JP6680907B2 - Curable composition, cured film, color filter, light shielding film, solid-state imaging device, image display device, and method for producing cured film - Google Patents

Description

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

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

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

JP, 2013-83932, A

  The present inventors 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, the pattern shape means 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 (henceforth "it has the effect of this invention.").
Another object of the present invention is to provide a cured film, a color filter, a light shielding film, a solid-state image sensor, an image display device, and a method for manufacturing a cured film.

  Means for Solving the Problems As a result of intensive studies to achieve the above object, the present inventors have found that the above object 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 an oxime compound represented by the formula (1). Which is a curable composition.
[2] The curable composition according to [1], wherein R ¹ in the formula (1) has 13 or more carbon atoms.
[3] The curable composition according to [1] or [2], wherein the content mass ratio of the content of the oxime compound to the content of the polyfunctional thiol compound in the curable composition is 1 to 10.
[4] The curable composition according to any one of [1] to [3], wherein the content mass ratio of the content of the oxime compound to the content of the polyfunctional thiol compound in the curable composition is 4 to 10. Stuff.
[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 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. -, And n is an integer of 3-10, The curable composition as described in [5].
[7] The curable composition according to any one of [1] to [6], wherein the colorant is an organic pigment.
[8] The curable composition according to any one of [1] to [6], wherein the colorant is 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 containing 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, which comprises:
[15] The cured film according to [14], wherein the curable composition layer forming step is a step of forming a curable composition layer on the support by applying the curable composition on the support. Production method.
[16] The method for producing a cured film according to [14] or [15], which further includes a developing step of developing the exposed curable composition layer.

According to the present invention, it is possible to provide a curable composition capable of obtaining a cured film having an excellent pattern shape.
Further, according to the present invention, a cured film, a color filter, a light shielding film, a solid-state image sensor, an image display device, and a method for manufacturing a cured film can be provided.

It is sectional drawing which showed typically the manufacturing process of the cured film which used 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 which used 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 which used the curable composition which does not contain a polyfunctional thiol compound for every process. It is sectional drawing which showed 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 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 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 components described below may be made based on typical embodiments of the present invention, but the present invention is not limited to such embodiments.
In this specification, a numerical range represented by using “to” means a range including numerical values described before and after “to” as a lower limit and an upper limit.
In the description of the group (atomic group) in the present specification, the notation in which substitution and non-substitution are not included includes not only those having no substituent but also those having a substituent. For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
The term “actinic ray” or “radiation” as used herein means, for example, deep ultraviolet rays, extreme ultraviolet rays (EUV), X-rays, electron beams and the like. Moreover, in this specification, "light" means actinic rays and radiation. Unless otherwise specified, "exposure" in the present specification includes not only exposure with deep 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” means acrylate and methacrylate. In the present specification, “(meth) acrylic” means acrylic and methacrylic. In the present specification, “(meth) acryloyl” represents acryloyl and methacryloyl. As used herein, “(meth) acrylamide” refers to acrylamide and methacrylamide.
In the present specification, “monomer” and “monomer” have the same meaning. A monomer is a compound having a weight average molecular weight of 2,000 or less, which is distinguished from an oligomer and a polymer. In the present specification, the polymerizable compound means a compound having a polymerizable group and may be a monomer or a polymer. The polymerizable group means a group involved in the polymerization reaction.

[Curable composition]
The curable composition according to the embodiment of the present invention contains a photopolymerization initiator, a polyfunctional thiol compound, a polymerizable compound, and a colorant, and the photopolymerization initiator is represented by Formula (1) described below. One of the features is that it is an oxime compound (hereinafter, also referred to as a "specific oxime compound").

