the edge 32a, resulting in a pattern that does not illuminate oncoming vehicles, for example, when driving on the left side of the road. In addition, the light intensity drops sharply at the cutout portion 33. Therefore, marks indicating conditions such as a curved road, an uphill slope, or a downhill slope can be displayed in the area 34 corresponding to the cutout portion 33. This improves safety when driving at night.

[0208] Furthermore, the light-shielding portion 14 is not limited to being fixedly positioned between the light source 12 and the lens 16. It can also be configured to enter the space between the light source 12 and the lens 16 as needed using a drive mechanism (not shown) to obtain a specific light distribution pattern. Alternatively, the light-shielding portion 14 may be configured as a shade member capable of blocking light from the light source 12. In this case, a drive mechanism (not shown) can be used to move the light source 12 between the light source 12 and the lens 16 as needed to obtain a specific light distribution pattern. [Examples]

[0209] The present invention will be described in more detail below based on examples. The materials, amounts used, proportions, processing content, and processing procedures shown in the following examples can be modified as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be interpreted as being limited by the examples shown below. In this embodiment, when the amount and content of added components are indicated simply as "parts" and "%", unless otherwise specified, they mean "parts by mass" and "mass%".

[0210] [Production of the composition] The method for producing the composition (coloring composition) is shown below.

[0211] [Resin manufacturing] First, resins (specific resins and comparative resins) were manufactured using the raw materials listed below and the method described later.

[0212] <Raw materials used in the manufacture of resin> (solvent) The solvents listed below were used in the production of the resin. • PGMEA: Propylene glycol monomethyl ether acetate Cyclopentanone

[0213] (monomer) The monomers listed below were used in the production of the resin.

[0214] • Monomer 1 ··A-1: Arronix M-5300, ω-carboxy-polycaprolactone monoacrylate (manufactured by Toagosei Co., Ltd.) ··A-2: Light ester HO-MS, 2-methacryloyloxyethyl succinate (manufactured by Kyoeisha Chemical Co., Ltd.) ··A-3: Acrylic acid ··A-4: βCEA, β-carboxyethyl acrylate (manufactured by Daicel Ornex Co., Ltd.) A-5: Vinyl benzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) ··A-6: Methacryloyloxyethylphthalic acid (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) ··A-7: Methacrylic acid ··A-8: Vinyl sulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) A-9: Vinylphosphonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) ·A-10:4-(4-(acryloyloxy)butoxy)benzoic acid

[0215] • Monomer 2 ··B-1: Product synthesized according to synthesis example B1 below ··B-2: Synthesized product according to the synthesis example B2 below. ··B-3: Bremmer PSE1300 (manufactured by NOF Corporation), stearoxy polyethylene glycol monomethacrylate ··B-4: Bremmer 75ANEP-600 (manufactured by NOF Corporation) Nonylphenoxy (ethylene glycol-polypropylene glycol) monoacrylate ··B-5: Bremmer 50POEP800B (manufactured by NOF Corporation) Octoxy polyethylene glycol - polypropylene glycol monomethacrylate

[0216] -Synthesis Example B1 (Synthesis of B-1)- The synthesis method for monomer B-1 (also simply called "B-1"), which contains a constituent unit consisting of an oxyalkylene carbonyl group, is shown below.

[0217] [ka]

[0218] ε-caprolactone (1256.62 parts) and 2-ethyl-1-hexanol (143.38 parts) were introduced into a flask to obtain a mixture. Next, the mixture was stirred while blowing in nitrogen. Next, 0.63 parts of monobutyltin oxide were added to the mixture, and the resulting mixture was heated to 90°C. After 6 hours, 1H-NMR (nuclear magnetic resonance) was used to confirm the disappearance of the signal originating from 2-ethyl-1-hexanol in the mixture, and the mixture was then heated to 110°C. The polymerization reaction was continued at 110°C under nitrogen for 2 hours, and after confirming the disappearance of the signal originating from ε-caprolactone by 1H-NMR, the mixture was cooled to 80°C, and 0.78 parts of 2,6-di-t-butyl-4-methylphenol were added to the mixture. Subsequently, 174.15 parts of 2-methacryloyloxyethyl isocyanate were added dropwise to the resulting mixture over 30 minutes. One hour after the completion of the dropwise addition, after confirming the disappearance of the signal originating from 2-methacryloyloxyethyl isocyanate (MOI) by 1H-NMR, propylene glycol monomethyl ether acetate (PGMEA) (1575.57 parts) was added to the mixture to obtain a 50% by mass solution of monomer (macromonomer) B-1. The structure of monomer B-1 was confirmed by 1H-NMR. The weight-average molecular weight of the obtained monomer B-1 was 3,000.

