WO2018135249A1

WO2018135249A1 - Curable composition, cured film, color filter, light-blocking film, solid-state imaging element, image display device, and method for manufacturing cured film

Info

Publication number: WO2018135249A1
Application number: PCT/JP2017/046511
Authority: WO
Inventors: 明夫水野; 貴規田口
Original assignee: 富士フイルム株式会社
Priority date: 2017-01-23
Filing date: 2017-12-26
Publication date: 2018-07-26
Also published as: JP6680907B2; TW201827401A; JPWO2018135249A1

Abstract

The purpose of the present invention is to provide a curable composition with which it is possible to obtain a cured film having an excellent pattern shape. The purpose of the present invention is also to provide a cured film, a color filter, a light-blocking film, a solid-state imaging element, an image display device, and a method for manufacturing the cured film. The curable composition contains a photoinitiator, a multifunctional thiol compound, a polymerizable compound, and a coloring agent, the photoinitiator being a specified oxime compound.

Description

Curable composition, cured film, color filter, light-shielding film, solid-state imaging device, image display apparatus, and method for producing cured film

The present invention relates to a curable composition, a cured film, a color filter, a light shielding film, a solid-state imaging device, an image display device, and a method for producing the cured film.

In a color filter used in an image display device, a cured film obtained by curing a curable composition is used as each colored pixel. Moreover, the cured film which hardened the curable composition is also used as a black matrix for shielding the light between each colored pixel and improving contrast.
A cured film is also used for the same purpose in the color filter used in the solid-state imaging device. The solid-state imaging device uses a cured film for the purpose of preventing noise and improving image quality.
Currently, portable terminals of electronic devices such as mobile phones and PDAs (Personal Digital Assistants) are equipped with small and thin imaging units. Such an imaging unit generally includes a solid-state imaging device such as a CCD (Charge Coupled Device) image sensor and a CMOS (Complementary Metal-Oxide Semiconductor) image sensor, a lens for forming a subject image on the solid-state imaging device, It has.

As a curable composition, for example, Patent Document 1 discloses (A) a colorant, (B) a binder resin, (C) a photopolymerization initiator having a predetermined structure, and (D) two or more polymerizable unsaturations. A coloring composition containing a compound having a bond and (E) a polyfunctional thiol is described.

JP 2013-83932 A

The inventors of the present invention have studied the coloring composition described in Patent Document 1, and have found that there is a problem that the pattern shape of the obtained cured film does not reach the level required recently. In addition, in this specification, a pattern shape intends the pattern shape of the cured film measured by the method described in the Example.

Then, this invention makes it a subject to provide the curable composition which can obtain the cured film which has the outstanding pattern shape (it is also called "it has the effect of this invention" hereafter).
Another object of the present invention is to provide a cured film, a color filter, a light shielding film, a solid-state imaging device, an image display device, and a method for producing the cured film.

As a result of intensive studies to achieve the above-mentioned problems, the present inventors have found that the above-described problems can be achieved by the following configuration.

[1] A curable composition containing a photopolymerization initiator, a polyfunctional thiol compound, a polymerizable compound, and a colorant, wherein the photopolymerization initiator is represented by formula (1) A curable composition.
[2] The curable composition according to [1], wherein R ¹ in Formula (1) has 13 or more carbon atoms.
[3] The curable composition according to [1] or [2], wherein the content ratio of the oxime compound content to the polyfunctional thiol compound content in the curable composition is 1 to 10.
[4] The curable composition according to any one of [1] to [3], wherein the content ratio of the oxime compound content to the polyfunctional thiol compound content in the curable composition is 4 to 10. object.
[5] The curable composition according to any one of [1] to [4], wherein the polyfunctional thiol compound is a compound represented by the formula (2).
[6] In the formula (2), R ²⁴ and R ²⁵ are each independently an alkyl group or —C (═O) —O—R ²³ , and M ²¹ is —C (═O) —O. The curable composition according to [5], wherein n is an integer of 3 to 10.
[7] The curable composition according to any one of [1] to [6], wherein the colorant comprises an organic pigment.
[8] The curable composition according to any one of [1] to [6], wherein the colorant comprises an inorganic pigment.
[9] A cured film obtained by curing the curable composition according to any one of [1] to [8].
[10] A color filter containing the cured film according to [9].
[11] A light-shielding film containing the cured film according to [9].
[12] A solid-state imaging device containing the cured film according to [9].
[13] An image display device comprising the cured film according to [9].
[14] A curable composition layer forming step of forming a curable composition layer on a support using the curable composition according to any one of [1] to [8], and a curable composition layer A method for producing a cured film, comprising exposing an exposure step.
[15] The cured film according to [14], wherein the curable composition layer forming step is a step of coating the curable composition on the support to form a curable composition layer on the support. Production method.
[16] The method for producing a cured film according to [14] or [15], further including a development step of developing the exposed curable composition layer.

ADVANTAGE OF THE INVENTION According to this invention, the curable composition which can obtain the cured film which has the outstanding pattern shape can be provided.
Moreover, according to this invention, the manufacturing method of a cured film, a color filter, a light shielding film, a solid-state image sensor, an image display apparatus, and a cured film can also be provided.

It is sectional drawing which showed typically the manufacturing process of the cured film using the curable composition which does not contain a polyfunctional thiol compound for every process. It is sectional drawing which showed typically the manufacturing process of the cured film using the curable composition which does not contain a polyfunctional thiol compound for every process. It is sectional drawing which showed typically the manufacturing process of the cured film using the curable composition which does not contain a polyfunctional thiol compound for every process. It is sectional drawing which showed typically the manufacturing process of the cured film using the curable composition which contains a polyfunctional thiol compound and does not contain a specific oxime compound for every process. It is sectional drawing which showed typically the manufacturing process of the cured film using the curable composition which contains a polyfunctional thiol compound and does not contain a specific oxime compound for every process. It is sectional drawing which showed typically the manufacturing process of the cured film using the curable composition which contains a polyfunctional thiol compound and does not contain a specific oxime compound for every process. It is a schematic sectional drawing which shows the solid-state imaging device which concerns on embodiment of this invention. It is a schematic sectional drawing which expands and shows the imaging part of FIG. It is a schematic sectional drawing which shows the structural example of the infrared sensor which concerns on embodiment of this invention.

Hereinafter, the present invention will be described in detail.
The description of the constituent elements described below may be made based on typical embodiments of the present invention, but the present invention is not limited to such embodiments.
In the present specification, a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
In the description of the group (atomic group) in this specification, the description which does not describe substitution and non-substitution includes what does not contain a substituent and what contains a substituent. For example, the “alkyl group” includes not only an alkyl group not containing a substituent (unsubstituted alkyl group) but also an alkyl group containing a substituent (substituted alkyl group).
“Actinic rays” or “radiation” in the present specification means, for example, deep ultraviolet rays, extreme ultraviolet lithography (EUV), X-rays, and electron beams. In this specification, “light” means actinic rays and radiation. Unless otherwise specified, “exposure” in this specification includes not only exposure with far ultraviolet rays, X-rays, EUV light, etc., but also drawing with particle beams such as electron beams and ion beams.
In the present specification, “(meth) acrylate” represents acrylate and methacrylate. In the present specification, “(meth) acryl” represents acryl and methacryl. In this specification, “(meth) acryloyl” represents acryloyl and methacryloyl. In this specification, “(meth) acrylamide” represents acrylamide and methacrylamide.
In the present specification, “monomer” and “monomer” are synonymous. A monomer is distinguished from an oligomer and a polymer, and refers to a compound having a weight average molecular weight of 2,000 or less. In the present specification, the polymerizable compound means a compound containing a polymerizable group, and may be a monomer or a polymer. The polymerizable group refers to a group that participates in a polymerization reaction.

[Curable composition]
The curable composition which concerns on embodiment of this invention contains a photoinitiator, a polyfunctional thiol compound, a polymeric compound, and a coloring agent, and photoinitiator is represented by Formula (1) mentioned later. One feature is that it is an oxime compound (hereinafter also referred to as “specific oxime compound”).

According to the curable composition of the present invention having such a configuration, a cured film having an excellent pattern shape can be obtained. The reason is not clear in detail, but the present inventors speculate as follows. The scope of the present invention is not limited by the following estimation. In other words, even when the effect is obtained by a mechanism other than the following speculation mechanism, it is included in the scope of the present invention.

A typical method for producing a cured film is a method in which a curable composition is applied on a support to obtain a curable composition layer, which is exposed in a pattern and developed. However, the optical density (also referred to as OD: optical density) of the curable composition layer gradually increases from the long wavelength side to the short wavelength side, and particularly increases on the short wavelength side. Therefore, for example, when the curable composition layer is exposed in a pattern with light in the ultraviolet region such as g-line, h-line, and i-line (in other words, light on the short wavelength side), the light is curable composition layer. It did not reach the inside, exposure was insufficient, and as a result, the curable composition did not cure as intended, and the pattern shape of the cured film sometimes deteriorated.
The mechanism by which the pattern shape deteriorates due to the above will be described with reference to FIGS. 1 to 6 schematically showing the manufacturing process of the cured film for each process. First, FIGS. 1 to 3 are cross-sectional views schematically showing a production process of a cured film using a curable composition not containing a polyfunctional thiol compound for each process.
First, as shown in FIG. 1, a curable composition layer 102 is formed on a support 101 using a curable composition. Next, the curable composition layer 102 is exposed through the opening of the photomask 103 (in FIG. 1, arrows indicate the direction of light irradiation, and the line AB represents the end of the opening of the photomask. The same shall apply hereinafter.) Next, the curable composition layer 102 after the exposure is developed to form a patterned cured film 201.
During the exposure in the above procedure, since the optical density of the curable composition layer 102 is high, it is difficult for light to reach the inside of the curable composition layer 102 at the time of exposure, and under the curable composition layer 102, the exposure is insufficient. It becomes. Then, a curable composition will elute in the part in which the exposure in the curable composition layer 102 is inadequate by image development (FIG. 2). In such a state, when the post-baking process for heating the cured film 201 is performed, the film thickness is reduced at the end of the obtained post-baked cured film 301 as compared with the central portion, and the pattern shape is It is presumed that it is likely to deteriorate (FIG. 3).

On the other hand, FIGS. 4 to 6 are sectional views schematically showing, for each step, a process for producing a cured film using a curable composition containing a polyfunctional thiol compound and not containing a specific oxime compound described later. .
First, as shown in FIG. 4, a curable composition layer 401 is formed on a support 101 using a curable composition containing a polyfunctional thiol compound. Next, the curable composition layer 401 is exposed through the opening of the photomask 103.
At this time, in the exposed curable composition layer 401, the polymerization reaction is started by radicals generated from the photopolymerization initiator. The polyfunctional thiol compound functions as a chain transfer agent. Therefore, for example, even if a peroxy radical that hinders the polymerization reaction is generated by the reaction between the radical and oxygen, the thiol group in the polyfunctional thiol compound donates hydrogen to the peroxy radical, thereby deactivating the polymerization by oxygen. It is thought that a thiyl radical that is not easily received is generated and the polymerization reaction proceeds. Therefore, it is estimated that the curable composition containing a polyfunctional thiol compound is easily cured to the inside of the curable composition layer 401.
On the other hand, since the polyfunctional thiol compound is highly reactive and easily causes chain transfer, depending on conditions such as the composition of the curable composition, the exposure amount, and the pattern shape, the radical polymerization reaction is chained to the unexposed area. In particular, an unexposed portion of the curable composition layer on the light irradiation surface side may be unintentionally cured. In this case, when the curable composition layer after exposure is developed, the cured film 501 may unintentionally spread to an unexposed portion (FIG. 5). When such a defect occurs, the end portion of the post-baked cured film 601 unintentionally spreads and the pattern shape may deteriorate (FIG. 6).

The present inventors who discovered the above phenomenon for the first time have made extensive studies and have completed the present invention. The curable composition of the present invention is an oxime compound (specific oxime compound) containing, as a photopolymerization initiator, a hydrocarbon group having 8 or more carbon atoms in which R ^{1 of} formula (1) described later may contain a hetero atom. Containing. The specific oxime compound is bulky due to the influence of the group represented by R ¹ .
Since the specific oxime compound has a bulky structure as described above, it is presumed that the specific oxime compound is difficult to diffuse in the curable composition layer. Therefore, even when a highly functional polyfunctional thiol compound is used as the chain transfer agent, radical species are less likely to diffuse in the unexposed areas, and as a result, the curing reaction hardly occurs in the unexposed areas, resulting in an excellent pattern shape. It is presumed that a cured film was obtained.
Below, each component which the curable composition which concerns on embodiment of this invention contains is explained in full detail.

The curable composition according to the embodiment of the present invention contains a polyfunctional thiol compound, a polymerizable compound, a colorant, and a photopolymerization initiator, and the photopolymerization initiator is a specific oxime compound described later.

[Specific oxime compounds]
The curable composition which concerns on embodiment of this invention contains the specific oxime compound mentioned later. The specific oxime compound has a function as a photopolymerization initiator.
The content of the specific oxime compound in the curable composition is not particularly limited, but is generally preferably 1 to 8% by mass with respect to the total solid content of the curable composition. A specific oxime compound may be used individually by 1 type, or may use 2 or more types together. When using 2 or more types of specific oxime compounds together, it is preferable that total content is in the said range.
As the specific oxime compound, the N—O bond may be an (E) isomer or a (Z) isomer. As the specific oxime compound, the (E) isomer and the (Z) isomer may be used in combination.

In formula (1), R ¹ represents a hydrocarbon group having 8 or more carbon atoms which may contain a hetero atom. The hydrocarbon group may be linear, branched, cyclic, or a combination thereof. Among these, a linear, branched, or cyclic hydrocarbon having 13 or more carbon atoms, which may contain a heteroatom, is obtained in that a curable composition having the better effect of the present invention can be obtained. Groups are preferred.
Although R ¹ is not particularly limited, as a hetero atom containing a nitrogen atom, a sulfur atom, and an oxygen atom.
R ¹ includes, for example, a linear alkyl group having 8 or more carbon atoms, a branched alkyl group having 8 or more carbon atoms, a cycloalkyl group having 8 or more carbon atoms, or a carbon atom having 8 or more carbon atoms containing a cycloalkylene group. Examples thereof include a hydrogen group and a group represented by * -L ¹¹ -R ¹¹ . L ¹¹ represents a divalent linking group, R ¹¹ represents an alkyl group, and * represents a bonding position with a carbon atom.
Here, the divalent linking group of L ¹¹ is not particularly limited, and for example, an alkylene group, a carbonyl group, —O—, —S—, —NR ¹² —, and combinations thereof are preferable. , -O -, - S-, and, ^{-NR 12} - a combination of two or more selected from the group consisting of is more preferable. Here, R ¹² represents a hydrogen atom or an alkyl group.

R ¹ is a linear alkyl group having 13 or more carbon atoms or a group represented by * -L ¹¹ -R ¹¹ in that a curable composition having the better effect of the present invention can be obtained. A group represented by * -L ¹¹ -R ¹¹ is more preferred, and a group represented by the following formula (1-1) is still more preferred.

In Formula (1-1), R ¹³ represents an alkylene group having 1 to 3 carbon atoms, and Z ¹ represents at least one selected from the group consisting of —O—, —S—, and —NR ¹² —. , R ¹⁴ represents an alkyl group, and n ¹¹ represents an integer of 1 or more. R ¹² represents a hydrogen atom or an alkyl group. Incidentally, the formula (1-1) and ^{R 13,} during, ^{if Z 1} is more, each of ^{R 13} and ^{Z 1} may be the same as or different from each other, * represents a bonding position.

In Formula (1), X ² represents a single bond or a divalent linking group, and examples of the divalent linking group include an alkylene group (preferably having 1 to 12 carbon atoms), a cycloalkylene group, an alkenylene group, and an alkynylene. Group, carbonyl group, —S—, —O—, —NR ¹⁵ —, and a combination of these, and the like. From the viewpoint of obtaining a curable composition having more excellent effects of the present invention, X ² is preferably a single bond, an alkylene group, or a group in which an alkylene group and —S— are combined. R ¹⁵ represents a hydrogen atom or an alkyl group.

In formula (1), R ² represents an alkyl group or an aryl group. Among them, as R ² , a linear alkyl group having 1 to 25 carbon atoms, each of which may contain a substituent, in that a curable composition having the better effect of the present invention can be obtained. A branched alkyl group having 1 to 25 carbon atoms, an alicyclic alkyl group having 4 to 25 carbon atoms, or an aryl group containing a substituent is preferable. Examples of the substituent include, for example, a halogen atom (preferably a fluorine atom), an aryloxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, an acyl group, an alkyl group, an aryl group, and *- Examples include, but are not limited to, a group represented by X ⁶ -R ⁶ . Note that * represents a bonding position, and the forms of X ⁶ and R ⁶ will be described later.

In formula (1), X ³ represents a single bond or a carbonyl group. R ³ represents an aryl group and may contain a substituent. Among them, R ³ is represented by the following formula ( ³ ) in that a curable composition having a better effect of the present invention can be obtained. The group represented by 1-2) is preferred.
*-[Ar] -X ⁶ -R ⁶ formula (1-2)
In formula (1-2), * represents a bonding position with X ^3, and [Ar] represents an arylene group, which may be a single ring or a condensed ring. X ⁶ represents a single bond or a divalent linking group. Examples of the divalent linking group for X ⁶ include an alkylene group, an arylene group, a cycloalkylene group, an alkenylene group, an alkynylene group, a carbonyl group, —S—, —O—, —NR ⁶¹ —, and a combination thereof. Is mentioned. Here, R ⁶¹ represents a hydrogen atom or an alkyl group. Among these, X ⁶ is preferably a single bond, —S— or a carbonyl group in that a curable composition having the better effect of the present invention can be obtained.
In the above formula, R ⁶ represents a hydrogen atom or a substituent. The substituent is not particularly limited, and examples thereof include an alkyl group, —NO ₂ , an aryl group, and a heterocyclic group. As the substituent, an aryl group of R ² may be a substituent which may contain.

Examples of the specific oxime compound include compounds represented by the following formulas (1-A) to (1-D).

More specifically, compounds represented by the following formulas (1-a) to (1-d) can be mentioned.

In formulas (1-A) to (1-D) and formulas (1-a) to (1-d), R ¹ , R ² , X ² , and X ³ are each represented by formula (1 ) And R ¹ , R ² , X ² , and X ³ , and the preferred embodiments are also the same.
In the formulas (1-A) to (1-D) and the formulas (1-a) to (1-d), R ¹⁰ represents a hydrogen atom or a monovalent substituent. The monovalent substituent is not particularly limited. For example, —NO ₂ (hereinafter also referred to as a nitro group), a group represented by * —X ⁶ —R ⁶ , an aryl group which may contain a substituent And an aryl heterocyclic group which may contain a substituent.

In formulas (1-A) to (1-D) and formulas (1-a) to (1-d) (except for formulas (1-B) and (1-b)), R ⁷ represents —O—, —S—, or —NR ⁷¹ —. R ⁷¹ represents a substituent, and the substituent is not particularly limited, and for example, an alkyl group having 1 to 20 carbon atoms (which may be linear, branched or cyclic). And an alicyclic hydrocarbon group having 4 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, and an arylalkyl group having 7 to 30 carbon atoms. The above substituent may contain a heteroatom, and among them, a nitrogen atom, an oxygen atom, a halogen atom, etc. may be used as the heteroatom in that a curable composition having the effects of the present invention can be obtained. Are preferable, and a nitrogen atom, an oxygen atom, or a fluorine atom is more preferable.

In formula (1-B) and formula (1-b), R ⁸ represents a divalent linking group. The form of the divalent linking group for R ⁸ is the same as that already described as the divalent linking group for X ⁶ .

Specific examples of the specific oxime compound are shown in Tables 1-1 to 1-4 below, but the specific oxime compound is not limited thereto. In Table 1, the wavy line represents the coupling position, and “↑” represents the same as the column immediately above. The structure described in the column “—X ² —R ² ” represents a form in which the group represented by the linking group X ² and R ² are bonded. The contents of the “formula” column correspond to the above formulas (1-a) to (1-d), respectively, and each symbol (R ¹ , —X ² —R ² , X ³ , R ⁷ , R ⁸ , And R ¹⁰ ) corresponds to each symbol in each formula. “None” in the R ⁷ and R ⁸ columns indicates that the compound represented by the corresponding formula does not contain groups represented by R ⁷ and R ⁸ , respectively. The numbers of the specific oxime compounds (“INT-1” to “INT-50”) correspond to the numbers of the specific oxime compounds in the examples.

The specific oxime compound preferably has a maximum absorption wavelength in the wavelength region of 350 to 500 nm, more preferably has a maximum absorption wavelength in the wavelength region of 360 to 480 nm, and more preferably has a high absorbance at 365 nm and 405 nm.
The molar extinction coefficient at 365 nm or 405 nm of the oxime compound is preferably 1,000 to 300,000, more preferably 2,000 to 300,000, and further preferably 5,000 to 200,000 from the viewpoint of sensitivity.
The molar extinction coefficient of the compound can be measured by a known method. For example, the molar extinction coefficient is measured at a concentration of 0.01 g / L using an ultraviolet-visible spectrophotometer (Cary-5 spectrphotometer manufactured by Varian) using an ethyl acetate solvent. It is preferable.

The specific oxime compound can be synthesized by a known method. Typically, it can be synthesized by reaction of the corresponding oxime with an acid chloride in an inert solvent in the presence of a base or in a basic solvent. Examples of the base include triethylamine and pyridine. Examples of the inert solvent include tert-butyl methyl ether, tetrahydrofuran (THF), dimethylformamide, and the like. Examples of the base solvent include pyridine.

[Polyfunctional thiol compound]
The curable composition which concerns on embodiment of this invention contains a polyfunctional thiol compound. In the present specification, a polyfunctional thiol compound is intended to contain two or more thiol groups (that is, a group represented by —SH) in the same molecule.
The content of the polyfunctional thiol compound is not particularly limited, but is often 0.1 to 10% by mass with respect to the content of the colorant. Among these, 0.5 to 8.0% by mass is preferable with respect to the content of the colorant in that the curable composition has the more excellent effects of the present invention.
Further, the content of the polyfunctional thiol compound is preferably 0.1 to 8.0% by mass, and more preferably 0.3 to 6.0% by mass with respect to the total solid content of the curable composition.
In addition, a polyfunctional thiol compound may be used individually by 1 type, or may use 2 or more types together. When using 2 or more types together, it is preferable that the sum total is in the said range.