  According to the curable composition of the present invention having such a constitution, a cured film having an excellent pattern shape can be obtained. The reason for this is not clear in detail, but the present inventors presume as follows. The scope of the present invention is not limited by the following assumptions. In other words, even when the effect is obtained by a mechanism other than the inferred mechanism below, 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 onto a support to obtain a curable composition layer, which is exposed in a pattern and developed. However, the optical density (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 patternwise exposed 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. In some cases, the curable composition did not reach the inside, the exposure was insufficient, and as a result, the curable composition did not cure as intended, and the pattern shape of the cured film deteriorated.
The mechanism by which the pattern shape deteriorates as described above will be described with reference to FIGS. First, FIGS. 1-3 is sectional drawing which showed the manufacturing process of the cured film using the curable composition which does not contain a polyfunctional thiol compound typically for every 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, the arrow indicates the irradiation direction of light, and the line AB is the end of the opening of the photomask. It is an extension of the same. 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 during the exposure, and the exposure is insufficient in the lower portion of the curable composition layer 102. Becomes Then, due to the development, the curable composition elutes in the insufficiently exposed portion of the curable composition layer 102 (FIG. 2). When the post-baking treatment for heating the cured film 201 is performed in such a state, the film thickness at the end portion of the obtained post-baked cured film 301 is reduced as compared with the central portion, and the pattern shape becomes It is presumed that it is likely to deteriorate (Fig. 3).

On the other hand, FIGS. 4 to 6 are cross-sectional views schematically showing the steps of 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, inside the exposed curable composition layer 401, the polymerization reaction is started by the 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 interferes with the polymerization reaction is generated by the reaction of 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 considered that a thiyl radical that is hard to receive is generated and the polymerization reaction proceeds. Therefore, it is presumed that the curable composition containing the polyfunctional thiol compound is likely to be 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 the conditions such as the composition of the curable composition, the exposure amount, and the pattern shape, the radical polymerization reaction causes chain reaction to the unexposed portion. In particular, the unexposed portion of the curable composition layer on the light irradiation surface side may be inadvertently cured. In this case, when the curable composition layer after exposure is developed, the cured film 501 may unintentionally spread to the unexposed portion (FIG. 5). When such a problem occurs, the edge of the cured film 601 after post-baking may unintentionally spread, and the pattern shape may deteriorate (FIG. 6).

The present inventors, who discovered the above phenomenon for the first time, have conducted earnest studies and completed the present invention. The curable composition of the present invention is an oxime compound (specific oxime compound) containing a hydrocarbon group having 8 or more carbon atoms, in which R ¹ of the formula (1) described later may contain a hetero atom, as a photopolymerization initiator. Contains. 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 does not easily diffuse in the curable composition layer. Therefore, even when using a highly reactive polyfunctional thiol compound as a chain transfer agent, the radical species is less likely to diffuse in the unexposed area, and as a result, the curing reaction is less likely to occur in the unexposed area, resulting in an excellent pattern shape It is speculated that a cured film having the above 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 below.

[Specific oxime compound]
The curable composition according to the embodiment of the present invention contains a specific oxime compound described 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 mass% with respect to the total solid content of the curable composition. The specific oxime compound may be used alone or in combination of two or more. When two or more specific oxime compounds are used in combination, the total content is preferably within the above range.
As the specific oxime compound, the N—O bond may be in the (E) form or the (Z) form. As the specific oxime compound, the (E) form and the (Z) form 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 them, a linear, branched, or cyclic hydrocarbon having 13 or more carbon atoms, which may contain a hetero atom, in that a curable composition having a more excellent effect of the present invention can be obtained. Groups are preferred.
The hetero atom contained in R ¹ is not particularly limited, and examples thereof include a nitrogen atom, a sulfur atom, and an oxygen atom.
R ¹ is, 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, but for example, an alkylene group, a carbonyl group, —O—, —S—, —NR ¹² —, and combinations thereof are preferable, and an alkylene group is 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.

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

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 as the divalent linking group, an alkylene group (preferably having a carbon number of 1 to 12), a cycloalkylene group, an alkenylene group, an alkynylene. Group, a carbonyl group, -S-, -O-, -NR < ¹⁵ >-, and a group in which these are combined, and the like, and a curable composition having a more excellent effect of the present invention can be obtained. 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, R ² is a linear alkyl group having 1 to 25 carbon atoms, which may each have a substituent, in that a curable composition having a more excellent effect of the present invention can be obtained. A branched chain 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. The substituent is, for example, a halogen atom (among which a fluorine atom is preferable), an aryloxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, an acyl group, an alkyl group, an aryl group, and *- Examples thereof include a group represented by X ⁶ -R ⁶ , but are not limited thereto. In addition, * represents a bonding position, and the form of X ⁶ and R ⁶ will be described later.