[0219] -Synthesis Example B2 (Synthesis of B-2)- The synthesis method for monomer B-2 (also simply called "B-2"), which contains a constituent unit consisting of an oxyalkylene carbonyl group, is shown below.

[0220] [ka]

[0221] -B-2 Synthesis- ε-caprolactone (243.45 parts, corresponding to a cyclic compound), δ-valerolactone (60.86 parts, corresponding to a cyclic compound), and 2-ethyl-1-hexanol (35.69 parts, corresponding to a ring-opening polymerization initiator) were introduced into a flask to obtain a mixture. Next, the mixture was stirred while blowing in nitrogen. Next, 0.156 parts of monobutyltin oxide were added to the mixture, and the resulting mixture was heated to 90°C. After 6 hours, 1H-NMR (nuclear magnetic resonance) was used to confirm the disappearance of the signal originating from 2-ethyl-1-hexanol in the mixture, and the mixture was then heated to 110°C. The polymerization reaction was continued at 110°C under nitrogen for 12 hours, and after confirming the disappearance of the signals originating from ε-caprolactone and δ-valerolactone using 1H-NMR, the mixture was cooled to 80°C, and 0.19 parts of 2,6-di-t-butyl-4-methylphenol were added to the mixture. Subsequently, 42.52 parts of 2-methacryloyloxyethyl isocyanate were added dropwise to the resulting mixture over 30 minutes. One hour after the completion of the dropwise addition, after confirming the disappearance of the signal originating from 2-methacryloyloxyethyl isocyanate (MOI) by 1H-NMR, propylene glycol monomethyl ether acetate (PGMEA) (382.87 parts) was added to the mixture to obtain a 50% by mass monomer (macromonomer) B-2 solution. The structure of monomer B-2 was confirmed by 1H-NMR. The weight-average molecular weight of the obtained monomer B-2 was 3,000.

[0222] • Monomer 3 ··C-1:4-Vinylphenol (manufactured by Fujifilm Wako Pure Chemical Industries) ··C-2:4-Vinyl Catechol ··C-3:4-Hydroxyphenyl methacrylate (manufactured by Showa Denko Corporation) ··C-4:6-vinylnaphthalene-2-ol ··C-5:7-hydroxy-2-naphthylacrylate

[0223] • Monomer 4 ··D-1: Benzyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) ··D-2: 4-t-butylcyclohexyl methacrylate, Bremmer TBCHMA (manufactured by NOF Corporation) ··D-3: 2-Ethylhexyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) ··D-4: Acrylic ester HO (2-hydroxyethyl methacrylate, manufactured by Mitsubishi Chemical Corporation)

[0224] (Reactive compound) The reactive compounds listed below were used in the production of the resin. • E-1: 4HBAGE, 4-hydroxybutyl acrylate glycidyl ether (manufactured by Nippon Chemical Industries, Ltd.) • E-2: 3,4-Epoxycyclohexylmethyl acrylate (manufactured by Daicel Corporation) • E-3: Glycidyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) • E-4: GMA, Glycidyl Methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) • E-5: Allyl glycidyl ether (manufactured by Tokyo Chemical Industry Co., Ltd.) • E-6: Karenz AOI (2-isocyanatoethyl acrylate, manufactured by Showa Denko Corporation) • E-7: Karenz MOI (2-isocyanatoethyl methacrylate, manufactured by Showa Denko Corporation)

[0225] (catalyst) The catalysts listed below were used in the production of the resin. • F-1: Dimethyldodecylamine (manufactured by Tokyo Chemical Industry Co., Ltd.) • F-2: Dimethylbutylamine (manufactured by Tokyo Chemical Industry Co., Ltd.) F-3: Dimethylbenzylamine (manufactured by Tokyo Chemical Industry Co., Ltd.) • F-4: Tetrabutylammonium bromide (manufactured by Tokyo Chemical Industry Co., Ltd.) F-5: Dimethylaminoethylphenol (manufactured by Tokyo Chemical Industry Co., Ltd.) • F-6: Neostan U-600 (Bismustris (2-ethylhexanoate), manufactured by Nitto Kasei Co., Ltd.)