The relationship between the polyfunctional thiol compound and the content of the specific oxime compound is not particularly limited, but a cured film having a more excellent pattern shape can be obtained by the curable composition (having a more excellent effect of the present invention. ) In terms of the content ratio of the content of the specific oxime compound to the content of the polyfunctional thiol compound in the curable composition (content of specific oxime compound / content of polyfunctional thiol compound) 1 to 15 is preferable, 0.5 to 12 is more preferable, 1 to 10 is still more preferable, and 4 to 10 is particularly preferable.

The polyfunctional thiol compound is preferably represented by the following formula (2) in that the curable composition has more excellent effects of the present invention.

In formula (2), R ²⁴ and R ²⁵ are a hydrogen atom, an alkyl group, an aryl group, —C (═O) —R ²³ , —C (═O) —O—R ²³ , or —C Represents (═O) —NH—R ^23, and is preferably an alkyl group or —C (═O) —O—R ²³ . R ²³ represents an alkyl group or an aryl group, and a plurality of R ²⁴ , R ²⁵ , and M ²¹ (described later) may be the same or different, and when there are a plurality of R ²³ , they may be the same. May be different.

L ²¹ represents an n-valent organic linking group. n represents an integer of 2 to 10, preferably 3 to 10, and more preferably 3 to 6. When L ²¹ is a divalent organic linking group, for example, a divalent aliphatic hydrocarbon group (preferably having 1 to 8 carbon atoms), a divalent aromatic hydrocarbon group (preferably having 6 to 12 carbon atoms). , -O-, -S-, -N (Rx)-(Rx: a monovalent organic group), -C (= O)-, -C (= O) -O-, -O-C (= O ) —O—, —C (═O) —NH—, —O—C (═O) —NH—, —S (═O) —, —S (═O) —O—, —S (═O ) ₂ —, —S (═O) ₂ —O—, —CH═N—, or a combination thereof (for example, an alkyleneoxy group, an alkyleneoxycarbonyl group, and an alkylenecarbonyloxy group). It is done.
When L ²¹ is a trivalent or higher valent organic linking group, for example, isocyanur containing three trimethylolpropane residues, — (CH ₂ ) _k — (k represents an integer of 2 to 6, for example). Examples thereof include a trivalent linking group such as a ring, a tetravalent linking group such as a pentaerythritol residue, a pentavalent linking group, a hexavalent linking group such as a dipentaerythritol residue, and combinations thereof.
Examples of the n-valent organic linking group for L ²¹ include groups represented by any of the following formulas (A) to (D), or groups obtained by combining these groups.

In the above formulas (A) to (D),
L ⁴ represents a trivalent group. T ³ represents a single bond or a divalent linking group, and three T ^{3 s} may be the same as or different from each other.
L ⁵ represents a tetravalent group. T ⁴ represents a single bond or a divalent linking group, and the four T ^{4 s} may be the same as or different from each other.
L ⁶ represents a pentavalent group. T ⁵ represents a single bond or a divalent linking group, and the five T ^{5 s} may be the same as or different from each other.
L ⁷ represents a hexavalent group. T ⁶ represents a single bond or a divalent linking group, and the six T ^{6 s} may be the same as or different from each other.
^The definition of the divalent linking group represented by ^T ^3, T ^4, T ⁵ and ^{T 6} are the same as those defined divalent linking group represented by ^{L 21} as described above.

As the n-valent linking group for L ²¹ , for example, groups represented by the following formulas (E) to (J), or a group obtained by combining these are preferable.

In the above formulas (E) to (J),
R represents a hydrogen atom or a monovalent organic group. As the monovalent organic group, an alkyl group is preferable. * Indicates a binding position. t represents an integer of 2 or more.

L ²¹ may be a group represented by the following formulas (K) to (O), or a group obtained by combining these. In the formula, * represents a bonding position.

In the formula (2), M ²¹ represents a single bond, or —O—, —S—, —N (R ²³ ) —, —C (═O) —O—, —O—C (═O) —O. —, —C (═O) —NH—, —C (═O) —, an alkylene group, or a group in which two or more of these are combined, —C (═O) —O— is preferred. R ²³ represents an alkyl group or an aryl group, and a plurality of M ²¹ may be the same or different.

Among them, as the polyfunctional thiol compound, at least one selected from the group consisting of R ²⁴ and R ^{25 in} the formula (2) in that the curable composition has more excellent development residue suppressing performance. Is preferably other than a hydrogen atom (secondary thiol compound), more preferably both R ²⁴ and R ²⁵ are other than a hydrogen atom (tertiary thiol compound), and R ²⁴ and R ²⁵ are More preferably, they are each independently an alkyl group or —C (═O) —O—R ²³ .
Incidentally, R ^{24 and} are not particularly limited as the number of carbon atoms in the case R ²⁵ each is other than a hydrogen atom, in that the curable composition has a better developing residual渣抑system performance, one or more independently preferably , R ²⁴ and R ²⁵ are more preferably 2 or more. Although it does not restrict | limit especially as an upper limit of carbon number, Generally 5 or less is preferable.
M ²¹ is preferably —C (═O) —O—, and n is preferably an integer of 3 to 10.
In addition, in this specification, the development residue suppression performance intends the physical properties of the curable composition evaluated by the method described in Examples.

Specific examples of the polyfunctional thiol compound are shown below, but the polyfunctional thiol compound contained in the curable composition according to the embodiment of the present invention is not limited thereto. In the table, L ²¹ , M ²¹ , R ²⁴ , R ²⁵ , and n each correspond to each symbol in formula (2). In Tables 2-1 to 2-3, “*” and “●” represent bonding positions, “*” represents the bonding position between L ²¹ and M ²¹ , and “●” represents M ²¹ and −C ( R ²⁴ ) (R ²⁵ ) represents a bonding position with —SH. The numbers (SH-1 to SH-31) of the respective polyfunctional thiol compounds correspond to the numbers of the respective polyfunctional thiol compounds in the examples.

[Colorant]
The curable composition which concerns on embodiment of this invention contains a coloring agent. The content of the colorant in the curable composition is not particularly limited, but is generally preferably 30 to 70% by mass with respect to the total solid content of the curable composition. A coloring agent may be used individually by 1 type, or may use 2 or more types together. When two or more colorants are used in combination, the total content is preferably within the above range.
In addition, when using a cured film as a light shielding film, although it does not restrict | limit especially as content of the coloring agent in a curable composition, 40 masses by the point from which the cured film (light shielding film) which has the more outstanding light-shielding property is obtained. % Or more is preferable.
In addition, although the upper limit of content of a coloring agent is not restrict | limited in particular, Generally 70 mass% or less is preferable with respect to the total solid of a curable composition. When the content of the colorant is not more than the upper limit value, the curable composition has more excellent coatability.
Examples of the colorant include pigments and dyes. Hereinafter, the colorant will be described in detail.

(Pigment)
The pigment is not particularly limited, and a known inorganic pigment and / or organic pigment can be used. The curable composition according to this embodiment preferably contains an inorganic pigment as a colorant. Moreover, it is also preferable that the curable composition which concerns on this embodiment contains an organic pigment as a coloring agent.

-Inorganic pigment It does not restrict | limit especially as said inorganic pigment, A well-known inorganic pigment can be used.
Examples of inorganic pigments include zinc white, lead white, lithopone, titanium oxide, chromium oxide, iron oxide, precipitated barium sulfate and barite powder, red lead, iron oxide red, yellow lead, zinc yellow (one zinc yellow, 2 types of zinc yellow), ultramarine blue, prussian blue (potassium ferrocyanide) zircon gray, praseodymium yellow, chrome titanium yellow, chrome green, peacock, Victoria green, bitumen (unrelated to Prussian blue), vanadium zirconium blue, Examples include chrome tin pink, ceramic red, and salmon pink. The black inorganic pigment includes a metal oxide or metal containing at least one metal element selected from the group consisting of Co, Cr, Cu, Mn, Ru, Fe, Ni, Sn, Ti, and Ag. Nitrogen, metal oxynitride, etc. are mentioned.

As inorganic pigments, carbon black, titanium black, metal pigments and the like (hereinafter referred to as “black”) are obtained in that a curable composition capable of forming a cured film having a high optical density can be obtained even if the content is small. Also referred to as “pigment”). Examples of the metal pigment include a metal oxide containing at least one metal element selected from the group consisting of Nb, V, Co, Cr, Cu, Mn, Ru, Fe, Ni, Sn, Ti, and Ag. And metal nitrogenous substances.
The inorganic pigment is preferably at least one selected from the group consisting of titanium nitride, titanium oxynitride, niobium nitride, vanadium nitride, silver or tin-containing metal pigments, and silver and tin-containing metal pigments. More preferred is at least one selected from the group consisting of titanium nitride, titanium oxynitride, niobium nitride, and vanadium nitride. The niobium nitride and vanadium nitride may be niobium oxynitride and vanadium oxynitride.
Carbon black can also be used as the inorganic pigment. Specific examples of carbon black are commercially available C.I. I. Examples thereof include, but are not limited to, inorganic pigments such as CI Pigment Black 7.

The curable composition may contain a pigment having infrared absorptivity other than the pigment described as a black pigment.
As the pigment having infrared absorptivity, a tungsten compound or a metal boride is preferable, and among them, a tungsten compound is more preferable because it is excellent in light-shielding properties at wavelengths in the infrared region.

Two or more of these pigments may be used in combination, or may be used in combination with a dye described later. In order to adjust the color tone and to improve the light-shielding property in a desired wavelength region, for example, chromatic colors such as red, green, yellow, orange, purple, and blue are added to black pigments or infrared light-shielding pigments. The aspect which mixes the pigment or the dye mentioned later is mentioned. It is preferable to mix a red pigment or a red dye, or a violet pigment or a violet dye with a black pigment or an infrared light shielding pigment, and it is more preferable to mix a red pigment with a black pigment or an infrared light shielding pigment. .
Furthermore, you may add the near-infrared absorber or infrared absorber mentioned later to the said curable composition.

As the black pigment, titanium black or niobium oxynitride is preferable. Titanium black is black particles containing titanium atoms. Preferred are low-order titanium oxide, titanium oxynitride, titanium nitride, and the like. The surface of titanium black can be modified as necessary for the purpose of improving dispersibility and suppressing aggregation. Specifically, titanium black can be coated with silicon oxide, titanium oxide, germanium oxide, aluminum oxide, magnesium oxide, or zirconium oxide. Titanium black can also be treated with a water repellent material as disclosed in JP-A-2007-302836.
Titanium black is typically titanium black particles, and preferably has a small primary particle size and average primary particle size of each particle. The same applies to niobium oxynitride.
Specifically, an average primary particle diameter in the range of 10 nm to 45 nm is preferable.

In addition, the average primary particle diameter of a pigment can be measured using a transmission electron microscope (Transmission Electron Microscope, TEM). As the transmission electron microscope, for example, a transmission microscope HT7700 manufactured by Hitachi High-Technologies Corporation can be used.
In the present specification, the average primary particle diameter of the pigment is the maximum length of a particle image obtained using a transmission electron microscope (Dmax: the maximum length at two points on the contour of the particle image), and the maximum vertical length ( DV-max: When an image is sandwiched between two straight lines parallel to the maximum length, the shortest length connecting the two straight lines vertically is measured, and the geometric mean value (Dmax × DV-max) 1 / 2 was the particle size. The average primary particle diameter of the pigment is determined by measuring the particle diameter of 100 particles by this method and intending the arithmetic average value thereof.

The specific surface area of titanium black and niobium oxynitride is not particularly limited. However, since the water repellency after surface treatment of titanium black and niobium oxynitride with a water repellent becomes a predetermined performance, BET (Brunauer, Emmett, Teller) ) Is preferably 5 to 150 m ² / g, more preferably 20 to 120 m ² / g.
Examples of commercially available titanium black include titanium black 10S, 12S, 13R, 13M, 13M-C, 13R, 13R-N, 13M-T (trade name, manufactured by Mitsubishi Materials Corporation), Tilack D (trade name, manufactured by Ako Kasei Co., Ltd.) and titanium nitride 50 nm (trade name, manufactured by Wako Pure Chemical Industries, Ltd.).

Titanium oxynitride, titanium nitride, or niobium oxynitride is preferably used as the colorant, and titanium nitride or niobium oxynitride is more preferable, and niobium oxynitride is more preferable because the resulting cured film has better moisture resistance. preferable. This is presumably because these colorants are hydrophobic.

Furthermore, it is also preferable to contain titanium black as a dispersion containing titanium black and Si atoms.

In this embodiment, titanium black is contained as a dispersion in the curable composition, and the content ratio (Si / Ti) of Si atoms and Ti atoms in the dispersion is 0.00 on a mass basis. 05 or more is preferable, 0.05 to 0.5 is more preferable, and 0.07 to 0.4 is still more preferable.
Here, the to-be-dispersed bodies include both those in which titanium black is in the state of primary particles and those in the state of aggregates (secondary particles).
In order to change the content ratio (Si / Ti) of the object to be dispersed (for example, 0.05 or more), the following means can be used.
First, a dispersion is obtained by dispersing titanium oxide and silica particles using a disperser, and the dispersion is subjected to reduction treatment at a high temperature (for example, 850 to 1000 ° C.), whereby titanium black particles are mainly formed. A dispersed material containing Si and Ti as components can be obtained. The reduction treatment can also be performed in an atmosphere of a reducing gas such as ammonia.
Examples of titanium oxide include TTO-51N (trade name, manufactured by Ishihara Sangyo).
Examples of commercially available silica particles include AEROSIL (registered trademark) 90, 130, 150, 200, 255, 300, 380 (trade name, manufactured by Evonik).
A dispersing agent may be used for the dispersion of titanium oxide and silica particles. Examples of the dispersant include those described in the section of the dispersant described later.
The dispersion may be performed in a solvent. Examples of the solvent include water and organic solvents. Examples of the organic solvent include those described in the column of organic solvent described later.
Titanium black having an adjusted content ratio (Si / Ti) can be produced, for example, by the method described in paragraphs [0005] and [0016] to [0021] of JP-A-2008-266045.

Curing including this dispersion by adjusting the content ratio (Si / Ti) of Si atoms and Ti atoms in the dispersion including titanium black and Si atoms to a suitable range (for example, 0.05 or more). When a cured film is formed using the curable composition, residues derived from the curable composition outside the region where the cured film is formed are reduced. The residue includes components derived from a curable composition such as titanium black particles and a resin component.
The reason why the residue is reduced is not yet clear, but the above-mentioned dispersed object tends to have a small particle diameter (for example, the particle diameter is 30 nm or less). By increasing the components contained, the adsorptivity of the entire film with the base is reduced. This is presumed to contribute to the improvement of the development removability of an uncured curable composition (particularly titanium black) in the formation of a cured film.
Titanium black is excellent in light-shielding property for light in a wide wavelength range from ultraviolet light to infrared light, and therefore the above-described dispersion to be dispersed containing titanium black and Si atoms (preferably the content ratio (Si / Ti) is A cured film formed using a material having a mass conversion of 0.05 or more exhibits excellent light shielding properties.
The content ratio (Si / Ti) of Si atoms to Ti atoms in the dispersion is, for example, the method (1-1) or the method (1-2) described in paragraph 0033 of JP2013-249417A ).
Whether the content ratio (Si / Ti) of Si atoms and Ti atoms in the dispersion is 0.05 or more with respect to the dispersion to be contained in the cured film obtained by curing the curable composition Can be determined by the method (2) described in paragraph 0035 of JP2013-249417A.

In the dispersion containing titanium black and Si atoms, the above-described titanium black can be used.
In this dispersion, for the purpose of adjusting dispersibility, colorability, etc. together with titanium black, composite oxides such as Cu, Fe, Mn, V, and Ni, cobalt oxide, iron oxide, carbon black, and A black pigment composed of aniline black or the like may be used alone or in combination of two or more. In this case, it is preferable that 50% by mass or more of the total dispersion is occupied by the dispersion made of titanium black.
In this dispersion, other colorants (such as organic pigments and / or dyes) may be used in combination with titanium black, if desired, for the purpose of adjusting the light shielding property and the like, as long as the effects of the present invention are not impaired. Good.
Hereinafter, materials used for introducing Si atoms into the dispersion will be described. When Si atoms are introduced into the dispersion, a Si-containing material such as silica may be used.
Examples of silica that can be used include precipitated silica, fumed silica, colloidal silica, and synthetic silica. These may be appropriately selected and used.
Further, when the particle diameter of the silica particles is smaller than the film thickness when the cured film is formed, the light shielding property is more excellent. Therefore, it is preferable to use fine particle type silica as the silica particles. Examples of the fine particle type silica include silica described in paragraph 0039 of JP2013-249417A, and the contents thereof are incorporated in the present specification.

Further, as the pigment, a tungsten compound and a metal boride can also be used.
Below, a tungsten compound and a metal boride are explained in full detail.
Tungsten compounds and metal borides have high absorption for infrared rays (light having a wavelength of about 800 to 1200 nm) (that is, high light-blocking properties (shielding properties) for infrared rays) and low absorption for visible light. Infrared shielding material. For this reason, a curable composition can form a pattern with high light-shielding property in an infrared region, and high translucency in a visible light region by containing a tungsten compound and / or a metal boride.
Tungsten compounds and metal borides have low absorption even for light having a wavelength shorter than the visible range, which is used for exposure of high pressure mercury lamps, KrF, ArF, and the like used for image formation. For this reason, while combining with the polymeric compound mentioned later and alkali-soluble resin, while being able to obtain the outstanding pattern, a development residue can be suppressed more in pattern formation.

Examples of the tungsten compound include a tungsten oxide compound, a tungsten boride compound, a tungsten sulfide compound, and the like, and a tungsten oxide compound represented by the following formula (composition formula) (I) is preferable.
M _x W _y O _z (I)
M represents a metal, W represents tungsten, and O represents oxygen.
0.001 ≦ x / y ≦ 1.1
2.2 ≦ z / y ≦ 3.0

As the metal of M, for example, alkali metal, alkaline earth metal, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, Tl, Sn, Pb, Ti, Nb, V, Mo, Ta, Re, Be, Hf, Os, Bi, and the like can be given, and an alkali metal is preferable. 1 type or 2 types or more may be sufficient as the metal of M.

M is preferably an alkali metal, more preferably Rb or Cs, and even more preferably Cs.

When x / y is 0.001 or more, infrared rays can be sufficiently shielded, and when it is 1.1 or less, generation of an impurity phase in the tungsten compound can be more reliably avoided. it can.
When z / y is 2.2 or more, chemical stability as a material can be further improved, and when it is 3.0 or less, infrared rays can be sufficiently shielded.

Specific examples of the tungsten oxide compound represented by the above formula (I) include Cs _0.33 WO ₃ , Rb _0.33 WO ₃ , K _0.33 WO ₃ , Ba _0.33 WO _{3 and the} like. Cs _0.33 WO ₃ or Rb _0.33 WO ₃ is preferable, and Cs _0.33 WO ₃ is more preferable.

The tungsten compound is preferably fine particles. The average primary particle diameter of the tungsten fine particles is preferably 800 nm or less, more preferably 400 nm or less, and even more preferably 200 nm or less. When the average primary particle diameter is in such a range, it becomes difficult for the tungsten fine particles to block visible light by light scattering, and thus the translucency in the visible light region can be further ensured. From the viewpoint of avoiding light scattering, the average primary particle size is preferably as small as possible. However, for reasons such as ease of handling during production, the average primary particle size of the tungsten fine particles is usually 1 nm or more.

Two or more tungsten compounds can be used.

Tungsten compounds are commercially available. For example, tungsten oxide compounds can be obtained by a method of heat-treating a tungsten compound in an inert gas atmosphere or a reducing gas atmosphere (see Japanese Patent No. 4096205). ).
The tungsten oxide compound is also available as a dispersion of tungsten fine particles such as YMF-02 manufactured by Sumitomo Metal Mining Co., Ltd.

As the metal boride, lanthanum boride (LaB ₆ ), praseodymium boride (PrB ₆ ), neodymium boride (NdB ₆ ), cerium boride (CeB ₆ ), yttrium boride (YB ₆ ), titanium boride ( TiB ₂ ), zirconium boride (ZrB ₂ ), hafnium boride (HfB ₂ ), vanadium boride (VB ₂ ), tantalum boride (TaB ₂ ), chromium boride (CrB, CrB ₂ ), molybdenum boride ( _{_{_{MoB 2, Mo 2 B 5,}}} MoB), and, one or more, such as tungsten boride _(W 2 _{B 5),} and the like, lanthanum boride (LaB ₆₎ is preferred.

The metal boride is preferably fine particles. The average primary particle diameter of the metal boride fine particles is preferably 800 nm or less, more preferably 300 nm or less, and further preferably 100 nm or less. When the average primary particle diameter is in such a range, the metal boride fine particles are less likely to block visible light by light scattering, and thus the translucency in the visible light region can be further ensured. From the viewpoint of avoiding light scattering, the average primary particle size is preferably as small as possible. However, for reasons such as ease of handling during production, the average primary particle size of the metal boride fine particles is usually 1 nm or more.

Two or more metal borides can be used.

The metal boride is available as a commercial product, for example, as a dispersion of metal boride fine particles such as KHF-7 manufactured by Sumitomo Metal Mining Co., Ltd.

.. Titanium nitride-containing particles As the inorganic pigment, titanium nitride-containing particles containing Fe atoms can also be used. For production of titanium nitride-containing particles, a gas phase reaction method is usually used, and specific examples include an electric furnace method and a thermal plasma method. Among these production methods, the thermal plasma method is preferable because it is less contaminated with impurities, easily has a uniform particle diameter, and has high productivity.
Examples of the method for generating thermal plasma include direct current arc discharge, multiphase arc discharge, radio frequency (RF) plasma, hybrid plasma, and the like, and high frequency plasma with less impurities from the electrodes is preferable. As a specific method for producing titanium nitride-containing particles by the thermal plasma method, for example, titanium powder is evaporated by high-frequency thermal plasma, nitrogen is introduced into the apparatus as a carrier gas, and titanium powder is nitrided in the cooling process. And a method of synthesizing titanium nitride-containing particles. The thermal plasma method is not limited to the above.

The method for producing titanium nitride-containing particles is not particularly limited, but the production methods described in paragraphs <0037> to <0089> of International Publication No. 2010/147098 can be referred to. For example, instead of the Ag powder of International Publication No. 2010/147098, using a component containing Fe and / or a component containing Si, which will be described later, and a mixture of this and a titanium powder material (titanium particles) as a raw material The titanium nitride-containing particles contained in the curable composition can be produced.