In formula (1), X ³ represents a single bond or a carbonyl group. In addition, R ³ represents an aryl group and may contain a substituent, and in particular, R ³ is represented by the following formula (from the viewpoint that a curable composition having more excellent effects of the present invention can be obtained). The group represented by 1-2) is preferable.
^{* - [Ar] -X 6 -R} 6 formula (1-2)
In the 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. As the divalent linking group for X ⁶ , an alkylene group, an arylene group, a cycloalkylene group, an alkenylene group, an alkynylene group, a carbonyl group, —S—, —O—, —NR ⁶¹ —, and a group in which these are combined. Is mentioned. Here, R ⁶¹ represents a hydrogen atom or an alkyl group. Among them, X ⁶ is preferably a single bond, —S—, or a carbonyl group, because a curable composition having a more excellent effect of the present invention can be obtained.
Further, 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. The substituent may be a substituent which the aryl group of R ² may contain.

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

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

In Formula (1-A) to Formula (1-D) and Formula (1-a) to Formula (1-d), R ¹ , R ² , X ² , and X ³ are respectively represented by Formula (1 ) Has the same meaning as R ¹ , R ² , X ² , and X ^{3 in} (), and the preferred forms are also the same.
In formula (1-A) to formula (1-D) and formula (1-a) to formula (1-d), R ¹⁰ represents a hydrogen atom or a monovalent substituent. The monovalent substituent is not particularly limited, but is, for example, —NO ₂ (hereinafter, also referred to as nitro group), a group represented by * —X ⁶ —R ⁶ , or an aryl group which may have a substituent. , And an aryl heterocyclic group which may have a substituent.

In formula (1-A) to formula (1-D) and formula (1-a) to formula (1-d) (however, formula (1-B) and formula (1-b) are excluded), R ⁷ is -O -, - S-, or, ^{-NR 71} - represents a. R ⁷¹ represents a substituent, and the substituent is not particularly limited, but is, for example, an alkyl group having 1 to 20 carbon atoms (which may be linear, branched, or cyclic). A C4 to C20 alicyclic hydrocarbon group, a C6 to C30 aryl group, and a C7 to C30 arylalkyl group. The above-mentioned substituent may contain a hetero atom, and among them, in that a curable composition having a more excellent effect of the present invention can be obtained, the hetero atom is a nitrogen atom, an oxygen atom, and a halogen atom or the like. Are preferred, and a nitrogen atom, an oxygen atom, or a fluorine atom is more preferred.

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 described above for 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 addition, in Table 1, a wavy line represents a bonding position, and “↑” represents the same as the immediately preceding column. Further, "- X ² -R ^2" structure shown in the column of the represent form groups represented by the linking group X ² and R ² are bonded. The contents of the "formula" column, the formula (1-a) correspond to ~ (1-d), each symbol ^{(R 1, -X 2 -R 2} , X 3, R 7, R 8, And R ¹⁰ ) correspond to the respective symbols in each formula. Further, “none” in the R ⁷ and R ⁸ columns means that the compound represented by the corresponding formula does not contain the groups represented by R ⁷ and R ⁸ , respectively. The numbers (“INT-1” to “INT-50”) of the specific oxime compounds 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 further preferably has high absorbance at 365 nm and 405 nm.
From the viewpoint of sensitivity, the molar absorption coefficient of the oxime compound at 365 nm or 405 nm is preferably 1,000 to 300,000, more preferably 2,000 to 300,000, and even more preferably 5,000 to 200,000.
The molar extinction coefficient of a compound can be measured by a known method, for example, it is measured at a concentration of 0.01 g / L using an ethyl acetate solvent with an ultraviolet-visible spectrophotometer (Cary-5 spctrophotometer manufactured by Varian). It is preferable.

  The specific oxime compound can be synthesized by a known method. Typically, it can be synthesized by reacting the corresponding oxime with an acid chloride in the presence of a base in an inert solvent 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 and the like.