[0226] (Polymerization inhibitor) The polymerization inhibitors listed below were used in the production of the resin. · G-1: 2,2,6,6-tetramethylpiperidine 1-oxyl (TEMPO) · G-2: 4-hydroxy-2,2,6,6-tetramethylpiperidine 2-oxyl (4-hydroxy-TEMPO) G-3: p-methoxyphenol

[0227] <Synthesis of resins> (Synthesis of resin PA-1) A mixture was obtained by introducing a monomer B-1 solution with a concentration (solid content) of 50% by mass (24.0 parts (PGMEA: 12.0 parts, B-1: 12.0 parts)), ω-carboxy-polycaprolactone monoacrylate (82.0 parts, A-1), 4-vinylphenol (6.0 parts, C-1), and PGMEA (221.3 parts) into a three-necked flask. The mixture was stirred while blowing nitrogen into it. Next, the mixture was heated to 75°C while flowing nitrogen into the flask. Then, dodecyl mercaptan (1.88 parts) and then 2,2'-azobis(methyl 2-methylpropionate) (0.47 parts, hereinafter also referred to as "V-601") were added to the mixture to start the polymerization reaction. The mixture was heated at 75°C for 2 hours, after which 0.47 parts of V-601 were added to the mixture. After 2 hours, another 0.47 parts of V-601 were added to the mixture, and the temperature was raised to 90°C and stirred for 3 hours. The polymerization reaction was completed by the above procedure. After the reaction was complete, dimethyldodecylamine (3.12 parts, F-1) and 2,2,6,6,-tetramethylpiperidine 1-oxyl (TEMPO, 0.72 parts, G-1) were added under air, followed by the dropwise addition of 4-hydroxybutyl acrylate glycidyl ether (17.8 parts, E-1). After the dropwise addition was complete, the reaction was continued under air at 90°C for 48 hours. The completion of the reaction was confirmed by measuring the acid value, and a 34% by mass solution of resin PA-1 was obtained. The obtained resin PA-1 had a weight-average molecular weight of 25,400 and an acid value of 105.8 mgKOH / mg.

[0228] (Synthesis of resin PA-14) A mixture was obtained by introducing a monomer B-1 solution with a concentration (solid content) of 50% by mass (21.0 parts (PGMEA: 10.5 parts, B-1: 10.5 parts)), methacrylic acid (25.0 parts, A-7), 2-hydroxyethyl methacrylate (16.0 parts, D-4), benzyl methacrylate (42.5 parts, D-1), 4-vinylphenol (6.0 parts, C-1), and PGMEA (222.8 parts) into a three-necked flask. The mixture was stirred while blowing nitrogen into it. Next, the mixture was heated to 75°C while flowing nitrogen into the flask. Then, dodecyl mercaptan (2.39 parts) and then 2,2'-azobis(methyl 2-methylpropionate) (0.6 parts, hereinafter also referred to as "V-601") were added to the mixture to start the polymerization reaction. The mixture was heated at 75°C for 2 hours, after which 0.6 parts of V-601 were added to the mixture. After 2 hours, another 0.6 parts of V-601 were added to the mixture, and the mixture was heated to 90°C and stirred for 3 hours. The polymerization reaction was completed by the above procedure. After the reaction was complete, Neostan U-600 (manufactured by Nitto Chemical Co., Ltd.) (0.56 parts, F-6) and 2,2,6,6,-tetramethylpiperidine 1-oxyl (TEMPO, 0.60 parts, G-1) were added under air, and then 2-isocyanatoethyl acrylate (16.4 parts, E-6) was added dropwise. After the dropwise addition was complete, the reaction was continued under air at 60°C for 24 hours to obtain a 40% by mass solution of resin PA-14. The obtained resin PA-14 had a weight-average molecular weight of 18,600 and an acid value of 71.5 mgKOH / mg.

[0229] (Synthesis of resins other than PA-1 and PA-14) Resins PA-2 to PA-13, PA-15 to PA-17, and PZ-1 to PZ-2 were synthesized by referring to the resin synthesis method described above. Resins PA-1 to PA-17 are classified as specific resins (resins having structural units A to C), while resins PZ-1 to PZ-2 are comparative resins that do not fall under the category of specific resins. Furthermore, in the polymers synthesized at the end of the polymerization reaction (before the addition of the reactive compound) for each resin, the ratio of the content of constituent units derived from each monomer to the total mass of the polymer was substantially the same as the mass ratio of each monomer added during synthesis.

[0230] The table below shows the amount (mass%) of each component added in the synthesis of resins PA-1 to PA-17 and PZ-1 to PZ-2, with the total amount of monomers, reactive compounds, catalysts, and polymerization inhibitors used being set to 100% by mass. In addition, dodecyl mercaptan and V-601 were added in all resin synthesis processes, and the amounts added were adjusted as appropriate so that the resulting resin would have the desired weight-average molecular weight, as shown in the table.