The titanium powder material (titanium particles) used for the production of titanium nitride-containing particles is preferably of high purity. The titanium powder material is not particularly limited, but the titanium element preferably has a purity of 99.99% or more, more preferably 99.999% or more.

The titanium powder material (titanium particles) used for the production of titanium nitride-containing particles may contain atoms other than titanium atoms. Examples of other atoms that can be contained in the titanium powder material include Fe atoms and Si atoms.
When the titanium powder material contains Fe atoms, the content of Fe atoms is preferably more than 0.001% by mass with respect to the total mass of the titanium powder material.
When the titanium powder material contains Si atoms, the content of Si atoms is preferably more than 0.002% by mass and less than 0.3% by mass with respect to the total mass of the titanium powder material. The content is more preferably from 0.15% by mass, and even more preferably from 0.02 to 0.1% by mass. When the content of Si atoms is more than 0.002% by mass, the patterning property of the cured film is further improved. When the content of Si atoms is less than 0.3% by mass, the polarity of the outermost layer of the obtained titanium nitride-containing particles is further stabilized. Thereby, when disperse | distributing a titanium nitride containing particle, the adsorptivity of a dispersing agent to a titanium nitride containing particle improves, and the non-dispersed material of a titanium nitride containing particle reduces.
The water content in the titanium powder material (titanium particles) used for the production of titanium nitride-containing particles is preferably less than 1% by mass and less than 0.1% by mass with respect to the total mass of the titanium powder material. It is more preferable that it is not substantially contained.

The titanium nitride-containing particles are obtained by using a thermal plasma method, whereby a diffraction angle 2θ of a peak derived from the (200) plane when CuKα rays are used as an X-ray source (details will be described later) is 42.6. It becomes easy to adjust to a range of more than 4 ° to 43.5 °.

The method for causing the titanium nitride-containing particles to contain Fe atoms is not particularly limited. For example, in the stage of obtaining titanium particles (titanium powder) used as a raw material for the above-described titanium nitride-containing particles, Fe atoms are introduced. The method etc. are mentioned. More specifically, when titanium is produced by the crawl method or the like, a reaction vessel made of a material containing Fe atoms such as stainless steel is used, or a press machine and a crusher for crushing titanium are used. By using a material containing Fe atoms as a material, Fe atoms can be attached to the surface of the titanium particles.
When the thermal plasma method is used in the production of titanium nitride-containing particles, components such as Fe particles and Fe oxide are added to the raw material titanium particles, and these are nitrided by the thermal plasma method. The titanium nitride-containing particles can contain Fe atoms.
Fe atoms contained in titanium nitride-containing particles are ions, metal compounds (including complex compounds), intermetallic compounds, alloys, oxides, composite oxides, nitrides, oxynitrides, sulfides, and oxysulfides. And may be included in any form. The Fe atom contained in the titanium nitride-containing particle may exist as an impurity at a position between crystal lattices, or may exist as an impurity in an amorphous state at a crystal grain boundary.

The content of Fe atoms in the titanium nitride-containing particles is preferably more than 0.001% by mass and less than 0.4% by mass with respect to the total mass of the titanium nitride-containing particles. Of these, 0.01 to 0.2% by mass is more preferable, and 0.02 to 0.1% by mass is even more preferable. The content of Fe atoms in the titanium nitride-containing particles can be measured by ICP (Inductively Coupled Plasma) emission spectroscopy.

The titanium nitride-containing particles preferably further contain Si atoms (silicon atoms). Thereby, the patterning property of a cured film improves more. The reason why the patterning property is improved by containing Si atoms is considered to be the same as the above-described Fe atoms.
The content of Si atoms in the titanium nitride-containing particles is preferably more than 0.002% by mass and less than 0.3% by mass with respect to the total mass of the titanium nitride-containing particles, and 0.01 to 0.15 The mass is more preferably 0.02 to 0.1% by mass. The content of Si atoms in the titanium nitride-containing particles can be measured by the same method as that for Fe atoms.

The method for incorporating Si atoms into the titanium nitride-containing particles is not particularly limited. For example, Si atoms are introduced at the stage of obtaining titanium particles (titanium powder) used as a raw material for the above-described titanium nitride-containing particles. The method etc. are mentioned. More specifically, when titanium is produced by a crawl method or the like, a reaction vessel made of a material containing Si atoms is used, or Si atom is used as a material for a press machine and a crusher when crushing titanium. Si atoms can be attached to the surface of the titanium particles.
When the thermal plasma method is used in the production of titanium nitride-containing particles, components such as Si particles and Si oxide are added in addition to the titanium particles as raw materials, and these are nitrided by the thermal plasma method. The titanium nitride-containing particles can contain Si atoms.
Si atoms contained in titanium nitride-containing particles are ions, metal compounds (including complex compounds), intermetallic compounds, alloys, oxides, complex oxides, nitrides, oxynitrides, sulfides, and oxysulfides. And may be included in any form. Si atoms contained in the titanium nitride-containing particles may be present as impurities at the position between the crystal lattices, or may be present as impurities in the amorphous state at the crystal grain boundaries.

The content of titanium atoms (Ti atoms) in the titanium nitride-containing particles is preferably 10 to 85% by mass and preferably 15 to 75% by mass with respect to the total mass of the titanium nitride-containing particles. More preferred is 20 to 70% by mass. The content of Ti atoms in the titanium nitride-containing particles can be measured by ICP emission spectroscopy.
The content of nitrogen atoms (N atoms) in the titanium nitride-containing particles is preferably 3 to 60% by mass and preferably 5 to 50% by mass with respect to the total mass of the titanium nitride-containing particles. More preferably, it is 10 to 40% by mass. The nitrogen atom content can be analyzed by an inert gas melting-thermal conductivity method.
Titanium nitride-containing particles contain titanium nitride (TiN) as a main component, and usually become noticeable when oxygen is mixed during the synthesis and when the particle diameter is small. A part of oxygen atoms may be contained.
The content of oxygen atoms in the titanium nitride-containing particles is preferably 1 to 40% by mass, more preferably 1 to 35% by mass with respect to the total mass of the titanium nitride-containing particles. More preferably, it is ˜30% by mass. The oxygen atom content can be analyzed by an inert gas melting-infrared absorption method.

From the viewpoint of dispersion stability and light-shielding property, the specific surface area of the titanium nitride-containing particles is preferably 5 ~ 100m ² / g, more preferably 10 ~ ^60m 2 / g. The specific surface area can be determined by the BET (Brunauer, Emmett, Teller) method.

The titanium nitride-containing particles may be composite fine particles composed of titanium nitride particles and metal fine particles.
Composite fine particles refer to particles in which titanium nitride particles and metal fine particles are complexed or in a highly dispersed state. Here, “composite” means that the particles are constituted by both components of titanium nitride and metal, and “highly dispersed state” means titanium nitride particles and metal particles. Means that the small amount of particles are uniformly and uniformly dispersed without aggregation.
The metal fine particles are not particularly limited. For example, copper, silver, gold, platinum, palladium, nickel, tin, cobalt, rhodium, iridium, ruthenium, osmium, manganese, molybdenum, tungsten, niobium, tantalum, calcium, titanium, bismuth. , Antimony and lead, and alloys thereof. Among these, at least one selected from copper, silver, gold, platinum, palladium, nickel, tin, cobalt, rhodium and iridium, and alloys thereof is preferable, and copper, silver, gold, platinum and tin, and these It is more preferable that it is at least one selected from these alloys. From the viewpoint of better moisture resistance, silver is preferred.
The content of the metal fine particles in the titanium nitride-containing particles is preferably 5 to 50% by mass, and more preferably 10 to 30% by mass with respect to the total mass of the titanium nitride-containing particles.

The titanium nitride-containing particles preferably have a diffraction angle 2θ of a peak derived from the (200) plane when CuKα rays are used as an X-ray source and more than 42.6 ° and 43.5 ° or less. A cured film (for example, a black matrix) obtained by using a curable composition containing titanium nitride-containing particles having such characteristics can achieve a high OD (optical density) value.

When an X-ray diffraction spectrum of a titanium compound is measured using CuKα rays as an X-ray source, TiN has a peak derived from the (200) plane as the strongest peak, and TiO has (200 ) A peak derived from the surface is seen in the vicinity of 2θ = 43.4 °. On the other hand, although not the strongest peak, the peak derived from the (200) plane of anatase TiO ₂ is in the vicinity of 2θ = 48.1 °, and the peak derived from the (200) plane of rutile TiO ₂ is 2θ = 39. Observed around 2 °. Therefore, the peak position shifts to the higher angle side with respect to 42.5 ° as the crystal state contains more oxygen atoms.

The diffraction angle 2θ of the peak derived from the (200) plane of the titanium nitride-containing particle is preferably more than 42.6 ° and less than 43.5 ° from the viewpoint of the stability of the particle over time. From the viewpoint of excellent process margin, 42.7 ° or more and less than 43.5 ° is more preferable, and from the viewpoint of excellent reproducibility of particle performance, it is more preferably 42.7 ° or more and less than 43.4 °. When titanium oxide TiO ₂ is contained as an accessory component, the peak derived from anatase TiO ₂ (101) as the strongest peak is in the vicinity of 2θ = 25.3 °, and the peak derived from rutile TiO ₂ (110). Is seen around 2θ = 27.4 °. However, since TiO ₂ is white and causes a reduction in the light shielding properties of the black matrix, it is preferably reduced to such an extent that it is not observed as a peak.

The crystallite size constituting the titanium nitride-containing particles can be determined from the half width of the X-ray diffraction peak, and is calculated using Scherrer's formula.

The crystallite size is preferably 20 nm or more, and more preferably 20 to 50 nm. By forming a black matrix using titanium nitride-containing particles having a crystallite size of 20 nm or more, the transmitted light of the cured film exhibits a blue to blue purple color having a peak wavelength of 475 nm or less, and has high light-shielding properties. A black matrix having both ultraviolet sensitivity can be obtained. When the crystallite size is 20 nm or more, the proportion of the active particle surface with respect to the volume of the particle is reduced, providing a good balance, and the titanium nitride-containing particles have better heat resistance and / or durability. It becomes.

..Metal nitride-containing particles containing atom A Further, as the inorganic pigment, metal nitride-containing particles that are metal nitride-containing particles and contain a predetermined atom A can also be used.
Examples of the metal in the metal nitride-containing particles include Nb, V, Cr, Y, Zr, Nb, Hf, Ta, W, and Re, and the effect of the present invention in which the curable composition is more excellent. Nb or V is more preferable in that
Examples of the atom A include B, Al, Si, Mn, Fe, Ni, and Ag.
When the metal nitride-containing particles contain the atom A, the content is not particularly limited, but the content of the atoms A in the metal nitride-containing particles is preferably 0.00005 to 10% by mass.

The method for producing the metal nitride-containing particles containing the atom A is not particularly limited, and a known method can be used.
For the production of metal nitride-containing particles, a gas phase reaction method is usually used, and specific examples include an electric furnace method and a thermal plasma method. Among these production methods, the thermal plasma method is preferable because it is less contaminated with impurities, has a uniform particle diameter, and has high productivity.
As a specific method for producing metal nitride-containing particles by the thermal plasma method, for example, a method using a metal fine particle production apparatus (an apparatus similar to a “black composite fine particle production apparatus” described later) can be mentioned. The metal fine particle manufacturing apparatus includes, for example, a plasma torch that generates thermal plasma, a material supply device that supplies metal raw material powder into the plasma torch, a chamber that includes a cooling function, a cyclone that classifies the generated metal fine particles, and metal fine particles It is comprised by the collection | recovery part which collect | recovers.
In the present specification, the metal fine particles mean particles having a primary particle diameter of 20 nm to 40 μm containing a metal element.

Organic pigment Examples of the organic pigment include, for example, 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, 16 7,168,169,170,171,172,173,174,175,176,177,179,180,181,182,185,187,188,193,194,199,213,214, etc.
C. I. Pigment Orange 2, 5, 13, 16, 17: 1, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 71, 73, etc. ,
C. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48: 1, 48: 2, 48: 3, 48: 4 49, 49: 1, 49: 2, 52: 1, 52: 2, 53: 1, 57: 1, 60: 1, 63: 1, 66, 67, 81: 1, 81: 2, 81: 3 83, 88, 90, 105, 112, 119, 122, 123, 144, 146, 149, 150, 155, 166, 168, 169, 170, 171, 172, 175, 176, 177, 178, 179, 184 185, 187, 188, 190, 200, 202, 206, 207, 208, 209, 210, 216, 220, 224, 226, 242, 246, 254, 255, 264, 270, 272, 279, etc.
C. I. Pigment Green 7, 10, 36, 37, 58, 59, etc.
C. I. Pigment violet 1, 19, 23, 27, 32, 37, 42, and the like; I. Pigment Blue 1, 2, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, 66, 79, 80, etc.
Is mentioned. In addition, a pigment may be used individually by 1 type, or may use 2 or more types together.

(dye)
Examples of the dye include, for example, JP-A No. 64-90403, JP-A No. 64-91102, JP-A No. 1-94301, JP-A No. 6-11614, No. 2592207, and US Pat. No. 4,808,501. No. 5,667,920, U.S. Pat. No. 505950, JP-A-5-333207, JP-A-6-35183, JP-A-6-51115, JP-A-6-194828, etc. Can be used. When classified as chemical structures, pyrazole azo compounds, pyromethene compounds, anilinoazo compounds, triphenylmethane compounds, anthraquinone compounds, benzylidene compounds, oxonol compounds, pyrazolotriazole azo compounds, pyridone azo compounds, cyanine compounds, phenothiazine compounds, and pyrrolopyrazole azomethines Compounds and the like. A dye multimer may be used as the dye. Examples of the dye multimer include compounds described in JP2011-213925A and JP2013-041097A. A polymerizable dye having polymerizability in the molecule may be used, and examples of commercially available products include RDW series manufactured by Wako Pure Chemical Industries, Ltd.

(Infrared absorber)
The colorant may further contain an infrared absorber.
The infrared absorber means a compound having absorption in the wavelength region in the infrared region (preferably, a wavelength of 650 to 1300 nm). The infrared absorber is preferably a compound having a maximum absorption wavelength in a wavelength region of 675 to 900 nm.
Examples of colorants having such spectral characteristics include pyrrolopyrrole compounds, copper compounds, cyanine compounds, phthalocyanine compounds, iminium compounds, thiol complex compounds, transition metal oxide compounds, squarylium compounds, naphthalocyanine compounds, quaterylenes. Examples include compounds, dithiol metal complex compounds, and croconium compounds.
As the phthalocyanine compound, naphthalocyanine compound, iminium compound, cyanine compound, squarylium compound, and croconium compound, the compounds disclosed in paragraphs 0010 to 0081 of JP 2010-1111750 A may be used. Incorporated. As the cyanine compound, for example, “functional pigment, Shin Okawara / Ken Matsuoka / Keijiro Kitao / Kensuke Hirashima, written by Kodansha Scientific”, the contents of which are incorporated herein.

As the colorant having the above-mentioned spectral characteristics, compounds disclosed in paragraphs 0004 to 0016 of JP-A-07-164729 and / or compounds disclosed in paragraphs 0027 to 0062 of JP-A-2002-146254, JP-A-2011-16483 It is also possible to use near-infrared absorbing particles comprising a crystallite of an oxide containing Cu and / or P disclosed in paragraphs 0034 to 0067 of the publication and having a number average aggregate particle diameter of 5 to 200 nm.

The compound having a maximum absorption wavelength in the wavelength region of 675 to 900 nm is preferably at least one selected from the group consisting of a cyanine compound, a pyrrolopyrrole compound, a squarylium compound, a phthalocyanine compound, and a naphthalocyanine compound.
The infrared absorber is preferably a compound that dissolves 1% by mass or more in 25 ° C. water, and more preferably a compound that dissolves 10% by mass or more in 25 ° C. water. By using such a compound, the solvent resistance is improved.
The pyrrolopyrrole compound can be referred to paragraphs 0049 to 0062 of JP 2010-222557 A, the contents of which are incorporated herein. The cyanine compounds and squarylium compounds are disclosed in paragraphs 0022 to 0063 of International Publication No. 2014/088063, paragraphs 0053 to 0118 of International Publication No. 2014/030628, paragraphs 0028 to 0074 of JP 2014-59550 A, and International Publication No. 2012/0074. 169447, paragraphs 0013 to 0091, JP2015-176046, paragraphs 0019 to 0033, JP2014-63144, paragraphs 0053 to 00099, JP201452431, paragraphs 0085 to 0150, JP Paragraphs 0076 to 0124 of Japanese Patent Application Laid-Open No. 2014-44301, Paragraphs 0045 to 0078 of Japanese Patent Application Laid-Open No. 2012-8532, Paragraphs 0027 to 0067 of Japanese Patent Application Laid-Open No. 2015-172102, and Paragraph 002 of Japanese Patent Application Laid-Open No. 2015-172004. To 0067, paragraphs 0029 to 0085 of JP-A-2015-40895, paragraphs 0022 to 0036 of JP-A-2014-126642, paragraphs 0011 to 0017 of JP-A-2014-148567, and JP-A-2015-157893. Paragraphs 0010 to 0025, paragraphs 0013 to 0026 of JP 2014-095007 A, paragraphs 0013 to 0047 of JP 2014-80487 A, paragraphs 0007 to 0028 of JP 2013-227403 A, and the like can be referred to. The contents are incorporated herein.

The infrared absorber is preferably at least one selected from the group consisting of compounds represented by the following formulas 1 to 3.
Formula 1

In Formula 1, A ¹ and A ² each independently represent an aryl group, a heteroaryl group, or a group represented by Formula 1-A below.
Formula 1-A

In Formula 1-A, Z ^1A represents a nonmetallic atomic group that forms a nitrogen-containing heterocyclic ring, R ^2A represents an alkyl group, an alkenyl group, or an aralkyl group, d represents 0 or 1, A wavy line represents a connecting hand.
Formula 2

In Formula 2, R ^1a and R ^1b each independently represent an alkyl group, an aryl group, or a heteroaryl group,
R ² to R ⁵ each independently represents a hydrogen atom or a substituent, and R ² and R ³ , R ⁴ and R ⁵ may be bonded to each other to form a ring,
R ⁶ and R ⁷ each independently represents a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group, —BR ^A R ^B , or a metal atom, and R ^A and R ^B each independently represent a hydrogen atom Represents an atom or substituent,
R ⁶ may be covalently or coordinated with R ^1a or R ^3, and R ⁷ may be covalently or coordinated with R ^1b or R ⁵ .
Formula 3

In Formula 3, Z ¹ and Z ² are each independently a nonmetallic atomic group that forms a 5-membered or 6-membered nitrogen-containing heterocyclic ring that may be condensed,
R ¹⁰¹ and R ¹⁰² each independently represents an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group, or an aryl group,
L ¹ represents a methine chain composed of an odd number of methines;
a and b are each independently 0 or 1,
When a is 0, a carbon atom and a nitrogen atom are bonded by a double bond, and when b is 0, a carbon atom and a nitrogen atom are bonded by a single bond,
When the site represented by Cy in the formula is a cation moiety, X ¹ represents an anion, c represents the number necessary for balancing the charge, and the site represented by Cy in the formula is an anion moiety. X ¹ represents a cation, c represents a number necessary to balance the charge, and when the charge at the site represented by Cy in the formula is neutralized in the molecule, c is 0.

(Pigment derivative)
The curable composition may contain a pigment derivative. The pigment derivative is preferably a compound having a structure in which a part of an organic pigment is substituted with an acidic group, a basic group or a phthalimidomethyl group. As the pigment derivative, from the viewpoint of dispersibility and dispersion stability of the colorant A, a pigment derivative having an acidic group or a basic group is preferable. Particularly preferred are pigment derivatives having a basic group. The combination of the resin (dispersant) and the pigment derivative described above is preferably a combination in which the dispersant is an acidic dispersant and the pigment derivative has a basic group.

Examples of the organic pigment for constituting the pigment derivative include diketopyrrolopyrrole pigments, azo pigments, phthalocyanine pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, perinone pigments, perylene pigments, thioindigo pigments , Isoindoline pigments, isoindolinone pigments, quinophthalone pigments, selenium pigments, metal complex pigments, and the like.
The acidic group possessed by the pigment derivative is preferably a sulfonic acid group or a salt thereof, or a carboxylic acid group or a salt thereof, more preferably a carboxylic acid group or a sulfonic acid group, and still more preferably a sulfonic acid group. As a basic group which a pigment derivative has, an amino group is preferable and a tertiary amino group is more preferable.

When the curable composition contains a pigment derivative, the content of the pigment derivative is preferably 1 to 30% by mass and more preferably 3 to 20% by mass with respect to the mass of the pigment. Only one pigment derivative may be used, or two or more pigment derivatives may be used in combination.

(Polymerizable compound)
The curable composition contains a polymerizable compound. In the present specification, the polymerizable compound means a compound containing a polymerizable group and a component different from the resin (dispersant and binder resin).

The content of the polymerizable compound in the curable composition is not particularly limited, but is generally preferably 5 to 30% by mass with respect to the total solid content of the curable composition. A polymeric compound may be used individually by 1 type, or may use 2 or more types together. When using 2 or more types of polymeric compounds together, it is preferable that total content is in the said range.

The polymerizable compound is preferably a compound containing at least one group containing an ethylenically unsaturated bond, more preferably a compound containing 2 or more, further preferably containing 3 or more, and containing 5 or more. Is particularly preferred. The upper limit is 15 or less, for example. Examples of the group containing an ethylenically unsaturated bond include a vinyl group, a (meth) allyl group, and a (meth) acryloyl group.

As the polymerizable compound, for example, compounds described in paragraph 0050 of JP2008-260927A and paragraph 0040 of JP2015-68893A can be used. Incorporated into.

As a polymeric compound, any of chemical forms, such as a monomer, a prepolymer, an oligomer, these mixtures, these multimers, etc., may be sufficient, for example.
The polymerizable compound is preferably a 3 to 15 functional (meth) acrylate compound, more preferably a 3 to 6 functional (meth) acrylate compound.

As the polymerizable compound, a compound having at least one group containing an ethylenically unsaturated bond and having a boiling point of 100 ° C. or higher under normal pressure is preferable. For example, compounds described in paragraph 0227 of JP2013-29760A and paragraphs 0254 to 0257 of JP2008-292970A can be used, the contents of which are incorporated herein.