[Polyfunctional thiol compound]
The curable composition according to the embodiment of the present invention contains a polyfunctional thiol compound. In the present specification, the polyfunctional thiol compound is intended to include a compound containing two or more thiol groups (that is, a group represented by —SH) in the same molecule.
Although the content of the polyfunctional thiol compound is not particularly limited, it is often 0.1 to 10 mass% with respect to the content of the colorant. Among these, 0.5 to 8.0 mass% is preferable with respect to the content of the colorant in that the curable composition has the more excellent effect of the present invention.
In addition, the content of the polyfunctional thiol compound is preferably 0.1 to 8.0 mass% and more preferably 0.3 to 6.0 mass% with respect to the total solid content of the curable composition.
The polyfunctional thiol compounds may be used alone or in combination of two or more. When two or more kinds are used in combination, it is preferable that the total is within the above range.

  The relationship between the polyfunctional thiol compound and the content of the specific oxime compound is not particularly limited, but a curable composition gives a cured film having a more excellent pattern shape (having a more excellent effect of the present invention. ), The content mass ratio of the content of the specific oxime compound to the content of the polyfunctional thiol compound in the curable composition (content of the specific oxime compound / content of the polyfunctional thiol compound) is 0. 1-15 are preferable, 0.5-12 are more preferable, 1-10 are more preferable, 4-10 are especially preferable.

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

In formula (2), R ²⁴ and R ²⁵ are each a hydrogen atom, an alkyl group, an aryl group, —C (═O) —R ²³ , —C (═O) —O—R ²³ , or —C. (= O) represents ^{-NH-R 23,} an alkyl group, ^{or, -C (= O) -O-} R 23 are preferred. Note that 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 connecting 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 a carbon number of 1 to 8) or a divalent aromatic hydrocarbon group (preferably having a carbon number of 6 to 12) , -O-, -S-, -N (Rx)-(Rx: monovalent organic group), -C (= O)-, -C (= O) -O-, -OC (= 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 group in which these are combined (for example, an alkyleneoxy group, an alkyleneoxycarbonyl group, an alkylenecarbonyloxy group, etc.) and the like. To be
When L ²¹ is a trivalent or higher-valent organic linking group, for example, isocyanuric containing 3 trimethylolpropane residues and-(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 or a pentavalent linking group, a hexavalent linking group such as a dipentaerythritol residue, and a combination 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 in which these are combined.

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 the three T ³ may be the same or different from each other.
L ⁵ represents a tetravalent group. T ⁴ represents a single bond or a divalent linking group, and four T ⁴ may be the same or different from each other.
L ⁶ represents a pentavalent group. T ⁵ represents a single bond or a divalent linking group, and 5 T ^{5 s} may be the same or different from each other.
L ⁷ represents a hexavalent group. T ⁶ represents a single bond or a divalent linking group, and 6 T ⁶ may be the same or different from each other.
The definition of the divalent linking group represented by T ³ , T ⁴ , T ^5, and T ⁶ is the same as the definition of the divalent linking group represented by L ²¹ described above.

The n-valent linking group for L ²¹ is preferably, for example, a group represented by any of the following formulas (E) to (J), or a group obtained by combining these.

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 bonding position. t represents an integer of 2 or more.

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

Wherein ^{(2), M 21} is 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 thereof are combined, and -C (= O) -O- is preferable. R ²³ represents an alkyl group or an aryl group, and a plurality of M ²¹ may be the same or different.

Among them, at least one selected from the group consisting of R ²⁴ and R ²⁵ in formula (2), as the polyfunctional thiol compound, in that the curable composition has more excellent development residue suppression performance. Is preferably other than a hydrogen atom (secondary thiol compound), more preferably both R ²⁴ and R ²⁵ are other than hydrogen atom (tertiary thiol compound), R ²⁴ and R ²⁵ are It is further preferable that each independently is an alkyl group or —C (═O) —O—R ²³ .
The number of carbon atoms when R ²⁴ and R ²⁵ are each other than a hydrogen atom is not particularly limited, but is preferably 1 or more independently for the curable composition to have more excellent development residue suppression performance. It is more preferable that at least one of R ²⁴ and R ²⁵ is 2 or more. The upper limit of the carbon number is not particularly limited, but generally 5 or less is preferable.
Further, M ²¹ is preferably —C (═O) —O—, and n is preferably an integer of 3 to 10.
In the present specification, the development residue suppressing performance means the physical properties of the curable composition evaluated by the method described in the 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 addition, L ²¹ , M ²¹ , R ²⁴ , R ²⁵ , and n in the table correspond to the respective symbols in the formula (2). Further, in Tables 2-1 to 2-3, "*" and "●" respectively represent bonding positions, "*" represents the bonding position of 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 polyfunctional thiol compounds correspond to the numbers of the polyfunctional thiol compounds in the examples.