[0231] The "Amount (%)" column in the table shows the amount (mass %) added to each component. Note that the values ​​listed in this column are rounded, so it is acceptable if the sum of the "Amount (%)" of each component in each resin does not equal 100%. In the table, the "C=C value (mmol / g)" column indicates the ethylenically unsaturated bond value of each resin. The C=C value was measured by the method described in the specification. The "Salt Structure Crosslinkable Unit Ratio (mol%)" column shows the content (mol%) of the constituent unit represented by Equation 6 relative to 100 mol% of constituent unit A in each resin. The "Salt Structure Crosslinkable Unit Ratio (mol%)" was calculated. Specifically, it was confirmed that the tertiary amine catalysts (F-1 to F-3, F-5) used during resin synthesis were not detected in the resin solution after the resin synthesis was completed, and it was determined that the tertiary amine catalysts were incorporated into the resin and became components of the salt structure crosslinkable units (constituent units represented by Equation 6). In other words, the "Salt Structure Crosslinkable Unit Ratio (mol%)" was calculated assuming that the same number of salt structure crosslinkable units (constituent units represented by Equation 6) as the number of molecules of the tertiary amine catalyst used during resin synthesis were formed. The "acid value (mgKOH / g)" of each resin was determined by neutralization titration using an aqueous sodium hydroxide solution. Specifically, the solution obtained by dissolving the resin in a solvent was titrated with an aqueous sodium hydroxide solution using potentiometric assay to calculate the number of millimoles of acid contained in 1g of solid resin. This value was then multiplied by the molecular weight of KOH, which is 56.1. The weight-average molecular weight (Mw) of each resin was calculated by GPC (Gel permeation chromatography) measurement under the following measurement conditions. Equipment: HLC-8220GPC (manufactured by Tosoh Corporation) Detector: Differential refractometer (RI detector) Pre-column TSKGUARDCOLUMN MP(XL) 6mm x 40mm (manufactured by Tosoh Corporation) Sample-side columns: The following four columns are directly connected (all manufactured by Tosoh Corporation) TSK-GEL Multipore-HXL-M 7.8mm×300mm Reference column: Same as sample column Constant temperature bath temperature: 40℃ Mobile phase: tetrahydrofuran Sample-side mobile phase flow rate: 1.0 mL / min Reference mobile phase flow rate: 0.3 mL / min Sample concentration: 0.1% by mass Sample injection volume: 100 μL Data acquisition time: 16 to 46 minutes after sample injection. Sampling pitch: 300 msec The weight-average molecular weight of the synthesized macromonomers was also determined using the same method.

[0232] [Table 1]

[0233] [Ingredients of the composition] The following lists the components used in the preparation of the composition.

[0234] <Resin> The resins PA-1 to PA-17 and PZ-1 to PZ-2, manufactured using the method described above, were used in the production of the composition. Furthermore, in the manufacture of the composition, the resin was used as the resin itself (solid component), not as a solution containing the resin.

[0235] <Other resins> The following components were used as other resins in the production of the composition. P1: Resin with the structure shown below. The values ​​appended to the main chain are molar ratios. Mw = 11000. P2: Resin with the structure shown below. The values ​​appended to the main chain are molar ratios. Mw = 30000. • P3: Cardo resin V-259ME (manufactured by Nippon Steel & Sumitomo Metal Corporation)

[0236] [ka]

[0237] <Photopolymerization initiator> The following components were used as photopolymerization initiators in the preparation of the composition. • I1: IRGACURE OXE02 (manufactured by BASF) • I2: IRGACURE OXE03 (manufactured by BASF) • I3: IRGACURE OXE04 (manufactured by BASF) • I4: NCI-831 (manufactured by ADEKA) • I5: Omnirad 1312 (manufactured by IGM) • I6: Omnirad 1314 (manufactured by IGM) ·I7: Omnirad 1316 (manufactured by IGM)

[0238] <Polymerizable compound> The following components were used as polymerizable compounds in the production of the composition. • M1: A compound represented by the following formula (M), where a+b+c=3 • M2: A compound represented by the following formula (M), where a+b+c=4 • M3: Compound represented by the following formula (M3) • M4: A compound (mixture) represented by the following formula (M4)

[0239] [ka]

[0240] <Surfactants> The following components were used as surfactants in the manufacture of the composition. • H1: Megafuck F-781F (manufactured by DIC Corporation) • H2: KF-6001 (manufactured by Shin-Etsu Chemical Co., Ltd.) • H3: BYK-333 (manufactured by Big Chemie Japan Co., Ltd.)