Examples of the polymerizable compound include dipentaerythritol triacrylate (commercially available product KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (commercially available product KAYARAD D-320; manufactured by Nippon Kayaku Co., Ltd.). ), Dipentaerythritol penta (meth) acrylate (commercially available KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (meth) acrylate (commercially available KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., A -DPH-12E (manufactured by Shin-Nakamura Chemical Co., Ltd.), and structures in which these (meth) acryloyl groups are mediated by ethylene glycol or propylene glycol residues (for example, commercially available from Sartomer, SR454, SR499) Is preferred. These oligomer types can also be used. Moreover, NK ester A-TMMT (pentaerythritol tetraacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.), KAYARAD RP-1040 (manufactured by Nippon Kayaku Co., Ltd.), and the like can also be used.

The polymerizable compound may contain an acid group such as a carboxylic acid group, a sulfonic acid group, or a phosphoric acid group. As the polymerizable compound containing an acid group, an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid is preferable, and a non-aromatic carboxylic acid anhydride is reacted with an unreacted hydroxyl group of the aliphatic polyhydroxy compound. A polymerizable compound containing a group is more preferable, and in this ester, a compound in which the aliphatic polyhydroxy compound is pentaerythritol and / or dipentaerythritol is further preferable.
Examples of commercially available polymerizable compounds include Aronix TO-2349, M-305, M-510, and M-520 manufactured by Toa Gosei Co., Ltd.

The acid value of the polymerizable compound containing an acid group is preferably from 0.1 to 40 mgKOH / g, more preferably from 5 to 30 mgKOH / g. When the acid value of the polymerizable compound is 0.1 mgKOH / g or more, the curable composition has more excellent developability (characteristic that is easily dissolved in an alkali developer), and is 40 mgKOH / g or less. It is advantageous in the production and / or handling of the polymerizable compound and has a better photopolymerizability. As a result, the curable composition has better curability.

As the polymerizable compound, a compound containing a caprolactone structure is preferable.
The compound containing a caprolactone structure is not particularly limited as long as it is a compound containing a caprolactone structure in the molecule, and a known compound can be used.
Examples of the compound containing a caprolactone structure include trimethylolethane, ditrimethylolethane, trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, tripentaerythritol, glycerin, diglycerol, and trimethylolmelamine. Examples thereof include ε-caprolactone-modified polyfunctional (meth) acrylate obtained by esterifying a polyhydric alcohol, (meth) acrylic acid and ε-caprolactone. Of these, compounds containing a caprolactone structure represented by the following formula (Z-1) are preferred.

In the formula (Z-1), all six R are groups represented by the following formula (Z-2), or 1 to 5 of the six R are represented by the following formula (Z-2) And the remainder is a group represented by the following formula (Z-3).

In formula (Z-2), R ¹ represents a hydrogen atom or a methyl group, m is 1 or 2, and “*” represents a bonding position.

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

Polymerizable compounds containing a caprolactone structure are commercially available, for example, from Nippon Kayaku as the KAYARAD DPCA series. -2) is a compound in which the number of groups represented by 2 and R ¹ are all hydrogen atoms), DPCA-30 (wherein m is 1, and the number of groups represented by formula (Z-2) is 3, compound in which R ¹ is all hydrogen atoms), DPCA-60 (in the formula, m is 1, the number of groups represented by formula (Z-2) is 6, and R ¹ is all hydrogen atoms) And DPCA-120 (a compound in which m is 2, the number of groups represented by formula (Z-2) is 6, and all R ¹ are hydrogen atoms).

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

In formulas (Z-4) and (Z-5), each E independently represents — ((CH ₂ ) _y CH ₂ O) — or ((CH ₂ ) _y CH (CH ₃ ) O) —. Represents. y independently represents an integer of 0 to 10. X represents a (meth) acryloyl group, a hydrogen atom, or a carboxylic acid group each independently.
In formula (Z-4), the total number of (meth) acryloyl groups is 3 or 4, each m independently represents an integer of 0 to 10, and the total of each m is an integer of 0 to 40.
In formula (Z-5), the total number of (meth) acryloyl groups is 5 or 6, each n independently represents an integer of 0 to 10, and the total of each n is an integer of 0 to 60.

In the formula (Z-4), m is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4.
The total of each m is preferably an integer of 2 to 40, more preferably an integer of 2 to 16, and still more preferably an integer of 4 to 8.
In the formula (Z-5), n is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4.
The total of each n is preferably an integer of 3 to 60, more preferably an integer of 3 to 24, and still more preferably an integer of 6 to 12.
In formula (Z-4) or formula (Z-5), — ((CH ₂ ) _y CH ₂ O) — or ((CH ₂ ) _y CH (CH ₃ ) O) — A form in which the terminal is bonded to X is preferred.

The compounds represented by formula (Z-4) or formula (Z-5) may be used alone or in combination of two or more. In particular, in formula (Z-5), all six Xs are acryloyl groups, in formula (Z-5), all six Xs are acryloyl groups, and among six Xs, It is preferable to use in combination with a compound having at least one hydrogen atom. The curable composition containing the above compound has more excellent developability.

The total content of the compound represented by formula (Z-4) or formula (Z-5) in the polymerizable compound is preferably 20% by mass or more, and more preferably 50% by mass or more.
Of the compounds represented by the formula (Z-4) or the formula (Z-5), a pentaerythritol derivative and / or a dipentaerythritol derivative are more preferable.

The polymerizable compound may contain a cardo skeleton.
As the polymerizable compound containing a cardo skeleton, a polymerizable compound containing a 9,9-bisarylfluorene skeleton is preferable.
Although it does not restrict | limit especially as a polymeric compound containing a cardo frame | skeleton, For example, oncoat EX series (made by Nagase Sangyo Co., Ltd.), Og sole (made by Osaka Gas Chemical Co., Ltd.), etc. are mentioned.

[Optional ingredients]
The curable composition may contain other components as long as the effects of the present invention are achieved. Examples of other components include a resin, a polymerization inhibitor, a solvent, a surfactant, an ultraviolet absorber, and a silane coupling agent. Below, the arbitrary component contained in a curable composition is explained in full detail.

<Other polymerization initiators>
The curable composition may contain a polymerization initiator other than the specific oxime compound. Examples of the polymerization initiator other than the specific oxime compound include a thermal polymerization initiator and a photopolymerization initiator. The content of the other polymerization initiator in the curable composition is not particularly limited, but is generally preferably 0.1 to 5% by mass with respect to the total solid content of the curable composition. Other polymerization initiators may be used alone or in combination of two or more. When two or more kinds of other polymerization initiators are used in combination, the total content is preferably within the above range.

Examples of the thermal polymerization initiator include 2,2′-azobisisobutyronitrile (AIBN), 3-carboxypropionitrile, azobismaleonitrile, and dimethyl- (2,2 ′)-azobis (2 -Methylpropionate) [V-601] and the like, and organic peroxides such as benzoyl peroxide, lauroyl peroxide, and potassium persulfate.
Examples of the thermal polymerization initiator include compounds described on pages 65 to 148 of “Ultraviolet Curing System” written by Kiyoto Kato (published by General Technology Center Co., Ltd .: 1989).

Examples of the photopolymerization initiator include halogenated hydrocarbon derivatives (for example, those containing a triazine skeleton and those containing an oxadiazole skeleton), acylphosphine compounds such as acylphosphine oxide, and hexaarylbiimidazoles. Oxime compounds such as oxime derivatives (excluding specific oxime compounds), organic peroxides, thio compounds, ketone compounds, aromatic onium salts, aminoacetophenone compounds, and hydroxyacetophenones.
As the photopolymerization initiator, for example, paragraphs 0265 to 0268 of JP2013-29760A can be referred to, and the contents thereof are incorporated herein.

More specifically, as the photopolymerization initiator, for example, an aminoacetophenone initiator described in JP-A-10-291969 or an acylphosphine initiator described in Japanese Patent No. 4225898 can be used. The above content is incorporated herein.
As the hydroxyacetophenone compound, for example, IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, or IRGACURE-127 (trade name: all manufactured by BASF) can be used, but not limited thereto. .
As the aminoacetophenone compound, for example, commercially available products IRGACURE-907, IRGACURE-369, or IRGACURE-379EG (trade names: all manufactured by BASF) can be used, but are not limited thereto. As the aminoacetophenone compound, a compound described in JP-A-2009-191179 whose absorption wavelength is matched with a long wave light source of 365 nm or 405 nm can also be used, and the above contents are incorporated in the present specification.
As the acylphosphine compound, IRGACURE-819, IRGACURE-TPO (trade name: all manufactured by BASF) or the like can be used.

<Resin>
The curable composition preferably contains a resin. Examples of the resin include a dispersant and a binder resin.
The content of the resin in the curable composition is not particularly limited, but is generally preferably 5 to 40% by mass with respect to the total solid content of the curable composition. Resin may be used individually by 1 type, or may use 2 or more types together. When using 2 or more types of resin together, it is preferable that total content is in the said range.

(Dispersant)
The curable composition preferably contains a dispersant (corresponding to a resin). In addition, in this specification, a dispersing agent intends the compound different from the alkali-soluble resin mentioned later.
The content of the dispersant in the curable composition is not particularly limited, but is generally preferably 5 to 40% by mass with respect to the total solid content of the curable composition.
A dispersing agent may be used individually by 1 type, or may use 2 or more types together. When two or more dispersants are used in combination, the total content is preferably within the above range.

The dispersant is not particularly limited, and a known dispersant can be used.
Examples of the dispersant include a polymer dispersant. Examples of the polymer dispersant include polyamidoamine and its salt, polycarboxylic acid and its salt, high molecular weight unsaturated acid ester, modified polyurethane, modified polyester, modified poly (meth) acrylate, and (meth) acrylic copolymer. And naphthalenesulfonic acid formalin condensate.
Moreover, as a dispersing agent, polyoxyethylene alkyl phosphate ester, polyoxyethylene alkylamine, a pigment derivative, etc. can be used.
Among these, as the dispersant, a polymer compound is preferable. The polymer compounds can be further classified into linear polymers, terminal-modified polymers, graft polymers, and block polymers based on their structures.

-High molecular compound A high molecular compound adsorb | sucks to the surface of a coloring agent (henceforth "pigment"), and acts so that the re-aggregation of a to-be-dispersed body may be prevented. Therefore, a terminal-modified polymer, a graft-type (containing a polymer chain) polymer, and a block-type polymer that contain an anchor site to the pigment surface are preferable.

The polymer compound may contain a curable group.
Examples of the curable group include an ethylenically unsaturated group (for example, (meth) acryloyl group, vinyl group, and styryl group), and a cyclic ether group (for example, epoxy group, oxetanyl group, etc.) However, it is not limited to these.
Among these, an ethylenically unsaturated group is preferable as the curable group in that polymerization can be controlled by radical reaction. As the ethylenically unsaturated group, a (meth) acryloyl group is more preferable.

The resin containing a curable group preferably contains at least one selected from the group consisting of a polyester structure and a polyether structure. In this case, the main chain may contain a polyester structure and / or a polyether structure, and, as will be described later, when the resin contains a structural unit containing a graft chain, the graft chain May contain a polyester structure and / or a polyether structure.
As said resin, it is more preferable that the said graft chain contains a polyester structure.

The polymer compound preferably contains a structural unit containing a graft chain. In the present specification, “structural unit” is synonymous with “repeating unit”.
A polymer compound containing a structural unit containing such a graft chain has a better affinity with a solvent. A polymer compound containing a structural unit containing a graft chain has better affinity with a solvent, so that it is easier to disperse pigments and the like even if time passes after the pigments are dispersed The initial dispersion state is less likely to change (has better aging stability). Moreover, since the high molecular compound containing the structural unit containing a graft chain contains a graft chain, it has a better affinity with a polymerizable compound and / or other components described later. As a result, a polymer compound containing a structural unit containing a graft chain is less likely to produce a residue due to an unreacted polymerizable compound or the like during alkali development described later.
When the graft chain is long (the formula amount is large), the steric repulsion effect is enhanced, and the dispersibility of the pigment and the like is improved. On the other hand, if the graft chain is too long, the adsorptive power to the pigment or the like is lowered, and the dispersibility of the pigment or the like tends to be lowered. Therefore, the number of atoms in the graft chain (excluding hydrogen atoms) is preferably 40 to 10,000, more preferably 50 to 2000, and still more preferably 60 to 500.
Here, the graft chain is intended from the root of the main chain of the polymer compound (the atom bonded to the main chain in a group branched from the main chain) to the end of the group branched from the main chain.

The graft chain is preferably a polymer chain containing a polymer structure. The polymer structure contained in the polymer chain is not particularly limited, and examples thereof include a poly (meth) acrylate structure (for example, poly (meth) acrylic structure), a polyester structure, a polyurethane structure, a polyurea structure, a polyamide structure, and a poly structure. Examples include ether structures.
The polymer chain has a polyester film structure, a polyether structure, and a poly (meth) acrylate structure in that the polymer chain and the solvent have an even better affinity, and the polymer compound can more easily disperse pigments and the like. It is preferable to contain at least one selected from the group consisting of, and more preferable to contain at least one selected from the group consisting of a polyester structure and a polyether structure.

The macromonomer containing such a polymer chain (a monomer that contains a polymer structure and binds to the main chain of a polymer compound (for example, a copolymer) to form a graft chain) is not particularly limited, Macromonomers containing reactive double bond groups are preferred.

Commercially available macromonomers that correspond to structural units containing a polymer chain contained in the polymer compound and can be used for the synthesis of the polymer compound include, for example, AA-6, AA-10, AB-6, AS -6, AN-6, AW-6, AA-714, AY-707, AY-714, AK-5, AK-30, and AK-32 (all the above are trade names, manufactured by Toa Gosei Co., Ltd.) Blemmer PP-100, Blemmer PP-500, Blemmer PP-800, Blemmer PP-1000, Blemmer 55-PET-800, Blemmer PME-4000, Blemmer PSE-400, Blemmer PSE-1300, and Blemmer 43PAPE- 600B (all the above are trade names, manufactured by NOF Corporation); and the like.

The dispersant preferably contains at least one structure selected from the group consisting of polymethyl acrylate, polymethyl methacrylate, and cyclic or chain polyesters. Polymethyl acrylate, polymethyl methacrylate It is more preferable to contain at least one structure selected from the group consisting of chain polyesters, and from a polymethyl acrylate structure, a polymethyl methacrylate structure, a polycaprolactone structure, and a polyvalerolactone structure. More preferably, it contains at least one structure selected from the group consisting of:
The dispersant may contain one type of the above structure in the molecule, or may contain a plurality of types of this structure in the molecule.
Here, the polycaprolactone structure means a structure containing a ring-opened structure of ε-caprolactone as a repeating unit. The polyvalerolactone structure means a structure containing a ring-opened structure of δ-valerolactone as a repeating unit.
Examples of the dispersant containing a polycaprolactone structure include those in which j or k is 5 in the following formula (1) or the following formula (2). In addition, examples of the dispersant containing a polyvalerolactone structure include those in which j or k is 4 in the following formula (1) or the following formula (2).
Examples of the dispersant containing a polymethyl acrylate structure include those in which, in the following formula (4), X ⁵ is a hydrogen atom and R ⁴ is a methyl group.
Examples of the dispersant containing a polymethyl methacrylate structure include those in which X ⁵ is a methyl group and R ⁴ is a methyl group in the following formula (4).

Structural unit containing a graft chain The polymer compound contains at least one polymer chain selected from the group consisting of the following formulas (1) to (4) as a structural unit containing a graft chain. It is preferable to contain a structural unit, and at least one selected from the group consisting of the following formula (1A), the following formula (2A), the following formula (3A), the following formula (3B), and the following (4), More preferably, it contains a structural unit containing a polymer chain.

In the formulas (1) to (4), W ¹ , W ² , W ³ , and W ⁴ each independently represent an oxygen atom or NH. W ¹ , W ² , W ³ , and W ⁴ are preferably oxygen atoms.
In the formulas (1) to (4), X ¹ , X ² , X ³ , X ⁴ , and X ⁵ each independently represent a hydrogen atom or a monovalent organic group. X ¹ , X ² , X ³ , X ⁴ , and X ⁵ are each independently preferably a hydrogen atom or an alkyl group having 1 to 12 carbon atoms (the number of carbon atoms) from the viewpoint of synthesis constraints. Independently, a hydrogen atom or a methyl group is more preferable, and a methyl group is still more preferable.

In formulas (1) to (4), Y ¹ , Y ² , Y ³ , and Y ⁴ each independently represent a divalent linking group. The structure of the linking group is not particularly limited. Examples of the divalent linking group represented by Y ¹ , Y ² , Y ³ , and Y ⁴ include linking groups represented by the following formulas (Y-1) to (Y-21). . In the following formulas (Y-1) to (Y-21), A and B each represent a binding site. Of the structures shown below, (Y-2) or (Y-13) is more preferred because of the ease of synthesis.

In the formulas (1) to (4), Z ¹ , Z ² , Z ³ , and Z ⁴ each independently represent a monovalent organic group. The structure of the organic group is not particularly limited. Examples of the organic group include an alkyl group, a hydroxyl group, an alkoxy group, an aryloxy group, a heteroaryloxy group, an alkylthioether group, an arylthioether group, a heteroarylthioether group, and an amino group.
Among them, the organic groups represented by Z ¹ , Z ² , Z ³ , and Z ⁴ preferably have a steric repulsion effect in that pigments and the like are more easily dispersed. An alkyl group or an alkoxy group having 5 to 24 carbon atoms is more preferable, and a branched alkyl group having 5 to 24 carbon atoms, a cyclic alkyl group having 5 to 24 carbon atoms, or an alkoxy group having 5 to 24 carbon atoms is more preferable. . The alkyl group contained in the alkoxy group may be linear, branched, or cyclic.

In the formulas (1) to (4), n, m, p, and q each independently represents an integer of 1 to 500.
In formula (1) and formula (2), j and k each independently represents an integer of 2 to 8.
In the formula (1) and the formula (2), j and k are integers of 4 to 6 in that the curable composition has better stability over time and better developability. 5 is more preferable.
In Formula (1) and Formula (2), n and m are preferably integers of 10 or more, and more preferably 20 or more. Further, when the dispersant contains a polycaprolactone structure and a polyvalerolactone structure, the sum of the number of repetitions of the polycaprolactone structure and the number of repetitions of polyvalerolactone is preferably an integer of 10 or more, An integer is more preferable.

In the formula (3), R ³ represents a branched or straight chain alkylene group, preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 2 or 3 carbon atoms. When p is 2 to 500, a plurality of R ³ may be the same as or different from each other.
In formula (4), R ⁴ represents a hydrogen atom or a monovalent organic group. The structure of the monovalent organic group is not particularly limited. As R ⁴ , for example, a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group is preferable, and a hydrogen atom or an alkyl group is more preferable.
When R ⁴ is an alkyl group, the alkyl group may be a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, or a cyclic alkyl group having 5 to 20 carbon atoms. Preferably, a linear alkyl group having 1 to 20 carbon atoms is more preferable, and a linear alkyl group having 1 to 6 carbon atoms is still more preferable. In the formula (4), when q is 2 to 500, a plurality of X ⁵ and R ⁴ present in the structural unit containing a graft chain may be the same or different from each other.

The polymer compound may contain structural units containing two or more types of graft chains having different structures. That is, in the molecule of the polymer compound, structural units represented by the formulas (1) to (4) having different structures may be contained, and in the formulas (1) to (4), n, m , P, and q each represent an integer of 2 or more, in formula (1) and formula (2), j and k may contain structures different from each other in the side chain, and formula (3) and formula In (4), a plurality of R ³ , R ⁴ and X ⁵ present in the molecule may be the same or different from each other.

The structural unit represented by the formula (1) is a structural unit represented by the following formula (1A) in that the curable composition has better stability over time and better developability. More preferred.
As the structural unit represented by the formula (2), a structural unit represented by the following formula (2A) is more preferable in that the curable composition has more excellent temporal stability and developability.

In the formula ^(1A), X ^1, Y 1, ^{Z 1} and n are as previously described as ^X ^1, Y 1, ^{Z 1} and n in formula (1). In the formula ^(2A), X ^2, Y 2, ^{Z 2} and m are as previously described as ^X ^2, Y 2, ^{Z 2} and m in the formula (2).

The structural unit represented by the formula (3) is represented by the following formula (3A) or the formula (3B) in that the curable composition has better temporal stability and better developability. The structural unit is more preferable.

Wherein (3A) or ^(3B), X ^3, Y 3, ^{Z 3} and p in formula (3) ^{it is} as previously described as X ^3, Y 3, ^{Z 3} and p.

More preferably, the polymer compound contains a structural unit represented by the formula (1A) as a structural unit containing a graft chain, particularly a polymer chain.

The content of the structural unit containing a graft chain (for example, the structural unit represented by the above formula (1) to formula (4)) in the polymer compound is based on the total mass of the polymer compound in terms of mass. The range is preferably 2 to 90% by mass, and more preferably 5 to 30%. When the content of the structural unit containing a graft chain in the polymer compound is within the above range, the dispersant can easily disperse the pigment or the like, and the curable composition has more excellent developability.

-Hydrophobic structural unit It is preferable that a high molecular compound contains the hydrophobic structural unit different from the structural unit containing a graft chain (namely, it does not correspond to the structural unit containing a graft chain). However, in this specification, the hydrophobic structural unit is a structural unit that does not contain an acid group (for example, a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, a phenolic hydroxyl group, and the like).

The hydrophobic structural unit is preferably a structural unit derived from (corresponding to) a compound (monomer) having a ClogP value of 1.2 or more, which will be described later, and a structural unit derived from a compound having a ClogP value of 1.2 to 8.0. More preferred.