(Coloring agent)
The curable composition according to the embodiment of the present invention contains a colorant. Although the content of the colorant in the curable composition is not particularly limited, it is generally preferably 30 to 70 mass% with respect to the total solid content of the curable composition. The colorants may be used alone or in combination of two or more. When two or more colorants are used in combination, the total content is preferably within the above range.
When the cured film is used as a light-shielding film, the content of the colorant in the curable composition is not particularly limited, but 40 mass% in terms of obtaining a cured film (light-shielding film) having more excellent light-shielding properties. % Or more is preferable.
Although the upper limit of the content of the colorant is not particularly limited, it is generally preferably 70% by mass or less based on the total solid content of the curable composition. When the content of the colorant is at most the upper limit value, the curable composition has more excellent coatability.
Colorants include pigments and dyes. Hereinafter, the colorant will be described in detail.

(Pigment)
The pigment is not particularly limited, and known inorganic pigments and / or organic pigments can be used. The curable composition according to the present embodiment preferably contains an inorganic pigment as a colorant. Further, the curable composition according to the present embodiment also preferably contains an organic pigment as a colorant.

-Inorganic Pigment The inorganic pigment is not particularly limited, and known inorganic pigments can be used.
Examples of the inorganic pigment include zinc white, white lead, lithopone, titanium oxide, chromium oxide, iron oxide, precipitated barium sulfate and barite powder, red lead, iron oxide red, yellow lead, zinc yellow (zinc yellow type 1, Zinc Yellow 2), Ultramarine Blue, Prussian Blue (Potassium Ferrocyanide) Zircon Gray, Praseodymium Yellow, Chrome Titanium Yellow, Chrome Green, Peacock, Victoria Green, Navy Blue (unrelated to Prussian Blue), Vanadium Zirconium Blue, Examples include chrome tin pink, ceramic red, and salmon pink. The black inorganic pigments include metal oxides and metals containing at least one metal element selected from the group consisting of Co, Cr, Cu, Mn, Ru, Fe, Ni, Sn, Ti, and Ag. Examples thereof include nitrogen compounds and metal oxynitrides.

As the inorganic pigment, carbon black, titanium black, and metallic pigments (hereinafter, referred to as “black Also referred to as a "pigment"). Examples of the metal pigments include metal oxides 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 nitrogen compounds.
The inorganic pigment is preferably at least one selected from the group consisting of titanium nitride, titanium oxynitride, niobium nitride, vanadium nitride, silver, or a metal pigment containing tin, and a metal pigment containing silver and tin. More preferably, 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.
Note that carbon black can also be used as the inorganic pigment. Specific examples of carbon black include C.I. I. Pigment Black 7 and the like, but not limited to these.

The curable composition may contain a pigment having an infrared absorbing property other than the pigment described as the black pigment.
As the pigment having an infrared ray absorbing property, a tungsten compound or a metal boride is preferable, and above all, a tungsten compound is more preferable from the viewpoint of excellent light shielding properties at a wavelength in the infrared region.

These pigments may be used in combination of two or more, and may also be used in combination with a dye described below. In order to adjust the tint and to enhance the light shielding property in a desired wavelength region, for example, a black pigment or a pigment having an infrared light shielding property, a chromatic color such as red, green, yellow, orange, purple, and blue Examples include a mode in which a pigment or a dye described below is mixed. It is preferable to mix a red pigment or a red dye, or a purple pigment or a purple dye with a black pigment or a pigment having an infrared ray shielding property, and it is more preferable to mix a red pigment with a black pigment or a pigment having an infrared ray shielding property. .
Further, a near infrared ray absorbing agent or an infrared ray absorbing agent described later may be added to the curable composition.