[0241] <Pigments> The following components were used as pigments in the manufacture of the composition. • TiON: Titanium Oxidride • TiN: Titanium Nitride ZrN: Zirconium Nitride ZrON: Zirconium oxynitride • CB: Carbon Black • TiO2: Titanium Oxide • Irgaphor Black: Irgaphor Black S0100CF (manufactured by BASF) PR254: CIPigment Red 254 PR264: CIPigment Red 264 PY139: CIPigment Yellow 139 PY150: CIPigment Yellow 150 · PB15:6:CIPigment Blue 15:6 ·PV23:CIPigment Violet 23 PG58: CIPigment Green 58 PG36: CIPigment Green 36 PY185: CIPigment Yellow 185 • K1: Compound with the following structure

[0242] [ka]

[0243] <Dispersing agent> The following components were used as dispersing agents in the manufacture of the composition. • B1~B2: Compounds with the following structure

[0244] [ka]

[0245] <Polymerization inhibitor> The following components were used as polymerization inhibitors in the manufacture of the composition. · G-1: 2,2,6,6-tetramethylpiperidine 1-oxyl (TEMPO) · G-2: 4-hydroxy-2,2,6,6-tetramethylpiperidine 2-oxyl (4-hydroxy-TEMPO)

[0246] <Solvent> Cyclopentanone and / or PGMEA (propylene glycol monomethyl ether acetate) were used as solvents in the preparation of the composition.

[0247] [Method for manufacturing the composition] The composition was prepared using the method described below. In other words, first, a pigment dispersion was produced by mixing some of the components contained in the composition, and then the resulting pigment dispersion was mixed with the other components to complete the composition (colored composition).

[0248] <Manufacturing of Pigment Dispersion> The components listed below were mixed in the mass ratios shown in the table. Then, 230 parts by mass of 0.3 mm diameter zirconia beads were added, and the mixture was dispersed for 5 hours using a paint shaker. The beads were then separated by filtration to produce each pigment dispersion.

[0249] [Table 2]

[0250] [Table 3]

[0251] <Preparation of composition> The pigment dispersion produced by the method described above was mixed with further components to complete the composition. In other words, the components listed below were mixed in the mass ratios shown in the table to obtain the composition (colored composition). In the table, the "Pigment Concentration in Solid Content (mass%)" column shows the pigment content (mass%) relative to the total solid content in each composition.

[0252] [Table 4]

[0253] [Table 5]

[0254] [evaluation] The compositions of each example prepared using the method described above were evaluated.

[0255] 〔test〕 The testing methods used in the evaluation are as follows.

[0256] <Evaluation of pattern adhesion> The composition was applied to an 8-inch silicon wafer that had been pre-sprayed with hexamethyldisilazane using a spin coater to achieve a film thickness of 1.5 μm after drying, and then pre-baked at 100°C for 120 seconds. This resulted in a coated substrate having a substrate (silicon wafer) and a film (composition layer) made of the composition on the substrate. Using an i-line stepper exposure system FPA-i5+ (manufactured by Canon), the composition layer was passed through a mask having an island pattern of 1.1 μm squares at a wavelength of 365 nm, at a rate of 50-1700 mJ / cm². 2 The image was exposed with the following exposure level. After exposure, the film was developed using alkaline developer CD-2000 (manufactured by Fujifilm Electronic Materials Co., Ltd.) at 25°C for 40 seconds. Afterward, it was rinsed with running water for 30 seconds, then spray-dried to obtain a pattern (a patterned cured film). The obtained patterns of various sizes (island patterns) were observed from above using a scanning electron microscope (Hitachi S-9220) and their sizes were measured. Larger exposure resulted in larger patterns. Furthermore, adhesion was evaluated using an optical microscope. Based on the pattern size when all patterns were in close contact, the adhesion of patterns formed using each composition was evaluated on a five-point scale as follows. A rating of 2 or higher is preferable, and ratings of 4 and 5 indicate excellent performance. 5: Adherence to an area of ​​0.9 μm square or larger but less than 1.0 μm square. 4: Adherence to an area of ​​1.0 μm square or larger and less than 1.05 μm square. 3: Adherence in areas of 1.05 μm square or larger and less than 1.1 μm square. 2: Adherence in areas of 1.1 μm square or larger and less than 1.2 μm square. Adhesion will not occur unless the area is 1:1.2 μm square or larger.