ClogP values are available from Daylight Chemical Information System, Inc. It is a value calculated by the program “CLOGP” available from This program provides the value of “computation logP” calculated by Hansch, Leo's fragment approach (see below). The fragment approach is based on the chemical structure of a compound, which divides the chemical structure into substructures (fragments) and estimates the logP value of the compound by summing the logP contributions assigned to that fragment. Details thereof are described in the following documents. In this specification, the ClogP value is intended to be a value calculated by the program CLOGP v4.82.
A. J. et al. Leo, Comprehensive Medicinal Chemistry, Vol. 4, C.I. Hansch, P.A. G. Sammunens, J. et al. B. Taylor and C.M. A. Ramsden, Eds. , P. 295, Pergamon Press, 1990 C.I. Hansch & A. J. et al. Leo. Substituent Constants For Correlation Analysis in Chemistry and Biology. John Wiley & Sons. A. J. et al. Leo. Calculating logPoch from structure. Chem. Rev. , 93, 1281-1306, 1993.

log P means the common logarithm of the partition coefficient P (Partition Coefficient), and quantitatively determines how an organic compound is distributed in the equilibrium of a two-phase system of oil (generally 1-octanol) and water. It is a physical property value expressed as a numerical value, and is represented by the following formula.
logP = log (Coil / Cwater)
In the formula, Coil represents the molar concentration of the compound in the oil phase, and Cwater represents the molar concentration of the compound in the aqueous phase.
When the logP value increases to a positive value across 0, the oil solubility increases. When the logP value increases to a negative value, the water solubility increases. There is a negative correlation with the water solubility of the organic compound. It is widely used as a parameter for estimating aqueous properties.

The polymer compound may contain at least one structural unit selected from the group consisting of structural units derived from monomers represented by the following formulas (i) to (iii) as hydrophobic structural units. preferable.

In the above formulas (i) to (iii), R ¹ , R ² , and R ³ are each independently a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, etc.), or a carbon number Represents an alkyl group of 1 to 6 (for example, a methyl group, an ethyl group, a propyl group, etc.).
R ¹ , R ² and R ³ are preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom or a methyl group. R ² and R ³ are more preferably a hydrogen atom.
X represents an oxygen atom (—O—) or an imino group (—NH—), preferably an oxygen atom.

L is a single bond or a divalent linking group. Examples of the divalent linking group include a divalent aliphatic group (for example, an alkylene group, a substituted alkylene group, an alkenylene group, a substituted alkenylene group, an alkynylene group, and a substituted alkynylene group), a divalent aromatic group (for example, , Arylene groups, substituted arylene groups, etc.), divalent heterocyclic groups, oxygen atoms (—O—), sulfur atoms (—S—), imino groups (—NH—), substituted imino groups (—NR ³¹⁾ -, Wherein R ³¹ represents an aliphatic group, an aromatic group or a heterocyclic group), a carbonyl group (-CO-), and combinations thereof.

The divalent aliphatic group may contain a cyclic structure or a branched chain structure. The aliphatic group preferably has 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, and still more preferably 1 to 10 carbon atoms. The aliphatic group may be an unsaturated aliphatic group or a saturated aliphatic group, and is preferably a saturated aliphatic group. The aliphatic group may contain a substituent. Although it does not restrict | limit especially as a substituent, For example, a halogen atom, an aromatic group, a heterocyclic group, etc. are mentioned.

The carbon number of the divalent aromatic group is preferably 6 to 20, more preferably 6 to 15, and still more preferably 6 to 10. The aromatic group may contain a substituent. Although it does not restrict | limit especially as a substituent, A halogen atom, an aliphatic group, an aromatic group, a heterocyclic group, etc. are mentioned.

The divalent heterocyclic group preferably contains a 5-membered ring or a 6-membered ring as the heterocyclic ring. Another heterocyclic ring, an aliphatic ring or an aromatic ring may be condensed with the heterocyclic ring. The heterocyclic group may contain a substituent. The substituent is not particularly limited. For example, a halogen atom, a hydroxyl group, an oxo group (═O), a thioxo group (═S), an imino group (═NH), a substituted imino group (═N—R ³² , R ³² may be an aliphatic group, an aromatic group or a heterocyclic group), an aliphatic group, an aromatic group, a heterocyclic group, or the like.

L is preferably a single bond, an alkylene group or a divalent linking group containing an oxyalkylene structure. The oxyalkylene structure is more preferably an oxyethylene structure or an oxypropylene structure. L may contain a polyoxyalkylene structure containing two or more oxyalkylene structures. The polyoxyalkylene structure is preferably a polyoxyethylene structure or a polyoxypropylene structure. The polyoxyethylene structure is represented by — (OCH ₂ CH ₂ ) _n —, where n is preferably an integer of 2 or more, and more preferably an integer of 2 to 10.

Z includes an aliphatic group (for example, an alkyl group, a substituted alkyl group, an unsaturated alkyl group, and a substituted unsaturated alkyl group), an aromatic group (for example, an aryl group, a substituted aryl group, an arylene group, and Substituted arylene groups, etc.), heterocyclic groups, or combinations thereof. These groups include an oxygen atom (—O—), a sulfur atom (—S—), an imino group (—NH—), a substituted imino group (—NR ³¹ —, where R ³¹ is an aliphatic group or an aromatic group. Or a heterocyclic group) or a carbonyl group (—CO—).

The aliphatic group may contain a cyclic structure or a branched chain structure. The aliphatic group preferably has 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, and still more preferably 1 to 10 carbon atoms. The aliphatic group further contains a ring assembly hydrocarbon group or a bridged cyclic hydrocarbon group. Examples of the ring assembly hydrocarbon group include a bicyclohexyl group, a perhydronaphthalenyl group, a biphenyl group, and Examples include 4-cyclohexylphenyl group. Examples of the bridged cyclic hydrocarbon ring include pinane, bornane, norpinane, norbornane, and bicyclooctane ring (bicyclo [2.2.2] octane ring, bicyclo [3.2.1] octane ring, etc.) A tricyclic hydrocarbon ring such as adamantane, tricyclo [5.2.1.0 ^2,6 ] decane, and tricyclo [4.3.1.1 ^2,5 ] undecane ring Tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodecane, and tetracyclic hydrocarbon rings such as perhydro-1,4-methano-5,8-methanonaphthalene ring; and the like. Bridged cyclic hydrocarbon rings include fused cyclic hydrocarbon rings such as perhydronaphthalene (decalin), perhydroanthracene, perhydrophenanthrene, perhydroacenaphthene, perhydrofluorene, perhydroindene, and perhydroindene. A condensed ring formed by condensing a plurality of 5- to 8-membered cycloalkane rings such as a phenalene ring is also included.
As the aliphatic group, a saturated aliphatic group is preferable to an unsaturated aliphatic group. The aliphatic group may contain a substituent. Examples of the substituent include a halogen atom, an aromatic group, and a heterocyclic group. However, the aliphatic group does not contain an acid group as a substituent.

The carbon number of the aromatic group is preferably 6-20, more preferably 6-15, and still more preferably 6-10. The aromatic group may contain a substituent. Examples of the substituent include a halogen atom, an aliphatic group, an aromatic group, and a heterocyclic group. However, the aromatic group does not contain an acid group as a substituent.

It is preferable that a heterocyclic group contains a 5-membered ring or a 6-membered ring as a heterocyclic ring. Another heterocyclic ring, an aliphatic ring or an aromatic ring may be condensed with the heterocyclic ring. The heterocyclic group may contain a substituent. Examples of the substituent include a halogen atom, a hydroxyl group, an oxo group (═O), a thioxo group (═S), an imino group (═NH), a substituted imino group (═N—R ³² , where R ³² is aliphatic. Group, aromatic group or heterocyclic group), aliphatic group, aromatic group, heterocyclic group and the like. However, the heterocyclic group does not contain an acid group as a substituent.

In the above formula (iii), R ⁴ , R ⁵ , and R ⁶ are each independently a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, etc.), or a carbon number of 1-6. An alkyl group (for example, a methyl group, an ethyl group, a propyl group, etc.), Z, or LZ. Here, L and Z are as defined above. R ^4, ^{R 5} and, as the ^{R 6,} a hydrogen atom, or, preferably an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom.

As the monomer represented by the above formula (i), R ¹ , R ² , and R ³ are a hydrogen atom or a methyl group, and L is a single bond, an alkylene group, or an oxyalkylene structure A compound in which X is an oxygen atom or an imino group, and Z is an aliphatic group, a heterocyclic group or an aromatic group is preferable.
As the monomer represented by the above formula (ii), a compound in which R ¹ is a hydrogen atom or a methyl group, L is an alkylene group, and Z is an aliphatic group, a heterocyclic group or an aromatic group Is preferred. Examples of the monomer represented by the above formula (iii) include compounds in which R ⁴ , R ⁵ , and R ⁶ are a hydrogen atom or a methyl group, and Z is an aliphatic group, a heterocyclic group, or an aromatic group. preferable.

Examples of typical compounds represented by the formulas (i) to (iii) include radical polymerizable compounds such as acrylic acid esters, methacrylic acid esters, and styrenes.
As examples of typical compounds represented by formulas (i) to (iii), compounds described in paragraphs 0089 to 0093 of JP2013-249417A can be referred to, and the contents thereof are described in the present specification. Incorporated into.

The content of the hydrophobic structural unit is preferably 10 to 90% by mass and more preferably 20 to 80% by mass with respect to the total mass of the polymer compound. When the content of the hydrophobic structural unit is within the above range, the curable composition has a more excellent effect of the present invention.

Structural unit containing a functional group capable of forming an interaction with a pigment or the like A functional group capable of forming an interaction with a pigment or the like can be introduced into the polymer compound. Here, the polymer compound preferably further contains a structural unit containing a functional group capable of forming an interaction with a pigment or the like.
Examples of the functional group capable of forming an interaction with the pigment and the like include an acid group, a basic group, a coordination group, and a reactive functional group.
When the polymer compound contains an acid group, a basic group, a coordination group, or a reactive functional group, the structural unit containing an acid group, the structural unit containing a basic group, and a coordination group, respectively. It is preferable to contain a structural unit containing a coordinate group or a structural unit having reactivity.
In particular, when the polymer compound further contains an alkali-soluble group such as a carboxylic acid group as the acid group, developability for pattern formation by alkali development can be imparted to the polymer compound.
That is, by introducing an alkali-soluble group into the polymer compound, in the curable composition, the polymer compound as a dispersant that contributes to the dispersion of pigments and the like has alkali solubility at the same time. The curable composition containing such a polymer compound has better alkali developability (the unexposed portion is more easily dissolved by alkali development), and the resulting cured film has better light shielding. Have sex.

The polymer compound containing an acid group has a higher affinity with the solvent described later. Therefore, the curable composition containing the high molecular compound containing an acid group has more excellent coating property.
This is because the acid group in the structural unit containing an acid group is likely to interact with the pigment and the like, the polymer compound stably disperses the pigment and the like, and the viscosity of the polymer compound that disperses the pigment and the like further decreases. This is presumably because the polymer compound itself is easily dispersed stably.

The structural unit containing an alkali-soluble group as an acid group may be the same structural unit as the structural unit containing the graft chain or a different structural unit.
In the present specification, the structural unit containing an alkali-soluble group as an acid group intends a structural unit different from the hydrophobic structural unit (that is, does not correspond to the hydrophobic structural unit described above).

Among functional groups that can form an interaction with pigments, examples of the acid group include a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, and a phenolic hydroxyl group. And at least one selected from the group consisting of phosphoric acid groups is preferred, and carboxylic acid groups are more preferred in that they have better adsorptive power to pigments and the like and have better dispersibility. .
That is, the polymer compound preferably further contains a structural unit containing at least one selected from the group consisting of a carboxylic acid group, a sulfonic acid group, and a phosphoric acid group.

The polymer compound may have one or more structural units containing an acid group.
The polymer compound may or may not contain a structural unit containing an acid group.
The content of the structural unit containing an acid group in the polymer compound is preferably 5 to 80% by mass with respect to the total mass of the polymer compound, in that damage of image strength due to alkali development is further suppressed. 10 to 60% by mass is more preferable.

Among the functional groups capable of forming an interaction with a pigment or the like, the basic group includes, for example, a primary amino group, a secondary amino group, a tertiary amino group, a heterocyclic group containing an N atom, and And an amide group. Among these, a tertiary amino group is preferable in that it has a better adsorptive power to pigments and the like and has a better dispersibility. The polymer compound may contain one basic group alone or two or more basic groups.
The polymer compound may or may not contain a structural unit containing a basic group.
The content of the structural unit containing a basic group in the polymer compound is preferably 0.01 to 50% by mass with respect to the total mass of the polymer compound, and the curable composition has better developability. In view of the above, 0.01 to 30% by mass is more preferable.

Among the functional groups capable of forming an interaction with a pigment or the like, as a coordinating group and a reactive functional group, for example, an acetylacetoxy group, a trialkoxysilyl group, an isocyanate group, an acid anhydride group, and And acid chloride groups. Of these, an acetylacetoxy group is preferable in that it has a better adsorbing power to pigments and the like and is more easily dispersed. The polymer compound may contain a coordinating group and a reactive functional group alone, or may contain two or more kinds. The polymer compound may or may not contain any of a structural unit containing a coordinating group and a structural unit containing a reactive functional group.
The content of the structural unit containing a coordinating group and the reactive functional group in the polymer compound is preferably 10 to 80% by mass relative to the total mass of the polymer compound, and is curable. 20-60 mass% is more preferable at the point which the composition shows the outstanding developability.

When the polymer compound contains a functional group capable of forming an interaction with a pigment or the like in addition to the graft chain, the polymer compound may contain a functional group capable of forming an interaction with the pigment or the like. Although it is not particularly limited how the polymer is introduced, the polymer compound contains one or more structural units selected from structural units derived from monomers represented by the following formulas (iv) to (vi). It is preferable to contain.

In formulas (iv) to (vi), R ¹¹ , R ¹² , and R ¹³ each independently represent a hydrogen atom, a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom, etc.), or a carbon number Represents an alkyl group of 1 to 6 (for example, a methyl group, an ethyl group, a propyl group, etc.).
In formulas (iv) to (vi), R ¹¹ , R ¹² and R ¹³ are each independently preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and each independently a hydrogen atom Or a methyl group is more preferable. In formula (iv), R ¹² and R ¹³ are each more preferably a hydrogen atom.

X ₁ in the formula (iv) represents an oxygen atom (—O—) or an imino group (—NH—), and preferably an oxygen atom.
Y in the formula (v) represents a methine group or a nitrogen atom.

L ₁ in the formulas (iv) to (v) represents a single bond or a divalent linking group. The definition of the divalent linking group is the same as the definition of the divalent linking group represented by L in the above-described formula (i).

L ₁ is preferably a single bond or a divalent linking group containing an alkylene group or an oxyalkylene structure. The oxyalkylene structure is more preferably an oxyethylene structure or an oxypropylene structure. L ₁ may contain a polyoxyalkylene structure containing two or more oxyalkylene structures repeatedly. The polyoxyalkylene structure is preferably a polyoxyethylene structure or a polyoxypropylene structure. The polyoxyethylene structure is represented by — (OCH ₂ CH ₂ ) n—, where n is preferably an integer of 2 or more, and more preferably an integer of 2 to 10.

In formulas (iv) to (vi), Z ₁ represents a functional group capable of forming an interaction with a pigment or the like other than the graft chain, and is preferably a carboxylic acid group or a tertiary amino group. Is more preferable.

In the formula (vi), R ¹⁴ , R ¹⁵ , and R ¹⁶ are each independently a hydrogen atom, a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom, etc.), or an alkyl having 1 to 6 carbon atoms. group (e.g., methyl group, ethyl group, and propyl group), - _{Z 1,} or an _L 1 -Z _1. Wherein _{L 1} and _{Z 1} are the same meaning as _{L 1} and _{Z 1} in the above, it is the preferable examples. R ¹⁴ , R ¹⁵ and R ¹⁶ are each independently preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom.

As the monomer represented by the formula (iv), R ¹¹ , R ¹² , and R ¹³ are each independently a hydrogen atom or a methyl group, and L ₁ contains an alkylene group or an oxyalkylene structure. And a compound in which X ₁ is an oxygen atom or an imino group and Z ₁ is a carboxylic acid group.
As the monomer represented by the formula (v), R ¹¹ is a hydrogen atom or a methyl group, L ₁ is an alkylene group, Z ₁ is a carboxylic acid group, and Y is a methine group. Certain compounds are preferred.
As the monomer represented by the formula (vi), R ¹⁴ , R ¹⁵ , and R ¹⁶ are each independently a hydrogen atom or a methyl group, L ₁ is a single bond or an alkylene group, and Z ₁ A compound in which is a carboxylic acid group is preferred.

The following are typical examples of monomers (compounds) represented by the formulas (iv) to (vi).
Examples of the monomer include methacrylic acid, crotonic acid, isocrotonic acid, a compound containing an addition polymerizable double bond and a hydroxyl group in the molecule (for example, 2-hydroxyethyl methacrylate) and succinic anhydride. Product, a reaction product of a compound containing an addition polymerizable double bond and a hydroxyl group in the molecule with phthalic anhydride, a compound containing an addition polymerizable double bond and a hydroxyl group in the molecule and tetrahydroxyphthalic anhydride Reaction product, a reaction product of a compound containing an addition polymerizable double bond and hydroxyl group in the molecule and trimellitic anhydride, a compound containing an addition polymerizable double bond and hydroxyl group in the molecule and pyromellitic anhydride Reactants with, acrylic acid, acrylic acid dimer, acrylic acid oligomer, maleic acid, itaconic acid, fumaric acid, 4-vinylbenzoic acid, vinylphenol, and 4-hydroxyphenyl methacrylamide.

In the polymer compound, the content of the structural unit containing a functional group capable of forming an interaction with a pigment or the like is high from the viewpoint of the interaction with the pigment or the like, stability over time, and permeability to a developer. The amount is preferably 0.05 to 90% by mass, more preferably 1.0 to 80% by mass, and still more preferably 10 to 70% by mass with respect to the total mass of the molecular compound.

-Other structural units Furthermore, for the purpose of improving various performances such as image strength, the polymer compound is a structural unit containing a graft chain, a hydrophobic structural unit, and a pigment as long as the effects of the present invention are not impaired. Other structural units (for example, structural units containing functional groups having an affinity for the solvent used in the dispersion composition, etc.) are different from structural units containing functional groups capable of forming an interaction with Further, it may be contained.
Examples of the other structural unit include a structural unit derived from a radical polymerizable compound selected from the group consisting of acrylonitriles and methacrylonitriles.
The polymer compound may contain one other structural unit alone and may contain two or more kinds.
The content of other structural units in the polymer compound is preferably 0% to 80% by mass and more preferably 10 to 60% by mass with respect to the total mass of the polymer compound. When the content of other structural units is 0 to 80% by mass, the curable composition has more excellent pattern forming properties.

-Physical properties of the polymer compound The acid value of the polymer compound is not particularly limited, but is preferably 0 to 250 mgKOH / g, more preferably 10 to 200 mgKOH / g, and still more preferably 20 to 120 mgKOH / g.
When the acid value of the polymer compound is 250 mgKOH / g or less, peeling of the cured film from the support is further suppressed in the development step described later. When the acid value of the polymer compound is 10 mgKOH / g or more, the curable composition has more excellent alkali developability.
When the acid value of the polymer compound is 20 mgKOH / g or more, the precipitation of pigments and the like in the curable composition is further suppressed, and the number of coarse particles is smaller. Have sex.

The acid value of the polymer compound can be calculated, for example, from the average content of acid groups in the polymer compound. Moreover, the high molecular compound which has a desired acid value can be obtained by changing content of the structural unit containing the acid group in a high molecular compound.

The weight average molecular weight of the polymer compound is that GPC (Gel Permeation Chromatography) is a gel permeation chromatography in that the curable composition has better developability and the resulting cured film is more difficult to peel in the development process. The polystyrene-converted value by the (graph) method is preferably 4,000 to 300,000, more preferably 5,000 to 200,000, still more preferably 6,000 to 100,000, and particularly preferably 10,000 to 50,000. preferable.
The GPC method is based on a method using HLC-8020GPC (manufactured by Tosoh), TSKgel SuperHZM-H, TSKgel SuperHZ4000, TSKgel SuperHZ2000 (manufactured by Tosoh, 4.6 mm ID × 15 cm) as a column and THF (tetrahydrofuran) as an eluent. . The polymer compound can be synthesized based on a known method.

Specific examples of the polymer compound include “DA-7301” manufactured by Enomoto Kasei Co., Ltd., “Disperbyk-101 (polyamidoamine phosphate)” manufactured by BYK Chemie, 107 (carboxylic acid ester), and 110 (copolymer containing acid group). ), 111 (phosphate dispersant), 130 (polyamide), 161, 162, 163, 164, 165, 166, 170, 190 (polymer copolymer) ”,“ BYK-P104, P105 (non-high molecular weight) Saturated polycarboxylic acid) ”,“ EFKA 4047, 4050 to 4010 to 4165 (polyurethane) ”, EFKA 4330 to 4340 (block copolymer), 4400 to 4402 (modified polyacrylate), 5010 (polyesteramide), 5765 (polyester), manufactured by EFKA High molecular weight polycarboxylate), 6220 (fatty acid polyester) ), 6745 (phthalocyanine derivative), 6750 (azo pigment derivative), “Ajisper PB821, PB822, PB880, PB881” manufactured by Ajinomoto Fine Techno Co., Ltd., “Floren TG-710 (urethane oligomer)” manufactured by Kyoeisha Chemical Co., Ltd., “Polyflow” No. 50E, No. 300 (acrylic copolymer) ”,“ Disparon KS-860, 873SN, 874, # 2150 (aliphatic polycarboxylic acid), # 7004 (polyether ester), DA, manufactured by Enomoto Kasei Co., Ltd. -703-50, DA-705, DA-725 "," Demol RN, N (Naphthalenesulfonic acid formalin polycondensate), MS, C, SN-B (aromatic sulfonic acid formalin polycondensate) "manufactured by Kao Corporation "Homogenol L-18 (polymeric polycarboxylic acid)", "Emulgen 920" 930, 935, 985 (polyoxyethylene nonylphenyl ether) ”,“ acetamine 86 (stearylamine acetate) ”,“ Solsperse 5000 (phthalocyanine derivative), 22000 (azo pigment derivative), 13240 (polyesteramine), manufactured by Nippon Lubrizol, 3000, 12000, 17000, 20000, 27000 (polymers containing a functional part at the end), 24000, 28000, 32000, 38500 (graft copolymer) ”,“ Nikkor T106 (polyoxyethylene sorbitan mono) manufactured by Nikko Chemicals Oleart), MYS-IEX (polyoxyethylene monostearate), Kawano Fine Chemical's Hinoact T-8000E, Shin-Etsu Chemical Organosiloxane Polymer KP341, Yusho W001: Cationic surfactant ", polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate Nonionic surfactants such as sorbitan fatty acid esters, anionic surfactants such as “W004, W005, W017”, “EFKA-46, EFKA-47, EFKA-47EA, EFKA polymer 100, EFKA polymer 400 manufactured by Morishita Sangyo , EFKA Polymer 401, EFKA Polymer 450 ", Sannopco" Disperse Aid 6, Disperse Aid 8, Disperse Aid 15, Dispa Polymer dispersants such as Suede 9100, manufactured by ADEKA "Adeka Pluronic L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, P -123 ", Sanyo Kasei" Ionet (trade name) S-20 ", and the like. Also, Acrybase FFS-6752, Acrybase FFS-187, Acrycure-RD-F8, and Cyclomer P can be used.
Also, DISPERBYK-130, DISPERBYK-140, DISPERBYK-142, DISPERBYK-145, DISPERBYK-180, DISPERBYK-187, DISPERBYK-2001, DISPERBYK-2001, DISPERBYK-2010, DISPERBY20-ER, and DISPERBY20-ERB made by BYK Chemie. BYK-9076, Ajisper PB821, Azisper PB822, Azisper PB881 manufactured by Ajinomoto Fine Techno Co., etc. can also be used.
These polymer compounds may be used alone or in combination of two or more.