[0257] <Evaluation of development residue suppression (residue suppression in unexposed areas)> Each composition from each example or comparative example was applied to a glass substrate using spin coating and dried to form a composition layer with a thickness of 1.0 μm. The spin coating conditions were as follows: first, rotation speed: 300 rpm (rotations per minute) for 5 seconds, and then 800 rpm for 20 seconds. The drying conditions were 100°C for 80 seconds. The composition layer obtained as described above was exposed to light with a wavelength of 365 nm at a rate of 10 to 1,600 mJ / cm² through a pattern mask with a line and space of 1 μm using an i-line stepper exposure system FPA-3000i5+ (manufactured by Canon). 2 The material was irradiated with the specified exposure dose. Next, the exposed composition layer was developed using 60% by mass CD-2000 (manufactured by Fujifilm Electronic Materials Co., Ltd.) developer at 25°C for 60 seconds to obtain a patterned cured film. After that, the patterned cured film was rinsed with running water for 20 seconds and then air-dried. The cured film (pattern with a line width of 1.0 μm) obtained with an exposure dose that resulted in a pattern line width of 1.0 μm after development was heated in a 220°C oven for 1 hour along with the glass substrate. After heating the cured film, the number of residues present in the areas on the glass substrate that were not irradiated with light during the exposure process (unexposed areas) was observed using an SEM (Scanning Electron Microscope, magnification: 20,000x) and the residues in the unexposed areas were evaluated. The evaluation was performed according to the following criteria. In practical terms, an evaluation of 3 or higher is preferable, and evaluations 4 and 5 are considered to have excellent performance. 5: A pattern was formed, and no residue was observed in the unexposed areas. 4: A pattern was formed, and 1 to 3 residues were observed in the unexposed area, 1.0 μm square. 3: A pattern was formed, and 4 to 10 residues were observed in the unexposed area, 1.0 μm square. 2: A pattern was formed, and 11 or more residues were observed in the unexposed area of ​​1.0 μm square. 1: The pattern was not formed due to a development error.

[0258] <Measurement of optical density> Each composition was applied to a transparent substrate (glass substrate) and then dried to form a composition layer with a film thickness of 1.5 μm after drying. Next, the optical density (OD) of the obtained composition layer was evaluated using a V-4100F (manufactured by Hitachi High-Technologies Corporation) for light with wavelengths of 400 to 1100 nm according to the following criteria. OD = -log 10 (Transmittance (%) / 100) A: The minimum OD within the wavelength range of 400-1100nm is 3.0 or higher. B: The minimum OD within the wavelength range of 400-1100nm is 2.0 or greater and less than 3.0. C: The minimum OD within the wavelength range of 400-1100nm is 1.0 or greater and less than 2.0. D: Minimum OD is less than 1.0 within the wavelength range of 400-1100nm.

[0259] 〔result〕 The evaluation results and the characteristics of the compositions used in the tests are shown in the table below. In the table, the "Pigment" column shows the type of pigment contained in each composition and the pigment content (mass %) relative to the total solids of the composition. The "Resin" column indicates the type and characteristics of the specific resin or comparative resin contained in each resin.

[0260] [Table 6]

[0261] [Table 7]

[0262] As shown in the table, the composition of the present invention was confirmed to have excellent adhesion and be able to form patterns with high color value. Furthermore, it was confirmed that the composition of the present invention also exhibits excellent ability to suppress development residue when a pattern is formed.

[0263] In particular, it was confirmed that a higher color value pattern could be obtained when the pigment content in the composition was 30% by mass or more relative to the total solid content. It was confirmed that a pattern with an even higher color value can be obtained when the pigment content in the composition is 48% by mass or more relative to the total solids. (See the results of Examples 2 and 29, etc.)

[0264] It was confirmed that when the composition contains titanium black (titanium nitride and titanium oxynitride), zirconium nitride, or zirconium oxynitride as a pigment, the adhesion of the formed pattern is superior. (See the results of Example 10, etc.)

[0265] It was confirmed that when a specific resin contains the constituent units represented by formula 6, the development residue suppression and / or the adhesion of the formed pattern are superior (see the results of Examples 17, 20, and 21, etc.). It was confirmed that when the content of the constituent unit represented by formula 6 in the specific resin is 20 mol% or more relative to the total constituent unit A, the development residue suppression performance is further improved (see the results of Examples 18 and 19, etc.).

[0266] It was confirmed that when a specific resin contains the constituent units represented by formula 6, the development residue suppression and / or the adhesion of the formed pattern are superior (see the results of Examples 17, 20, and 21, etc.). It was confirmed that when the content of the constituent unit represented by formula 6 in the specific resin is 20 mol% or more relative to the total constituent unit A, the development residue suppression performance is further improved (see the results of Examples 18 and 19, etc.).