As the polymer compound, compounds described in paragraphs 0127 to 0129 of JP2013-249417A can be used, and the contents thereof are incorporated in the present specification.

As the dispersant, a graft copolymer described in JP-A 2010-106268, paragraphs 0037 to 0115 (corresponding paragraphs 0075 to 0133 of US2011 / 0124824) can also be used, and the contents thereof are incorporated herein. It is.
As a dispersant, a constituent component having a side chain structure in which acidic groups in paragraphs 0028 to 0084 of JP 2011-153283 A (corresponding paragraphs 0075 to 0133 of US2011 / 0279759) are bonded via a linking group Can also be used, the contents of which are incorporated herein.
As the dispersant, resins described in paragraphs 0033 to 0049 of JP-A No. 2016-109763 can also be used, the contents of which are incorporated herein.

(Binder resin)
The curable composition preferably contains a binder resin.
The content of the binder resin is preferably 0.1 to 30% by mass with respect to the total solid content of the curable composition.
Binder resin may be used individually by 1 type, or may use 2 or more types together. When using 2 or more types of binder resin together, it is preferable that the total amount is in the said range.

It is preferable to use a linear organic polymer as the binder resin. As such a linear organic polymer, a well-known thing can be used arbitrarily. Preferably, a linear organic polymer that is soluble or swellable in water or weak alkaline water is selected to enable water development or weak alkaline water development. Especially, as binder resin, alkali-soluble resin (resin containing group which accelerates | stimulates alkali solubility) is especially preferable.

The alkali-soluble resin means a resin containing a group that promotes alkali-solubility (alkali-soluble group), and a resin different from the dispersant already described.
Examples of the alkali-soluble resin include resins containing at least one alkali-soluble group in the molecule, such as polyhydroxystyrene resin, polysiloxane resin, (meth) acrylic resin, (meth) acrylamide resin, and (meth) acrylic. / (Meth) acrylamide copolymer, epoxy resin, and polyimide resin.

Specific examples of the alkali-soluble resin include a copolymer of an unsaturated carboxylic acid and an ethylenically unsaturated compound.
Although it does not restrict | limit especially as unsaturated carboxylic acid, Monocarboxylic acids, such as (meth) acrylic acid, crotonic acid, and vinyl acetic acid; Dicarboxylic acids, such as itaconic acid, maleic acid, and fumaric acid, or its acid anhydride And polycarboxylic acid monoesters such as monophthalic acid (2- (meth) acryloyloxyethyl).

Examples of the copolymerizable ethylenically unsaturated compound include methyl (meth) acrylate. The compounds described in paragraphs 0027 of JP2010-97210A and paragraphs 0036 to 0037 of JP2015-68893A can also be used, and the above contents are incorporated herein.

Also, a copolymerizable ethylenically unsaturated compound that contains an ethylenically unsaturated group in the side chain may be used in combination. As the ethylenically unsaturated group, a (meth) acrylic acid group is preferable. Acrylic resin containing an ethylenically unsaturated group in the side chain, for example, an addition reaction of an ethylenically unsaturated compound containing a glycidyl group or an alicyclic epoxy group to a carboxylic acid group of an acrylic resin containing a carboxylic acid group Can be obtained.

Examples of the alkali-soluble resin include JP-A-59-44615, JP-B-54-34327, JP-B-58-12777, JP-B-54-25957, JP-A-54-92723, JP-A-59-. Radical polymers containing a carboxylic acid group in the side chain described in JP-A No. 53836 and JP-A-59-71048; European Patent No. 993966, European Patent No. 1204000, and JP-A No. 2001-318463 An acetal-modified polyvinyl alcohol binder resin containing an alkali-soluble group described in each of the above publications; polyvinyl pyrrolidone; polyethylene oxide; alcohol-soluble nylon; and 2,2-bis- (4-hydroxyphenyl) -propane Polyether, etc., which is a reaction product with epichlorohydrin; International Publication No. And the like can be used; polyimide resin described in JP 008/123097.

As the alkali-soluble resin, for example, compounds described in paragraphs 0225 to 0245 of JP-A-2016-75845 can be used, and the above contents are incorporated in the present specification.

A polyimide precursor can also be used as the alkali-soluble resin. The polyimide precursor intends a resin obtained by subjecting a compound containing an acid anhydride group and a diamine compound to an addition polymerization reaction at 40 to 100 ° C.
As a polyimide precursor, resin containing the repeating unit represented by Formula (1) is mentioned, for example. Examples of the structure of the polyimide precursor include an amic acid structure represented by the following formula (2), the following formula (3) in which the amic acid structure is partially imide ring-closed, and / or the following formula in which all imide rings are closed: The thing containing the imide structure shown by (4) is mentioned.
In this specification, a polyimide precursor having an amic acid structure may be referred to as a polyamic acid.

In the above formulas (1) to (4), R ₁ represents a tetravalent organic group having 2 to 22 carbon atoms, R ₂ represents a divalent organic group having 1 to 22 carbon atoms, and n is 1 or 2 Represents.

Examples of the polyimide precursor include compounds described in paragraphs 0011 to 0031 of JP-A-2008-106250, compounds described in paragraphs 0022 to 0039 of JP-A-2016-122101, and JP-A-2016-68401. The compounds described in paragraphs 0061 to 0092 of the publication are listed, and the above contents are incorporated in the present specification.

The alkali-soluble resin preferably contains at least one selected from the group consisting of a polyimide resin and a polyimide precursor in that the pattern shape of the cured film obtained from the curable composition is more excellent.
The polyimide resin containing an alkali-soluble group is not particularly limited, and a known polyimide resin containing an alkali-soluble group can be used. Examples of the polyimide resin include a resin described in paragraph 0050 of JP-A-2014-137523, a resin described in paragraph 0058 of JP-A-2015-187676, and JP-A-2014-106326. Examples include the resins described in paragraphs 0012 to 0013, and the above contents are incorporated in the present specification.

<Polymerization inhibitor>
The curable composition preferably contains a polymerization inhibitor. It does not restrict | limit especially as a polymerization inhibitor, A well-known polymerization inhibitor can be used. Examples of the polymerization inhibitor include phenol-based polymerization inhibitors (for example, p-methoxyphenol, 2,5-di-tert-butyl-4-methylphenol, 2,6-di-tert-butyl-4-methylphenol). 4,4'-thiobis (3-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-methyl-6-tert-butylphenol), 4-methoxynaphthol, etc .; Hydroquinone polymerization prohibited Agents (for example, hydroquinone and 2,6-di-tert-butylhydroquinone); quinone polymerization inhibitors (for example, benzoquinone); free radical polymerization inhibitors (for example, 2,2,6, etc.) 6-tetramethylpiperidine 1-oxyl free radical and 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-o Sill free radicals, etc.); nitrobenzene-based polymerization inhibitor (e.g., nitrobenzene, and 4-nitrotoluene and the like); phenothiazine-based polymerization inhibitor (e.g., phenothiazine and 2-methoxy phenothiazine, etc.), and the like.
Among these, a phenol polymerization inhibitor or a free radical polymerization inhibitor is preferable in that the curable composition has the more excellent effects of the present invention.
The polymerization initiator may be mixed with other components at the time of preparing the curable composition, or the one used in the synthesis of the resin may be mixed with the other components together with the resin. May be.

The content of the polymerization inhibitor in the curable composition is not particularly limited, but the total solid of the curable composition in that the curable composition has better temporal stability and better curability. The content is preferably 0.0001 to 1% by mass relative to the minute.
A polymerization inhibitor may be used individually by 1 type, or may use 2 or more types together. When two or more polymerization inhibitors are used in combination, the total content is preferably within the above range.
The effect of the polymerization inhibitor is remarkable when used together with a resin containing a curable group. For example, during the preparation of the dispersion composition; after the preparation of the dispersion composition; during the preparation of the curable composition; after the preparation of the curable composition; Even when the resin containing a curable group is likely to be polymerized due to long-term storage or the like, it can be used without any problem.

<Solvent>
The curable composition may contain a solvent.
The solvent is not particularly limited, and a known solvent can be used.
The content of the solvent in the curable composition is not particularly limited, but in general, it is preferably adjusted so that the solid content of the curable composition is 20 to 90% by mass, and adjusted to be 30 to 90% by mass. More preferably.
A solvent may be used individually by 1 type, or may use 2 or more types together. When using 2 or more types of solvent together, it is preferable to adjust so that the total solid content of a curable composition may become in the said range.

As a solvent, water or an organic solvent is mentioned, for example.
Examples of the organic solvent include acetone, methyl ethyl ketone, cyclohexane, ethyl acetate, ethylene dichloride, tetrahydrofuran, toluene, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, acetylacetone. , Cyclohexanone, cyclopentanone, diacetone alcohol, ethylene glycol monomethyl ether acetate, ethylene glycol ethyl ether acetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether acetate, 3-methoxypropanol, methoxymethoxyethanol, diethylene glycol mono Chill ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxypropyl acetate, N, N-dimethylformamide, dimethyl sulfoxide, γ-butyrolactone, ethyl acetate, Examples thereof include, but are not limited to, butyl acetate, methyl lactate, N-methyl-2-pyrrolidone, and ethyl lactate.

<Surfactant>
The curable composition preferably contains a surfactant. The curable composition containing a surfactant has better coating properties.
The content of the surfactant in the curable composition is not particularly limited, but is preferably 0.001 to 2.0% by mass with respect to the total solid content of the curable composition.
Surfactant may be used individually by 1 type, or may use 2 or more types together. When two or more surfactants are used in combination, the total amount is preferably within the above range.

Examples of the surfactant include a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone-based surfactant.

For example, when the curable composition contains a fluorosurfactant, the liquid properties (particularly fluidity) of the curable composition are further improved. That is, when a curable composition layer is formed on a support using a curable composition containing a fluorosurfactant, the curability is reduced by reducing the interfacial tension between the support and the curable composition. The wettability of the composition to the support is improved, and the applicability of the curable composition is improved. For this reason, even when a curable composition layer of about several μm is formed with a small amount of liquid, it is possible to form a curable composition layer having a more uniform thickness with less thickness unevenness.

The fluorine content in the fluorosurfactant is not particularly limited, but is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and further preferably 7 to 25% by mass. According to the curable composition containing a fluorine-based surfactant having a fluorine content of 3 to 40% by mass, a curable composition layer having a more uniform thickness can be formed, and as a result The composition has superior liquid-saving properties. Moreover, it is easy to melt | dissolve a fluorine-type surfactant in a curable composition as it is in the said range.

Examples of the fluorosurfactant include Megafac F171, F172, F173, F176, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780 (above DIC Corporation), Florad FC430, FC431, FC171 (Sumitomo 3M Limited), Surflon S-382, SC-101, SC- 103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, K-H-40 (above, manufactured by Asahi Glass Co., Ltd.), PF636, PF656, PF6320, PF6520, PF7002 (made by OMNOVA) etc. are mentioned.
A block polymer can be used as the fluorosurfactant, for example, a compound described in JP-A-2011-89090 can be used, and the above contents are incorporated herein.

<Ultraviolet absorber>
The curable composition may contain an ultraviolet absorber. The cured film obtained by the curable composition containing an ultraviolet absorber has a more excellent pattern shape (fine pattern shape).
As the UV absorber, UV absorbers such as salicylate, benzophenone, benzotriazole, substituted acrylonitrile, and triazine can be used.
As the ultraviolet absorber, for example, compounds described in paragraphs 0137 to 0142 (corresponding paragraphs 0251 to 0254 of US2012 / 0068292) of JP2012-068418A can be used, and the above contents are incorporated in the present specification. It is.
As the ultraviolet absorber, a diethylamino-phenylsulfonyl ultraviolet absorber (manufactured by Daito Chemical Co., Ltd., trade name: UV-503) or the like can also be used.
As the ultraviolet absorber, the compounds described in paragraphs 0134 to 0148 of JP 2012-32556 A can also be used, and the above contents are incorporated herein.
The content of the ultraviolet absorber in the curable composition is not particularly limited, but is preferably 0.001 to 15% by mass, and 0.01 to 10% by mass with respect to the total solid content of the curable composition. More preferred is 0.1 to 5% by mass.

<Silane coupling agent>
The curable composition may contain a silane coupling agent.
In this specification, a silane coupling agent intends the compound which contains the following hydrolysable groups and other functional groups in a molecule | numerator. The hydrolyzable group is intended to be a substituent that is directly bonded to a silicon atom and can generate a siloxane bond by a hydrolysis reaction and / or a condensation reaction. Examples of the hydrolyzable group include a halogen atom, an alkoxy group, an acyloxy group, and an alkenyloxy group directly connected to a silicon atom. When the hydrolyzable group contains a carbon atom, the number of carbon atoms is preferably 6 or less, and more preferably 4 or less. In particular, an alkoxy group having 4 or less carbon atoms or an alkenyloxy group having 4 or less carbon atoms is preferable.

It is preferable that the silane coupling agent does not contain any silicon atom other than the silicon atom to which the hydrolyzable group is bonded, and no fluorine atom. When a cured film is formed on a support using the curable composition containing the silane coupling agent, the cured film has better adhesion to the support.

The content of the silane coupling agent in the curable composition is preferably 0.1 to 10% by mass, more preferably 0.5 to 8% by mass with respect to the total solid content in the curable composition. More preferably, the content is 0.0 to 6% by mass.
A silane coupling agent may be used individually by 1 type, or may use 2 or more types together. When using 2 or more types of silane coupling agents together, it is preferable that total content is in the said range.

[Method for producing curable composition]
The curable composition can be prepared by mixing the above components by a known mixing method (for example, a mixing method using a stirrer, a homogenizer, a high-pressure emulsifier, a wet pulverizer, a wet disperser, or the like). it can.
In preparing the curable composition, each component may be blended at once, or each component may be blended sequentially after being dissolved or dispersed in a solvent. Moreover, the order of input and the working conditions when blending are not particularly limited.

The curable composition is preferably filtered with a filter for the purpose of removing foreign substances and reducing defects. The filter is not particularly limited, and a known filter can be used.
The material of the filter is not particularly limited. For example, fluororesins such as PTFE (polytetrafluoroethylene), polyamide resins such as nylon, and polyolefin resins such as polyethylene and polypropylene (PP) (high density, super And a filter formed by high molecular weight). Of these, a filter formed of polypropylene (including high-density polypropylene) or nylon is preferable.
The pore size of the filter is not particularly limited, but is generally preferably 0.1 to 7.0 μm, more preferably 0.2 to 2.5 μm, still more preferably 0.2 to 1.5 μm, and 0.3 to 0. .7 μm is particularly preferred. By setting this range, it is possible to reliably remove fine foreign matters such as impurities and aggregates contained in the pigment while suppressing filtration clogging of the pigment.
When using filters, different filters may be combined. At that time, the filtering by the first filter may be performed only once or may be performed twice or more. When filtering two or more times by combining different filters, the pore diameter of the filter used for the second filtering is preferably the same or larger than the pore diameter of the filter used for the first filtering. In addition, filters having the same material and different pore diameters may be combined. The pore diameter here can refer to the nominal value of the filter manufacturer.
Examples of commercially available filters include filters manufactured by Nippon Pole, Advantech Toyo, Nippon Integris (formerly Nippon Microlith), and Kitz Microfilter.

As the second filter, a filter formed of the same material as the first filter can be used. The pore size of the second filter is not particularly limited, but is generally preferably 0.2 to 10.0 μm, more preferably 0.2 to 7.0 μm, still more preferably 0.3 to 6.0 μm.
It is preferable that the curable composition does not substantially contain impurities such as metals (particles and ions), metal salts containing halogens, acids, and alkalis. In the present specification, the phrase “substantially not contained” means that it cannot be detected by the following measurement method.
Although it does not restrict | limit especially as content of the impurity contained in a curable composition, the said component, the said filter, etc., respectively 1 mass ppm or less is preferable with respect to the total mass, 1 mass ppb or less is more preferable, 100 The mass ppt or less is more preferable, the mass ppt or less is particularly preferable, and it is most preferable that the mass is not substantially contained.
The content of the impurity can be measured by an inductively coupled plasma mass spectrometer (manufactured by Yokogawa Analytical Systems, Agilent 7500cs type).
Note that ppm represents parts per million, ppb represents parts per billion, and ppt represents parts per trigger.

〔container〕
The curable composition may be temporarily stored in the container until use. The container for storing the curable composition is not particularly limited, and a known container can be used.
As a container for storing the curable composition, a container having a high degree of cleanliness in the container and little elution of impurities is preferable. For example, you may use the thing of the use marketed for semiconductor uses.
Specific examples of containers that can be used include, but are not limited to, “Clean Bottle” series manufactured by Aicello Chemical Co., Ltd., “Pure Bottle” manufactured by Kodama Resin Co., Ltd., and the like.
For example, it is also preferable to use a multilayer bottle in which the inner wall of the container is configured in a six-layer structure with six types of resin, or a multilayer bottle in which the inner wall of the container is configured in a seven-layer structure with six types of resin. Examples of these containers include containers described in JP-A-2015-123351.

[Curing film and method for producing the cured film]
The cured film which concerns on embodiment of this invention is a cured film obtained by hardening | curing the said curable composition. The thickness of the cured film is not particularly limited, but is generally preferably 0.2 to 7 μm, and more preferably 0.4 to 5 μm.
The above thickness is an average thickness, and is a value obtained by measuring the thicknesses of five or more arbitrary points of the cured film and arithmetically averaging them.

Although the manufacturing method in particular of a cured film is not restrict | limited, The method of apply | coating a curable composition on a support body, forming a coating film, performing a hardening process with respect to a coating film, and manufacturing a cured film is mentioned.
The method of the curing treatment is not particularly limited, and examples thereof include a photocuring treatment or a thermosetting treatment, and a photocuring treatment (particularly a curing treatment by irradiation with actinic rays or radiation) is preferable from the viewpoint of easy pattern formation. .

The cured film which concerns on embodiment of this invention is a cured film obtained by hardening | curing the curable composition layer formed using the curable composition.
Although it does not restrict | limit especially as a manufacturing method of a cured film, It is preferable to contain the following processes.
-Curable composition layer formation process-Exposure process-Development process Hereinafter, each process is demonstrated.

<Curable composition layer forming step>
A curable composition layer formation process is a process of forming a curable composition layer using a curable composition. As a process of forming a curable composition layer using a curable composition, the process (application | coating process) of apply | coating a curable composition on a support body and forming a curable composition layer is mentioned, for example. Can be mentioned.
The type of the support is not particularly limited, but when a cured film is applied to a solid-state imaging device, for example, a silicon substrate is used, and when the cured film is used as a color filter (including a color filter for a solid-state imaging device). And a glass substrate (glass wafer).
Examples of the coating method of the curable composition on the support include various coating methods such as spin coating, slit coating, inkjet method, spray coating, spin coating, cast coating, roll coating, and screen printing. It is done.
The curable composition coated on the support is usually dried at 70 to 150 ° C. for about 1 to 4 minutes to form a curable composition layer.

<Exposure process>
In the exposure step, the curable composition layer formed in the curable composition layer forming step was exposed to light by irradiating actinic rays or radiation through a photomask having a pattern-shaped opening, and was irradiated with light. Only the curable composition layer is cured.
The exposure is preferably performed by irradiation with radiation, and ultraviolet rays such as g-line, h-line, and i-line are preferably used. The light source is preferably a high pressure mercury lamp. The irradiation intensity is not particularly limited, but generally 5 to 1500 mJ / cm ² is preferable.

<Development process>
Subsequent to the exposure step, development processing (development step) is performed to elute unexposed portions in the exposure step into the developer. Thereby, only the photocured part remains on the support.
Although it does not restrict | limit especially as a developing solution, For example, an alkali developing solution is mentioned, Especially, an organic alkali developing solution is preferable.
The development conditions are not particularly limited, but the development temperature is generally preferably 20 to 40 ° C., and the development time is generally preferably 20 to 180 seconds.
The alkaline aqueous solution (alkaline developer) is not particularly limited, but examples of the alkaline compound contained in the inorganic alkaline developer include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, sodium oxalate, and And sodium metasuccinate.
The content of the compound in the alkaline aqueous solution is not particularly limited, but is generally preferably 0.001 to 10% by mass and more preferably 0.005 to 0.5% by mass with respect to the total mass of the alkaline aqueous solution.
The alkaline compounds contained in the organic alkaline developer include ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxy. , Choline, pyrrole, piperidine, 1,8-diazabicyclo- [5,4,0] -7-undecene, and the like.
The content of the compound in the alkaline aqueous solution is not particularly limited, but is generally preferably 0.001 to 10% by mass and more preferably 0.005 to 0.5% by mass with respect to the total mass of the alkaline aqueous solution.

The alkaline aqueous solution may contain, for example, a water-soluble organic solvent such as methanol and ethanol. Further, the alkaline aqueous solution may contain a surfactant.
When such an alkaline aqueous solution is used as a developer, it is preferable to wash the developed curable composition layer with pure water or the like. In this specification, this process is called a washing | cleaning process, and it is preferable that the manufacturing method of a cured film contains a washing | cleaning process.

In addition, the manufacturing method of a cured film may contain another process.
There is no restriction | limiting in particular as another process, According to the objective, it can select suitably.
Examples of other processes include a substrate surface treatment process, a pre-heating process (pre-baking process), and a post-heating process (post-baking process).
The heating temperature in the preheating step and the postheating step is not particularly limited, but is generally preferably 80 to 300 ° C.
The heating time in the preheating step and the postheating step is not particularly limited, but is preferably 30 to 500 seconds.