[0267] R in the constituent unit represented by Equation 1 0 When the pigment is a hydrogen atom, it was confirmed that the development residue suppression and / or the adhesion of the formed pattern are superior (see the comparison between Example 15 and other examples that use TiON as a pigment and a specific resin in which the salt structure type crosslinkable unit ratio in the specific resin is 16.0 mol%). [Explanation of Symbols]

[0268] 10. Headlight Unit 12...Light source 14. Light-blocking section 16 lenses 20...Base 22. Light-shielding film 23...Opening 30... Beam Pattern 30a... Edge 31...area 32... Beam Patterns 32a... Edge 33.. Notch 34...area 100... Solid-state imaging device 101... Solid-state image sensor 102...Imaging Unit 103... Cover glass 104...Spacer 105...Laminated substrate 106... Chip board 107...Circuit board 108... Electrode Pads 109...External connection terminals 110...Through electrode 111... Lens layer 112...Lens material 113...Support 114, 115... Light-shielding film 201... Light-receiving element 202...Color Filter 203... Microlens 204... Circuit board 205b... Blue pixels 205r...Red pixels 205g...Green pixels 205bm...Black Matrix 206 p-well layer 207...Read gate section 208... Vertical Transfer Channel 209...Element isolation region 210...Gate Insulator 211... Vertical transfer electrode 212... Light-shielding film 213, 214... Insulating film 215...Planarization film 300... Infrared Sensor 310... Solid-state image sensor 311... Infrared absorption filter 312...Color Filter 313... Infrared transmission filter 314... Resin film 315... Microlens 316...Planarization film

Claims

1. Pigments and Solvents and, A resin having a polymerizable unit A, a phenolic hydroxyl unit B, and an acidic unit C, A photopolymerization initiator is included, The polymerizable group is an ethylenically unsaturated group, The aforementioned structural unit A is a structural unit represented by formula 1, The aforementioned constituent unit B is a constituent unit represented by formula 2-1, The aforementioned constituent unit C is a repeating unit represented by formula C, A colored composition in which the pigment content is 15% by mass or more relative to the total solid content of the colored composition. 【Chemistry 1】 In Formula 1, R1 to R3 each independently represent a hydrogen atom or an alkyl group. X1 represents -COO- or an arylene group. R4 represents a (n+1) valence linking group. X² represents an oxygen atom. R0 represents a hydrogen atom or an alkyl group. n represents either 1 or 2. The (n+1) valent linking group is an ether group, an ester group, -NR X-, an alkylene group which may have a hydroxyl group, a trivalent group represented by -CR Y<, an aromatic ring group, an alicyclic group which may have a hydroxyl group, an onium structure-containing group, or a group which is a combination thereof. R X represents a hydrogen atom or an alkyl group. RY represents a hydrogen atom or an alkyl group. 【Chemistry 2】 In formula 2-1, R １１ ~R １３ Each of these independently represents either a hydrogen atom or an alkyl group. L ＡＲ represents a single bond or a divalent linking group. The divalent linking group is an ether group, a carbonyl group, an ester group, or -NR Ｘ - represents a divalent hydrocarbon group, a divalent heterocyclic group, a heteroarylene group, or a group combining these. Ｘ represents a hydrogen atom or an alkyl group. Ar represents a (j+1) valent benzene ring group or naphthalene ring group. j represents an integer greater than or equal to 1. 【Transformation 3】 In formula C, R ｃ represents a hydrogen atom or an alkyl group. X ｃ represents a single bond, -COO-, -CONR Ｂ -, or an arylene group. R Ｂ represents a hydrogen atom, an alkyl group, or an aryl group. L ｃ X represents a group formed by bonding a total of two or more groups selected from the group consisting of an aliphatic hydrocarbon group having 1 to 20 carbon atoms, an arylene group having 6 to 20 carbon atoms, or an aliphatic hydrocarbon group having 1 to 20 carbon atoms and an arylene group having 6 to 20 carbon atoms, with a total of one or more groups selected from the group consisting of an ether group and an ester group. ｃ When L is a single bond or the aforementioned arylene group, ｃ It may be a single bond. AC represents a carboxyl group, a sulfonic acid group, or a phosphonic acid group.

2. The colored composition according to claim 1, wherein the constituent unit B is a constituent unit represented by formula 2. 【Chemistry 4】 In formula 2, R １１ ~R １３ Each of these independently represents either a hydrogen atom or an alkyl group. A represents -COO-, -CONR'-, -COO-R”-, -CONR'-R”-, or an arylene group. R' represents a hydrogen atom, an alkyl group, or an aryl group. R” represents a divalent linking group. m represents either 0 or 1. l represents an integer between 1 and 5.