The cured film preferably has a surface uneven structure. By doing so, the light reflectivity of a cured film can be reduced. Even if it has a concavo-convex structure on the surface of the cured film itself, a concavo-convex structure may be imparted by arranging a coat film on the cured film. The shape of the uneven surface structure is not particularly limited, but the surface roughness is preferably in the range of 0.55 to 1.5 μm or less.
The light reflectance of the cured film is preferably 5% or less, more preferably 3% or less, and still more preferably 2% or less.
The method for producing the surface concavo-convex structure is not particularly limited, but includes a method in which a cured film or a coating film contains an organic filler and / or an inorganic filler; a lithography method, an etching method, a sputtering method, a nanoimprint method, and the like A method of roughening the surface of the cured film and / or the coat film, etc.
Moreover, as a method for reducing the light reflectance of the cured film, for example, a method of disposing a low refractive index film on the cured film; a film having a different refractive index (for example, a high refractive index film) on the low refractive index film For example, a method of forming a low optical density layer and a high optical density layer described in JP-A-2015-1654.

The above-mentioned cured films are portable devices such as personal computers, tablets, mobile phones, smartphones, and digital cameras; OA (Office Automation) devices such as printer multifunction devices and scanners; surveillance cameras, barcode readers, automatic cash deposits Industrial equipment such as a payment machine (ATM: automated teller machine), high-speed camera, and equipment having a personal authentication function using face image authentication; in-vehicle camera equipment; endoscope, capsule endoscope, and Medical camera equipment such as catheters; biosensors, biosensors, military reconnaissance cameras, 3D map cameras, weather and ocean observation cameras, land resource exploration cameras, exploration cameras for space astronomy and deep space targets, etc. Used for space equipment; etc. Manabu filters and the light blocking member and the light-shielding film of the module, even can be used for anti-reflection member and the antireflection film or the like.

The cured film can also be used for applications such as micro LED (Light Emitting Diode) and micro OLED (Organic Light Emitting Diode). The cured film is suitable for members that provide a light shielding function or an antireflection function, as well as optical filters and optical films used in micro LEDs and micro OLEDs.
Examples of the micro LED and the micro OLED include those described in JP-T-2015-500562 and JP-T-2014-533890.

The said cured film is suitable as an optical filter and optical film used for a quantum dot display. Moreover, it is suitable as a member which provides a light shielding function and an antireflection function.
Examples of quantum dot displays include US Patent Application Publication No. 2013/0335677, US Patent Application Publication No. 2014/0036536, US Patent Application Publication No. 2014/0036203, and US Patent Application Publication No. 2014/0035960. What has been described.

[Solid-state imaging device and solid-state imaging device]
A solid-state imaging device and a solid-state imaging device according to an embodiment of the present invention contain the cured film. The form in which the solid-state imaging device contains a cured film is not particularly limited. For example, a plurality of photodiodes and polysilicon constituting a light receiving area of a solid-state imaging device (CCD image sensor, CMOS image sensor, etc.) on a support. And having the cured film on the light receiving element forming surface side of the support (for example, a portion other than the light receiving portion and / or a color adjusting pixel) or the opposite side of the forming surface. Is mentioned.
The solid-state imaging device contains the solid-state imaging element.

Configuration examples of the solid-state imaging device and the solid-state imaging device will be described with reference to FIGS. In FIGS. 7 to 8, in order to clarify each part, the ratio of the thickness and / or width of each component is partially exaggerated regardless of actuality.
As shown in FIG. 7, the solid-state imaging device 700 includes a rectangular solid-state imaging element 701 and a transparent cover glass 703 that is held above the solid-state imaging element 701 and seals the solid-state imaging element 701. Yes. Furthermore, a lens layer 711 is provided on the cover glass 703 with a spacer 704 interposed therebetween. The lens layer 711 includes a support 713 and a lens material 712. The lens layer 711 may have a configuration in which the support 713 and the lens material 712 are integrally formed. When stray light is incident on the peripheral region of the lens layer 711, the effect of condensing light on the lens material 712 is weakened due to light diffusion, and light reaching the imaging unit 702 is reduced. In addition, noise is generated due to stray light. Therefore, the peripheral region of the lens layer 711 is shielded from light by providing a light shielding film 714. The cured film according to the embodiment of the present invention (particularly when a black pigment is contained as a colorant) can also be used as the light shielding film 714.

The solid-state imaging device 701 photoelectrically converts an optical image formed in the imaging unit 702 serving as a light receiving surface thereof and outputs it as an image signal. This solid-state imaging device 701 includes a laminated substrate 705 in which two substrates (corresponding to a support) are laminated. The laminated substrate 705 includes a rectangular chip substrate 706 and a circuit substrate 707 having the same size, and the circuit substrate 707 is laminated on the back surface of the chip substrate 706.

The material of the substrate used as the chip substrate 706 is not particularly limited, and a known material can be used.

An imaging unit 702 is provided at the center of the surface of the chip substrate 706. Further, when stray light is incident on the peripheral area of the imaging unit 702, dark current (noise) is generated from the circuit in the peripheral area. Therefore, the peripheral area is shielded from light by being provided with a light shielding film 715. The cured film according to the embodiment of the present invention (especially when a black pigment is contained as a colorant) can also be used as the light shielding film 715.

A plurality of electrode pads 708 are provided on the surface edge of the chip substrate 706. The electrode pad 708 is electrically connected to the imaging unit 702 via a signal line (not shown) provided on the surface of the chip substrate 706 (which may be a bonding wire).

External connection terminals 709 are provided on the back surface of the circuit board 707 at positions substantially below the electrode pads 708, respectively. Each external connection terminal 709 is connected to an electrode pad 708 via a through electrode 710 that vertically penetrates the multilayer substrate 705. Further, each external connection terminal 709 is connected to a control circuit that controls driving of the solid-state image sensor 701 and an image processing circuit that performs image processing on an image signal output from the solid-state image sensor 701 via a wiring (not shown). Has been.

As shown in FIG. 8, the imaging unit 702 is configured by each unit provided on a substrate 804 such as a light receiving element 801, a color filter 802, and a micro lens 803. The color filter 802 includes a blue pixel 805b, a red pixel 805r, a green pixel 805g, and a black matrix 805bm. The cured film according to the embodiment of the present invention (especially when containing a black pigment as a colorant) can also be used as the black matrix 805bm.

As the material of the substrate 804, the same material as the above-described chip substrate 706 can be used. A p-well layer 806 is formed on the surface layer of the substrate 804. In the p-well layer 806, light receiving elements 801 that are n-type layers and generate and store signal charges by photoelectric conversion are arranged in a square lattice pattern.

On one side of the light receiving element 801, a vertical transfer path 808 made of an n-type layer is formed via a reading gate portion 807 on the surface layer of the p-well layer 806. Further, a vertical transfer path 808 belonging to an adjacent pixel is formed on the other side of the light receiving element 801 through an element isolation region 809 made of a p-type layer. The read gate portion 807 is a channel region for reading the signal charge accumulated in the light receiving element 801 to the vertical transfer path 808.

A gate insulating film 810 made of an ONO (Oxide-Nitride-Oxide) film is formed on the surface of the substrate 804. On the gate insulating film 810, a vertical transfer electrode 811 made of polysilicon or amorphous silicon is formed so as to cover the vertical transfer path 808, the read gate portion 807, and the element isolation region 809. The vertical transfer electrode 811 functions as a drive electrode for driving the vertical transfer path 808 to perform charge transfer and a read electrode for driving the read gate unit 807 to read signal charges. The signal charges are sequentially transferred from the vertical transfer path 808 to a horizontal transfer path (not shown) and an output unit (floating diffusion amplifier), and then output as a voltage signal.

A light shielding film 812 is formed on the vertical transfer electrode 811 so as to cover the surface thereof. The light shielding film 812 has an opening at a position immediately above the light receiving element 801 and shields the other areas. The cured film according to the embodiment of the present invention (especially when containing a black pigment as a colorant) can also be used as the light shielding film 812.
On the light shielding film 812, an insulating film 813 made of BPSG (borophosphosilicate glass), an insulating film (passivation film) 814 made of P-SiN, and a transparent intermediate layer made of a planarizing film 815 made of transparent resin or the like are provided. ing. The color filter 802 is formed on the intermediate layer.

[Black matrix]
A black matrix contains the cured film which concerns on embodiment of this invention. The black matrix may be contained in a color filter, a solid-state image sensor, and a liquid crystal display device.
As the black matrix, those already described above; a black edge provided at the periphery of a display device such as a liquid crystal display device; a grid pattern between red, blue, and green pixels, and / or a stripe pattern A black portion of the TFT; a dot-like and / or linear black pattern for shielding light from a TFT (thin film transistor); and the like. For the definition of this black matrix, see Taihei Kanno, “Liquid Crystal Display Manufacturing Dictionary”, 2nd edition, Nikkan Kogyo Shimbun, 1996, p. 64.
The black matrix preferably has a high light-shielding property in order to improve display contrast, and in the case of an active matrix liquid crystal display device using a thin film transistor (TFT), in order to prevent deterioration in image quality due to light current leakage. .

The production method of the black matrix is not particularly limited, but can be produced by the same method as the production method of the cured film. Specifically, a curable composition is applied on a support to form a curable composition layer, and exposed 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.

The material for the support is not particularly limited, but preferably has a transmittance of 80% or more for visible light. Specific examples of such materials include glass such as soda lime glass, alkali-free glass, quartz glass, and borosilicate glass; plastics such as polyester-based resins and polyolefin-based resins; In view of chemical resistance and heat resistance, alkali-free glass or quartz glass is preferable.

[Color filter]
The color filter according to the embodiment of the present invention contains a cured film.
The form in which the color filter contains a cured film is not particularly limited, and examples thereof include a color filter including a support and the black matrix. That is, a color filter including red, green, and blue colored pixels formed in the opening of the black matrix formed on the support can be exemplified.

A color filter containing a black matrix (cured film) can be produced, for example, by the following method.
First, a coating film (resin composition layer) of a resin composition containing a pigment corresponding to each colored pixel of a color filter is formed in an opening of a patterned black matrix formed on a support. In addition, it does not restrict | limit especially as a resin composition for each color, Although a well-known resin composition can be used, it is preferable to use the curable composition which concerns on embodiment of this invention.
Next, it exposes with respect to the resin composition layer through the photomask which has a pattern corresponding to the opening part of a black matrix. Next, after removing the unexposed portions by development processing, the colored pixels can be formed in the openings of the black matrix by baking. A color filter having a red pixel, a green pixel, and a blue pixel is manufactured by performing a series of operations using, for example, a resin composition for each color containing a red pigment, a green pigment, and a blue pigment. Can do.

[Image display device]
The image display apparatus according to the embodiment of the present invention includes a cured film. The form in which the image display device contains a cured film is not particularly limited, but examples include a form containing a color filter containing the black matrix (cured film) already described.

A typical example of the image display device according to the present embodiment is a liquid crystal display device. For example, a pair of supports arranged opposite to each other, and a liquid crystal compound sealed between the supports. The form provided with. The support is as described above as the support for the black matrix.

As a specific form of the liquid crystal display device, for example, from the user side, a polarizing plate / support / color filter / transparent electrode layer / alignment film / liquid crystal layer / alignment film / transparent electrode layer / TFT (Thin Film Transistor) The laminated body which contains an element / support body / polarizing plate / backlight unit in this order is mentioned.

The liquid crystal display device is not limited to the above. For example, “Electronic display device (Akio Sasaki, published by Industrial Research Co., Ltd., 1990)”, “Display device (written by Junaki Ibuki, Industrial Book Co., Ltd.) Liquid crystal display devices described in the " Further, for example, there is a liquid crystal display device described in “Next-generation liquid crystal display technology (Uchida, edited by Tatsuo, Kogyo Kenkyukai, published in 1994)”.

[Infrared sensor]
The infrared sensor which concerns on embodiment of this invention contains the said cured film.
The infrared sensor which concerns on the said embodiment is demonstrated using FIG. In the infrared sensor 900 shown in FIG. 9, reference numeral 910 denotes a solid-state image sensor.
The imaging region provided on the solid-state imaging device 910 is configured by combining the infrared absorption filter 911 and the color filter 912 according to the embodiment of the present invention.
The infrared absorption filter 911 transmits light in the visible light region (for example, light having a wavelength of 400 to 700 nm), and transmits light in the infrared region (for example, light having a wavelength of 800 to 1300 nm, preferably light having a wavelength of 900 to 1200 nm). Preferably, it is a film that shields light having a wavelength of 900 to 1000 nm, and a cured film containing an infrared absorber (as already described in the form of the infrared absorber) as a colorant can be used.
The color filter 912 is a color filter in which pixels that transmit and absorb light of a specific wavelength in the visible light region are formed. For example, red (R), green (G), and blue (B) pixels The formed color filter or the like is used, and the form thereof is as already described.
Between the infrared transmission filter 913 and the solid-state imaging device 910, a resin film 914 (for example, a transparent resin film or the like) that can transmit light having a wavelength transmitted through the infrared transmission filter 913 is disposed.
The infrared transmission filter 913 has a visible light shielding property and transmits infrared light having a specific wavelength, and is a colorant that absorbs light in the visible light region (for example, a perylene compound and / or a bisbenzoic acid). A cured film according to an embodiment of the present invention containing a furanone compound or the like and an infrared absorber (for example, a pyrrolopyrrole compound, a phthalocyanine compound, a naphthalocyanine compound, or a polymethine compound) can be used. For example, the infrared transmission filter 913 preferably blocks light having a wavelength of 400 to 830 nm and transmits light having a wavelength of 900 to 1300 nm.
A micro lens 915 is disposed on the incident light hν side of the color filter 912 and the infrared transmission filter 913. A planarization film 916 is formed so as to cover the microlens 915.
In the embodiment shown in FIG. 9, the resin film 914 is disposed, but an infrared transmission filter 913 may be formed instead of the resin film 914. That is, the infrared transmission filter 913 may be formed on the solid-state image sensor 910.
In the embodiment shown in FIG. 9, the film thickness of the color filter 912 and the film thickness of the infrared transmission filter 913 are the same, but the film thicknesses of both may be different.
In the embodiment shown in FIG. 9, the color filter 912 is provided on the incident light hν side with respect to the infrared absorption filter 911, but the order of the infrared absorption filter 911 and the color filter 912 is changed to change the infrared absorption filter 911. May be provided closer to the incident light hν than the color filter 912.
In the embodiment shown in FIG. 9, the infrared absorption filter 911 and the color filter 912 are stacked adjacent to each other. However, the two filters are not necessarily adjacent to each other, and other layers may be provided therebetween. . The cured film according to the embodiment of the present invention can be used as a light-shielding film such as an end or side surface of the surface of the infrared absorption filter 911, or can be used for an inner wall of an infrared sensor device to cause internal reflection or light reception. It is possible to prevent the incident of unintended light and improve the sensitivity.
According to this infrared sensor, since image information can be captured simultaneously, motion sensing or the like that recognizes a target whose motion is to be detected is possible. Furthermore, since distance information can be acquired, an image including 3D information can be taken.

Next, a solid-state imaging device to which the infrared sensor is applied will be described.
The solid-state imaging device includes a lens optical system, a solid-state imaging device, an infrared light emitting diode, and the like. As for each configuration of the solid-state imaging device, paragraphs 0032 to 0036 of JP 2011-233983 A can be referred to, and the contents thereof are incorporated in this specification.

Hereinafter, the present invention will be described in more detail based on examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the examples shown below.

[Synthesis of specific oxime compounds]
[Synthesis of INT-12]

Precursor A in the above formula was synthesized using the method described in paragraph 0026 of Japanese Patent No. 4223071. Next, with respect to the DMAc (N, N dimethylacetamide, 160 g) solution in which the precursor A (6.00 g, 12.6 mmol) was dissolved in an ice bath, myristic acid chloride (15.6 g, 63.2 mmol) was dissolved. After dropping, the mixture was stirred for 1 hour under the same temperature condition, and further stirred at 20 ° C. for 3 hours to obtain a reaction solution. Next, 400 mL of ethyl acetate and 200 mL of 4 mass% sodium bicarbonate aqueous solution were added to the reaction solution and stirred for 1 hour to generate solids in the reaction solution. Next, the generated solid was removed by Celite filtration, and the filtrate was further washed twice with 200 mL of an aqueous sodium bicarbonate solution, followed by liquid separation, and the organic phase was dried over magnesium sulfate. Next, the solvent was distilled off from the dried organic phase to obtain an oily liquid. Next, using silica gel column chromatography on the oily liquid, the developing solvent is a mixture of hexane and ethyl acetate, and the mixing ratio (volume ratio) is changed from hexane / ethyl acetate = 4/1 to hexane / acetic acid. The specific oxime compound INT-12 (9.18 mmol) was obtained after purification by changing to ethyl = 1/1. The structure of the obtained product was identified by NMR (nuclear magnetic resonance).
( ¹ H-NMR 300 MHz deuterated chloroform): 1.15 to 1.38 (m, 23H), 1.41 (d, 3H), 1.49 (t, 3H), 1.63 (quin., 2H) 2.15 (s, 3H), 2.34 (t, 2H), 3.47 (s, 3H), 3.55 (dd, 1H), 3.67 (dd, 1H), 4.43 ( q, 2H), 4.57-4.73 (m, 1H), 6.89 (dd, 1H), 6.93 (d, 1H), 6.89 (dd, 1H), 7.05 (d 1H), 7.45 (t, 2H), 8.05 (d, 1H), 8.18 (d, 1H), 8.40 (dd, 1H), 8.94 (d, 1H)

[Synthesis of INT-31]

Precursor B in the above formula was synthesized using the method described in paragraph 0379 of JP-A-2009-191061, and then cooled in an ice bath, precursor B (6.00 g, 11.3 mmol) Myristic acid chloride (3.34 g, 13.5 mmol) was added dropwise to a THF (tetrahydrofuran, 60 g) solution in which triethylamine (1.62 g, 16.0 mmol) was dissolved, and the mixture was stirred for 1 hour under the same temperature conditions after the addition. After that, the mixture was further stirred at 20 ° C. for 3 hours to obtain a reaction solution. Next, 400 mL of ethyl acetate and 200 mL of a 4% by mass aqueous sodium bicarbonate solution were added to the reaction solution and separated to obtain an organic phase. Next, the obtained organic phase was washed twice with 200 mL of an aqueous sodium bicarbonate solution and then dried over magnesium sulfate. Next, the solvent was distilled off from the dried organic phase to obtain an oily liquid. Next, using silica gel column chromatography on the oily liquid, the developing solvent is a mixture of hexane and ethyl acetate, and the mixing ratio (volume ratio) is changed from hexane / ethyl acetate = 4/1 to hexane / acetic acid. Purification was performed while changing the ethyl ratio to 1/1 to obtain an oxime compound INT-31 (8.51 g, 6.36 mmol). The structure of the obtained product was identified by NMR.
( ¹ H-NMR 300 MHz deuterated chloroform): 1.20-1.45 (m, 23H), 1.67 (quin., 2H), 2.39 (t, 2H), 3.02 to 3.23 ( m, 4H), 7.23 to 7.30 (m, 4H), 7.39 (d, 2H), 7.49 to 7.55 (m, 4H), 7.60 (t, 1H), 7 .75-7.85 (m, 4H), 8.02 (d, 2H)

[Synthesis of INT-17]

Precursor C in the above formula was synthesized using the method described in paragraph 0355 of JP-T-2016-531926. Next, similar to the synthesis of INT-31 already described, except that “precursor C (5.01 g, 11.3 mmol)” was used instead of “precursor B (6.00 g, 11.3 mmol)”. To obtain the oxime compound INT-17 (4.94 g, 7.56 mmol). The structure of the obtained product was identified by NMR.
( ¹ H-NMR 300 MHz deuterated chloroform): 0.90 (d, 6H), 1.20-1.70 (m, 26H), 2.39 (t, 2H), 2.66-2.89 (m 2H), 7.30-8.08 (m, 13H)

[Synthesis of INT-26]

Precursor D in the above formula was synthesized using the method described in paragraph 0368 of JP-A-2009-191061. Next, in place of “precursor B (6.00 g, 11.3 mmol)”, except that “precursor D (6.27 g, 11.3 mmol)” was used, the synthesis of INT-31 already described was performed. Similarly, the oxime compound INT-26 (4.72 g, 6.17 mmol) was obtained. The structure of the obtained product was identified by NMR.
( ¹ H-NMR 300 MHz deuterated chloroform): 1.19-1.44 (m, 23H), 1.49 (t, 3H), 1.70 (quin., 2H), 2.36 (s, 3H) 2.42 (t, 2H), 3.10-3.25 (m, 4H), 4.43 (q, 2H), 7.22-7.51 (m, 8H), 8.08 (dd 2H), 8.33 (dd, 2H), 8.56 (d, 1H), 8.87 (d, 1H)

The other specific oxime compounds described in Table 5 (Table 5-1 and Table 5-2) were synthesized by the same method as the above specific oxime compounds.

[Synthesis of polyfunctional thiol compounds]
[Synthesis of SH-16]

<Intermediate 1 synthesis step>
Pentaerythritol (PE) (13.5 g, 99.2 mmol) and N, N-dimethylacetamide (DMAc) (200 g) are added to a three-necked flask and stirred in a water bath at 20 ° C. under a nitrogen atmosphere to obtain a mixed solution. It was. Next, 2-bromoisobutyryl bromide (100.3 g, 595 mmol) was added dropwise to the mixture so that the temperature of the mixture did not exceed 30 ° C., and then stirred at room temperature for 2 hours to obtain a reaction solution. . Next, the reaction solution was added little by little to 1 mol / L hydrochloric acid (350 g) to stop the reaction to obtain a solution. Next, ethyl acetate (500 g) was added to the solution and the layers were separated to obtain an organic phase. Next, the organic phase was washed with saturated sodium bicarbonate water (250 g), water (250 g), and saturated brine (150 g), respectively. Next, sodium sulfate was added to the washed organic phase, and then filtered to obtain a filtrate. Next, the filtrate was concentrated under reduced pressure to obtain Intermediate 1 (70.1 g, 95.7 mmol) in the above formula.