3. The colored composition according to claim 1 or 2, wherein the constituent unit A includes a constituent unit represented by formula 3. 【Transformation 5】 In formula 3, R １ ~R ３ Each of these independently represents either a hydrogen atom or an alkyl group. X １ This represents -COO- or an arylene group. R ５ R is an ether group, ester group, -NR X-, alkylene group, aromatic ring group, alicyclic group, or a combination thereof. R X represents a hydrogen atom or alkyl group. L １ This represents a base expressed by formula 4 or formula 5. R ６ This represents a (n+1) valence linking group. X ２ This represents an oxygen atom. R ０ represents a hydrogen atom or an alkyl group. n represents either 1 or 2. The (n+1) valent linking group is an ether group, an ester group, a -NR X-, an alkylene group, a trivalent group represented by -CR Y<, an aromatic ring group, an alicyclic group, or a combination thereof. R X represents a hydrogen atom or an alkyl group. R Y represents a hydrogen atom or an alkyl group. In formula 4, X ３ represents an oxygen atom or -NH-. * indicates the joining position. In formula 5, X ４ This represents an oxygen atom or -COO-. R ｅ１ ~R ｅ３ Each of these independently represents either a hydrogen atom or an alkyl group. ｅ１ ~R ｅ３ At least two of these may be joined together to form a ring. * indicates the joining position.

4. The colored composition according to any one of claims 1 to 3, wherein the constituent unit A includes a constituent unit represented by formula 6. 【Transformation 6】 In formula 6, R １ ~R ３ Each of these independently represents either a hydrogen atom or an alkyl group. X １ This represents -COO- or an arylene group. R ７ This represents a structure containing a group from which one proton has been dissociated from an acidic group. R ８ ∫ represents an ether group, ester group, -NR X-, alkylene group, aromatic ring group, alicyclic group, or a combination thereof. R X represents a hydrogen atom or alkyl group. L ２ This represents the base expressed in Equation 5. R ６ This represents a (n+1) valence linking group. X ２ This represents an oxygen atom. n represents either 1 or 2. R Ｂ１ ~R Ｂ３ Each of these independently represents a hydrogen atom, an alkyl group, or an aryl group. R ０ represents a hydrogen atom or an alkyl group. The (n+1) valent linking group is an ether group, an ester group, a -NR X-, an alkylene group, a trivalent group represented by -CR Y<, an aromatic ring group, an alicyclic group, or a combination thereof. R X represents a hydrogen atom or an alkyl group. R Y represents a hydrogen atom or an alkyl group. In formula 5, X ４ This represents an oxygen atom or -COO-. R ｅ１ ~R ｅ３ Each of these independently represents either a hydrogen atom or an alkyl group. ｅ１ ~R ｅ３ At least two of these may be joined together to form a ring.

5. The colored composition according to claim 4, wherein the content of the constituent unit represented by formula 6 in the constituent unit A is 10 mol% or more.

6. The colored composition according to any one of claims 1 to 5, wherein the constituent unit B is a constituent unit represented by formula 7. 【Transformation 7】 In formula 7, R １１ represents a hydrogen atom or an alkyl group. A represents -COO-, -CONR'-, -COO-R”-, -CONR'-R”-, or an arylene group. R' represents a hydrogen atom, an alkyl group, or an aryl group. R” represents a divalent linking group. m represents either 0 or 1. k represents an integer between 1 and 3.

7. The colored composition according to any one of claims 1 to 6, wherein the constituent unit B is one or more selected from the group consisting of the constituent unit represented by formula 8, the constituent unit represented by formula 9, and the constituent unit represented by formula 10. 【Transformation 8】

8. The coloring composition according to any one of claims 1 to 7, wherein the pigment comprises one or more selected from the group consisting of carbon black, titanium black, zirconium nitride, and zirconium oxynitride.

9. The colored composition according to any one of claims 1 to 8, wherein the resin further comprises a constituent unit D represented by formula D. 【Chemistry 9】 In formula D, R Ｄ represents a hydrogen atom or an alkyl group. X Ｄ is an oxygen atom or -NR Ｃ Represents -. R Ｃ represents a hydrogen atom, an alkyl group, or an aryl group. L Ｄ This represents a single bond or a divalent linking group. Y １ and Y ２ Each of these independently represents either an alkylene oxy group or an alkylene carbonyl oxy group. Z １ This represents an aliphatic hydrocarbon group having 1 to 20 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms. p and q each independently represent non-negative integers. However, the value of p + q must be 1 or greater.

10. A cured film formed using the colored composition according to any one of claims 1 to 9.

11. A light-shielding film comprising the cured film described in claim 10.

12. A color filter comprising the cured film described in claim 10.

13. An optical element comprising the cured film described in claim 10.

14. A solid-state image sensor comprising the cured film described in claim 10.

15. An infrared sensor comprising the cured film described in claim 10.

16. A headlight unit for a vehicle, Light source and It has a light-shielding portion that blocks at least a portion of the light emitted from the light source, A headlight unit in which the light-shielding portion includes the cured film described in claim 10.

Images