<Intermediate 2 synthesis step>
Intermediate 1 (70.0 g, 95.6 mmol), DMAc (210 g), tetrabutylammonium bromide (TEAB) (12.8 g, 61.2 mmol) were added to a three-necked flask and stirred in a water bath under an air atmosphere. A mixture was obtained. Next, potassium thioacetate (51.0 g, 446 mmol) was added to the mixture in 4 portions and reacted at 50 ° C. for 4 hours to obtain a reaction solution. Next, ethyl acetate (310 g) and saturated aqueous sodium hydrogen carbonate solution (380 g) were added to the reaction solution, and the mixture was separated to obtain an organic phase. Next, the organic phase was washed once with 1 mol / L hydrochloric acid (350 g) and twice with saturated brine (350 g) to wash the organic phase. Next, sodium sulfate was added to the washed organic phase and filtered to obtain a filtrate. Next, the filtrate was concentrated under reduced pressure to obtain Intermediate 2 (65.8 g, 92.3 mmol) in the above formula.

<SH-16 synthesis process>
Intermediate 2 (65.0 g, 91.2 mmol) and DMAc (160 g) were added to a three-necked flask and stirred at 15 ° C. under a nitrogen atmosphere to obtain a mixed solution. Next, hydrazine hydrochloride (35.2 g, 514 mmol) and sodium acetate (84.4 g, 1.03 mol) were added to the mixed solution and reacted at a reaction temperature of 15 ° C. for 4 hours to obtain a reaction solution. Next, ethyl acetate (450 g) was added to the reaction solution, and the mixture was separated twice with 1 mol / L hydrochloric acid (280 g) and then twice with saturated brine (280 g) to obtain an organic phase, and the organic phase was washed. did. Next, magnesium sulfate was added to the washed organic phase, and then filtered to obtain a filtrate. Next, the filtrate was concentrated under reduced pressure to obtain a polyfunctional thiol compound SH-16 (48.6 g, 89.2 mmol). The structure of the obtained product was identified by NMR.
( ¹ H-NMR 300 MHz deuterated chloroform): 1.61 (s, 24H), 4.26 (s, 8H)

In addition, the other polyfunctional thiol compounds described in Table 5 were synthesized by the same method as SH-16.

[Preparation of curable composition]
The specific oxime compound, the polyfunctional thiol compound, the colorant, and other components described in each column of Table 5 were mixed to prepare the curable compositions of Examples and Comparative Examples. Table 3 shows the content of each component.

In addition, it adjusted with the organic solvent so that the final solid content of each curable composition might be 28 mass%. Moreover, the organic solvent was adjusted and used together so that the mass ratio in each curable composition might become PGMEA (propylene glycol monomethyl ether acetate) / butyl acetate / cyclohexanone = 27/18/27.

The compounds used in place of the specific oxime compounds in the curable compositions of Comparative Examples (referred to as Comparative Compound 1 and Comparative Compound 2 in Table 5-2, “CINT-1” and “CINT-2”, respectively) The structure is shown below.

(Preparation of colorant)
In addition, each coloring agent used for preparation of a curable composition was produced with the following method.

(Titanium nitride-containing particles (TiN-1))
First, Ti nanoparticles (TC-200, manufactured by Toho Tech Co., Ltd.) were formed into Ti nanoparticles by plasma treatment in Ar gas. The Ti nanoparticles after the plasma treatment were allowed to stand for 24 hours under an Ar gas atmosphere at an O ₂ concentration of 50 ppm or less and 30 ° C., and then O ₂ gas was introduced into the Ar atmosphere so that the O ₂ concentration was 100 ppm. In the state, it was left to stand at 30 ° C. for 24 hours (pretreatment of Ti particles).
Thereafter, the obtained Ti nanoparticles were classified using a TTSP separator manufactured by Hosokawa Micron under the condition of a yield of 10% to obtain a powder of Ti particles. The primary particle diameter of the obtained powder was 120 nm when the average particle diameter of 100 particles was determined by arithmetic average by TEM observation.
The titanium nitride-containing particles TiN-1 were produced using an apparatus according to the black composite fine particle production apparatus described in FIG. 1 of International Publication No. 2010/147098.
Specifically, in the black composite fine particle manufacturing apparatus, a high frequency voltage of about 4 MHz and about 80 kVA is applied to the high frequency oscillation coil of the plasma torch, and argon gas 50 L / min and nitrogen as plasma gas are supplied from the plasma gas supply source. A mixed gas of 50 L / min was supplied to generate an argon-nitrogen thermal plasma flame in the plasma torch. Moreover, 10 L / min carrier gas was supplied from the spray gas supply source of the material supply apparatus.
Then, with respect to the Ti particles obtained as described above, Fe powder (JIP270M, manufactured by JFE Steel) and Si powder (Silicon powder SI006031) have a mass ratio of Ti / Fe / Si = residue. /0.05/0.05 is mixed and supplied to the thermal plasma flame in the plasma torch together with the argon gas as the carrier gas, evaporated in the thermal plasma flame, and highly dispersed in the gas phase state. It was.
Further, nitrogen was used as a gas supplied into the chamber by the gas supply device. The flow rate in the chamber at this time was 5 m / sec, and the supply amount was 1000 L / min. The pressure in the cyclone was 50 kPa, and the supply rate of each raw material from the chamber to the cyclone was 10 m / s (average value).
In this way, titanium nitride-containing particles TiN-1 were obtained.

The obtained titanium nitride-containing particles TiN-1 were measured for the content of titanium (Ti) atoms, iron (Fe) atoms, and silicon (Si) atoms by ICP (Inductively Coupled Plasma) emission spectroscopy. For the ICP emission spectroscopic analysis, an ICP emission spectroscopic analyzer “SPS3000” (trade name) manufactured by Seiko Instruments Inc. was used.
The nitrogen atom content was measured using an oxygen / nitrogen analyzer “EMGA-620W / C” (trade name) manufactured by Horiba, Ltd., and calculated by an inert gas melting-thermal conductivity method. As a result, the mass ratio of each atom contained in the titanium nitride-containing particle TiN was Ti / N / Fe / Si = 57/34 / 0.0030 / 0.0020.

X-ray diffraction of titanium nitride-containing particles TiN-1 was measured by a wide-angle X-ray diffraction method (trade name “RU-200R” manufactured by Rigaku Corporation) with a powder sample placed in an aluminum standard sample holder. As measurement conditions, the X-ray source is CuKα ray, the output is 50 kV / 200 mA, the slit system is 1 ° -1 ° -0.15 mm-0.45 mm, the measurement step (2θ) is 0.02 °, and the scan speed is It was 2 ° / min.
And the diffraction angle of the peak derived from the TiN (200) plane observed in the vicinity of the diffraction angle 2θ (42.6 °) was measured. Furthermore, from the half width of the peak derived from the (200) plane, the crystallite size constituting the particle was determined using Scherrer's equation. As a result, the peak diffraction angle was 42.62 ° and the crystallite size was 10 nm. Note that no X-ray diffraction peak due to TiO ₂ was observed.

(Titanium nitride-containing particles TiN-2)
Instead of “TC-200” manufactured by Toho Tech Co., as “Ti-particles”, “578347” manufactured by Sigma-Aldrich Co. is used, and the Fe and Si powders have a mass ratio of Ti / Fe / Si = residue / Titanium nitride-containing particles TiN-2 were obtained in the same manner as TiN-1, except that the mixture was mixed to 0.5 / 1.
The peak diffraction angle measured by X-ray diffraction was 42.81 °, and the crystallite size was 12 nm.

(Titanium nitride-containing particles TiN-3)
Titanium nitride-containing particles TiN-3 are obtained in the same manner as TiN-1, except that Fe powder and Si powder are mixed so that the respective mass ratios are Ti / Fe / Si = residue / 1/2. It was.
The peak diffraction angle measured by X-ray diffraction was 43.1 °, and the crystallite size was 12 nm.

(Preparation of niobium nitride-containing particles containing Fe atoms (NbN))
Niobium nitride-containing particles containing Fe atoms were produced by the following method.
First, niobium (powder) <100-325 mesh> manufactured by Mitsuwa Chemicals was prepared as a raw material (hereinafter also referred to as “metal raw material powder”).
Next, the metal raw material powder was formed into Nb nanoparticles by plasma treatment in Ar gas (the treatment conditions were the following plasma treatment (1)).

・ Plasma treatment (1)
Plasma treatment (1) was performed by the following method. Plasma treatment (1) was performed under the following conditions using an apparatus according to the above black composite fine particle production apparatus.
・ High frequency voltage applied to the coil for high frequency oscillation: frequency, about 4 MHz, voltage, about 80 kVA
・ Plasma gas: Argon gas (Supply rate: 100 L / min)
Carrier gas: Argon gas (Supply amount: 10 L / min)
-Chamber atmosphere: Argon gas (Supply rate 1000L / min, Chamber flow rate 5m / sec)
・ Cyclone atmosphere: Argon gas, Internal pressure: 50 kPa
・ Material supply speed from chamber to cyclone: 10 m / s (average value)

Next, Fe powder (JIP270M, manufactured by JFE Steel Co., Ltd.) was prepared, and plasma treatment was performed under the conditions of the plasma treatment (1) to form Fe nanoparticles.

Next, the Nb nanoparticles and Fe nanoparticles obtained as described above were mixed to obtain a raw metal powder. The raw material metal powder was subjected to plasma treatment in nitrogen gas (treatment conditions were as described in the following plasma treatment (2)) to obtain niobium nitride-containing particles.

・ Plasma treatment (2)
Plasma treatment (2) was performed by the following method. The apparatus used is the same as in the plasma treatment (1).
・ High frequency voltage applied to the coil for high frequency oscillation: frequency, about 4 MHz, voltage, about 80 kVA
・ Plasma gas: Argon gas and nitrogen gas (Supply amount 50L / min each)
・ Carrier gas: Nitrogen gas (Supply amount: 10L / min)
・ Atmosphere in the chamber: Nitrogen gas (amount supplied: 1000 L / min, flow velocity in the chamber: 5 m / sec)
・ Cyclone atmosphere: Nitrogen gas, internal pressure 50kPa
・ Material supply speed from chamber to cyclone: 10 m / s (average value)

After completion of the plasma treatment (2), nitrogen gas at 20 ° C. is introduced under the condition that the relative humidity is 95% in the atmosphere by using a shunt type humidity supply device SRH manufactured by Nippon Shintec Co., Ltd. using Ar gas. Let stand for hours. Thereafter, the obtained particles were classified using a TTSP separator manufactured by Hosokawa Micron under the condition of a yield of 10% to obtain niobium nitride-containing particles (NbN). Nitrogen gas was supplied to the separator.
About the obtained niobium nitride containing particle | grains, when content of an iron (Fe) atom was measured by ICP emission spectroscopy analysis, it was 50 mass ppm.

(Production of vanadium nitride-containing particles (VN) containing Fe atoms)
In the production of niobium nitride-containing particles containing Fe atoms, Fe atoms were used in the same manner except that Niobium Metal Vanadium Powder VHO was used instead of Mitsuwa Chemical Niobium (Powder) <100-325 mesh>. Vanadium nitride-containing particles (VN) containing About the obtained vanadium nitride containing particle | grains, when content of an iron (Fe) atom was measured by ICP emission spectroscopy analysis, it was 50 mass ppm.

In Table 5, the colorants other than those described above are the colorants described in Table 4 below, or a mixture of colorants.

The structures of Compound SQ-23 and Compound A-52 in Table 4 are shown below.
Compound SQ-23

Compound A-52 (wherein Ph represents a phenyl group)

[Dispersant]
Dispersant A having the following structure was used as the dispersant. The numerical value described in each structural unit intends mass% of each structural unit with respect to the total structural unit.

[Binder resin]
As the binder resin, a resin A having the following structure was used. In the formula of resin A, each abbreviation represents the following. The numerical value described in each structural unit intends mass% of each structural unit with respect to the total structural unit. Resin A corresponds to an alkali-soluble resin.
-BzMA: benzyl methacrylate-MMA: methyl methacrylate

(Polymerizable compound)
As the polymerizable compound, a polymerizable compound M1 and a polymerizable compound M2 were used.
The structure of the polymerizable compound M1 (dipentaerythritol hexaacrylate) is as follows (product name “KAYARAD”, manufactured by Nippon Kayaku Co., Ltd.).

Polymerizable compound M2: PET-30 (pentaerythritol triacrylate, manufactured by Nippon Kayaku Co., Ltd.)

[Surfactant]
F-1: Compound represented by the following formula (weight average molecular weight (Mw) = 15311)
However, in the following formula, the structural units represented by the formulas (A) and (B) are 62 mol% and 38 mol%, respectively. In the structural unit represented by the formula (B), a, b, and c satisfy the relationships of a + c = 14 and b = 17, respectively.

[Evaluation of curable composition]
[Pattern shape]
Each curable composition was hermetically sealed in a 100 mL capacity Bloom bottle and stored for 7 days in a constant temperature bath at 60 ° C. (heating forced aging). Next, using each of the curable compositions after forced heating, the surface was rotated on a Si substrate (corresponding to a support) whose SiO _{2 was} treated so that the film thickness after drying was 1.5 μm. The number was adjusted and a coating film (curable composition layer) was formed by spin coating. Next, the formed coated substrate was placed on a hot plate and dried by heat treatment (prebaking) at 100 ° C. for 2 minutes. Next, using the i-line stepper (Canon FPA3000i5 +) on the substrate with the pre-baked coating film (curable composition layer), the coating film is passed through a photomask in which a line pattern of length 200 μm × width 20 μm is formed. Was exposed (negative). Next, the coated film after exposure is subjected to paddle development for 30 seconds using tetramethylammonium hydroxide as a developer using a coater developer ACT8 manufactured by Tokyo Electron, and then shower rinse for 20 seconds using pure water. Thus, a patterned cured film was obtained.
Next, the patterned cured film was post-baked (temperature: 220 ° C., time: 300 seconds). The pattern shape of the cured film after post-baking was measured by a length measuring SEM (Scanning Electron Microscope). Specifically, the film thickness at the end of the line pattern and the film thickness at the center were measured, and the ratio (film thickness at the pattern end / film thickness at the center) was calculated and evaluated according to the following criteria. In addition, evaluation "2" or more is a practical range. The results are shown in Table 5.
-7: The ratio is more than 0.98 and less than 1.00, and no difference is observed in the film thickness between the central part and the end part of the pattern by observation with SEM.
6: The ratio is more than 0.96 and not more than 0.98, and there is a slight difference in the film thickness between the central portion and the end portion of the pattern.
5: The ratio is more than 0.94 and not more than 0.96, and there is a difference in the film thickness between the center and end of the pattern.
-4: The ratio is more than 0.92 and less than 0.94, the film thickness at the end is thin, and it is slightly distorted, but there is no practical problem.
-3: The ratio is more than 0.90 and not more than 0.92, and the film thickness at the end is thin and distorted, but there is no practical problem.
-2: The ratio is more than 0.80 and 0.90 or less, and the film thickness at the end is thin, but the practical level is possible.
-1: The ratio is 0.80 or less, the film thickness at the end is thin, and is not acceptable.

[Development residue suppression performance]
By the same method as described above, a substrate with a coating film was produced using each constituent composition. Thereafter, development was performed in the same manner as described above, and the number of development residues on the Si substrate was measured. Specifically, when the coating film was exposed, the number of residues in the region not irradiated with light (unexposed portion) was observed with SEM (magnification: 20000 times) to evaluate the development residue suppression performance. The evaluation criteria are as follows. The results are shown in Table 5.
A: No residue is observed at all in the unexposed area.
B: One or more residues were observed in an unexposed area of 1.0 μm square.
C: 4 or more and 7 or less residues were observed in an unexposed area of 1.0 μm square.
D: 8 or more and 10 or less residues were observed in an unexposed area of 1.0 μm square.
E: 11 or more residues were observed in an unexposed area of 1.0 μm square.
“D” or more is preferable for practical use, and “A” and “B” are evaluated to have particularly excellent performance.

In Table 5, “content” of the specific oxime compound (A) and the polyfunctional thiol compound (B) is the specific oxime compound (A) when the total solid content of the curable composition is 100% by mass and It is content (mass%) of each of polyfunctional thiol compound (B).
-In Table 5, "A / B" represents content mass ratio of content of a specific oxime compound (A) with respect to content of the polyfunctional thiol compound (B) in a curable composition.
In Table 5, the types of colorants CP-1 to CP-8 represent chromatic pigments 1 to 8 in Table 4, respectively.

From the result shown in Table 5, the curable composition which concerns on each Example had the effect of this invention. On the other hand, the curable composition which concerns on a comparative example did not have the effect of this invention.
Compared with the curable composition of Example 8, the curable composition of Example 1 which contains the specific oxime compound whose carbon number of R < ¹ > of Formula (1) is 13 or more is a pattern of the cured film obtained. The shape was better.
The curable composition of Example 3 containing a polyfunctional thiol compound (secondary thiol compound) in which R ^{24 in} Formula (2) is other than a hydrogen atom is the curable composition of Example 4 (R ²⁴ and Compared with a primary thiol compound in which both R ²⁵ are hydrogen atoms, the development residue suppression performance was superior. Moreover, the curable composition of Example 35 containing a polyfunctional thiol compound (tertiary thiol compound) in which both R ²⁴ and R ²⁵ are other than a hydrogen atom has a further excellent development residue suppressing performance. It was.
In addition, the curable compositions of Examples 43 and 47 in which n in the formula (2) is 3 to 10 are obtained in comparison with the curable composition of Example 46 (n is 2). The film pattern shape was more excellent.
The curable composition of Example 12 in which the content ratio of the oxime compound content to the polyfunctional thiol compound content was 4 to 10 was compared with the curable compositions of Example 10 and Example 13. Thus, the pattern shape of the obtained cured film was more excellent.
Curing of Examples 15 to 19 and Examples 21 to 22 in which R ^{1 in the} formula (1) is a linear alkyl group having 13 or more carbon atoms or a group represented by * -L ¹¹ -R ¹¹ Compared with the curable composition of Example 20, the cured film obtained had a more excellent pattern shape.

[Example 71]
In place of TiN-1, TiN-1 and carbon black (trade name “Color Black S170”, manufactured by Degussa, average primary particle diameter 17 nm, BET specific surface area 200 m ² / g, carbon black manufactured by gas black method) When the evaluation was performed in the same manner as in Example 43 except that the solid content mass ratio was 7: 3, the same effect as in Example 43 was obtained.

[Example 72]
A curable composition was prepared and evaluated in the same manner as in Example 43 except that the surfactant was not used. As a result, the same result as in Example 43 was obtained.

[Example 73]
A curable composition was prepared and evaluated in the same manner as in Example 43 except that the polymerization inhibitor was not used. As a result, the same result as in Example 43 was obtained.

DESCRIPTION OF SYMBOLS 101 ...

Support body

102, 401 ... Curable composition layer 103 ...

Photomask

201, 501 ... Cured

film

301, 601 ... Post-baked cured film 700 ... Solid-state imaging device 701: Solid-state imaging device 702 ... Imaging unit 703 ... Cover glass 704 ... Spacer 705 ... Multilayer substrate 706 ... Chip substrate 707 ... Circuit board 708 ... Electrode pad 709 ..External connection terminal 710... Through electrode 711... Lens layer 712. Lens material 713... Support 714, 715... Cured film 801. ... Microlens 804 ... Substrate 805b ... Blue pixel 805r ... Red pixel 805g ... Green pixel 805bm ... Black matrix 806 ... p well layer 807... read gate portion 808. vertical transfer path 809... element isolation region 810... gate insulating film 811. vertical transfer electrode 812. Insulating film 815 ... Planarizing film 900 ... Infrared sensor 910 ... Solid-state imaging device 911 ... Infrared absorption filter 912 ... Color filter 913 ... Infrared transmission filter 914 ... Resin film 915 ..Microlens 916 ... Planarizing film

Claims

A curable composition containing a photopolymerization initiator, a polyfunctional thiol compound, a polymerizable compound, and a colorant,
The curable composition whose said photoinitiator is an oxime compound represented by the following formula | equation (1).

In Formula (1), R 1 represents a hydrocarbon group having 8 or more carbon atoms that may contain a hetero atom, R 2 represents an alkyl group or an aryl group, and X 2 represents a single bond, or Represents a divalent linking group, R 3 represents an aryl group, and X 3 represents a single bond or a carbonyl group.
The curable composition of Claim 1 whose carbon number of R1 in the said Formula (1) is 13 or more.
The curable composition according to claim 1 or 2, wherein the content ratio of the content of the oxime compound to the content of the polyfunctional thiol compound in the curable composition is 1 to 10.
The curable composition according to any one of claims 1 to 3, wherein the content ratio of the content of the oxime compound to the content of the polyfunctional thiol compound in the curable composition is 4 to 10. object.
The curable composition according to any one of claims 1 to 4, wherein the polyfunctional thiol compound is a compound represented by the following formula (2).

In the formula (2), R 24 and R 25 each independently represent a hydrogen atom, an alkyl group, an aryl group, —C (═O) —R 23 , —C (═O) —O—R 23 , or —C (═O) —NH—R 23 , L 21 represents an n-valent organic linking group, n represents an integer of 2 to 10, and M 21 represents a single bond, —O—, —S —, —N (R 23 ) —, —C (═O) —O—, —O—C (═O) —O—, —C (═O) —NH—, —C (═O) —, Represents an alkylene group or a group in which two or more of these are combined, R 23 represents an alkyl group or an aryl group, and a plurality of R 24 , R 25 and M 21 may be the same or different, When there are a plurality of R 23 s , they may be the same or different.
In the formula (2), R 24 and R 25 are each independently an alkyl group or —C (═O) —O—R 23 , and M 21 is —C (═O) —O—. The curable composition according to claim 5, wherein n is an integer of 3 to 10.
The curable composition according to any one of claims 1 to 6, wherein the colorant comprises an organic pigment.
The curable composition according to any one of claims 1 to 6, wherein the colorant comprises an inorganic pigment.
A cured film obtained by curing the curable composition according to any one of claims 1 to 8.
A color filter containing the cured film according to claim 9.
A light-shielding film containing the cured film according to claim 9.
A solid-state imaging device containing the cured film according to claim 9.
An image display device comprising the cured film according to claim 9.
A curable composition layer forming step of forming a curable composition layer on a support using the curable composition according to any one of claims 1 to 8,
The manufacturing method of the cured film containing the exposure process which exposes the said curable composition layer.
The curing according to claim 14, wherein the curable composition layer forming step is a step of applying the curable composition on the support to form the curable composition layer on the support. A method for producing a membrane.
Furthermore, the manufacturing method of the cured film of Claim 14 or 15 containing the image development process which develops the exposed said curable composition layer.