The black pigment is preferably titanium black or niobium oxynitride. 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 needed for the purpose of improving dispersibility, suppressing cohesion, and the like. Specifically, titanium black can be coated with silicon oxide, titanium oxide, germanium oxide, aluminum oxide, magnesium oxide, or zirconium oxide. Further, titanium black can be treated with a water-repellent substance as disclosed in JP2007-302836A.
Titanium black is typically titanium black particles, and it is preferable that each of the individual particles has a small primary particle diameter and an average primary particle diameter. The same applies to niobium oxynitride.
Specifically, the average primary particle diameter is preferably in the range of 10 nm to 45 nm.

The average primary particle diameter of the pigment can be measured using a 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 means the maximum length of a particle image obtained by using a transmission electron microscope (Dmax: maximum length at two points on the contour of the particle image), and the maximum vertical length ( DV-max: When the image is sandwiched by two straight lines parallel to the maximum length, the shortest length that connects the two straight lines vertically is measured, and the geometric mean value (Dmax × DV-max) 1 / 2 was defined as the particle size. The average primary particle diameter of the pigment is measured by measuring the particle diameter of 100 particles by this method, and intends the arithmetic mean value thereof.

The specific surface areas of titanium black and niobium oxynitride are not particularly limited, but since the water repellency after surface treatment of titanium black and niobium oxynitride with a water-repellent agent has a predetermined performance, BET (Brunauer, Emmett, Teller ) is preferably measured value is 5~150m ² / g by method, and more preferably 20~120m 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 Corp.), Tilack. Examples include D (trade name, manufactured by Ako Kasei Co., Ltd.) and titanium nitride 50 nm (trade name, manufactured by Wako Pure Chemical Industries, Ltd.).

  As the colorant, it is preferable to use titanium oxynitride, titanium nitride or niobium oxynitride, and titanium oxide or niobium oxynitride is more preferable, and niobium oxynitride is further preferable, because the obtained cured film has more excellent moisture resistance. preferable. This is probably because these colorants are hydrophobic.

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

In this form, titanium black is contained as a substance to be dispersed in the curable composition, and the content ratio (Si / Ti) of Si atoms and Ti atoms in the substance to be dispersed is 0. 05 or more is preferable, 0.05 to 0.5 is more preferable, and 0.07 to 0.4 is further preferable.
Here, the dispersed material includes both titanium black in the state of primary particles and aggregate in the state of agglomerates (secondary particles).
In order to change the content ratio (Si / Ti) of the substance to be dispersed (for example, 0.05 or more), the following means can be used.
First, titanium oxide and silica particles are dispersed using a disperser to obtain a dispersion, and the dispersion is subjected to reduction treatment at a high temperature (for example, 850 to 1000 ° C.) to mainly disperse titanium black particles. 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 dispersant may be used to disperse the titanium oxide and the silica particles. Examples of the dispersant include those described in the section of the dispersant described later.
The above dispersion may be carried out in a solvent. Examples of the solvent include water and organic solvents. Examples of the organic solvent include those described in the section of organic solvent described later.
The titanium black whose content ratio (Si / Ti) is adjusted can be produced, for example, by the method described in paragraphs [0005] and [0016] to [0021] of JP 2008-266045 A.

By adjusting the content ratio (Si / Ti) of Si atoms and Ti atoms in the dispersed material containing titanium black and Si atoms to a suitable range (for example, 0.05 or more), curing including this dispersed material When the cured film is formed using the curable composition, the residue derived from the curable composition outside the region where the cured film is formed is reduced. The residue contains components derived from the curable composition such as titanium black particles and resin components.
Although the reason why the residue is reduced is not yet clear, the above-mentioned dispersed substance tends to have a small particle size (for example, the particle size is 30 nm or less), and further, the Si atom of this dispersed substance is The increased content of components reduces the adsorptivity of the entire film with the underlying layer. It is presumed that this contributes to the improvement of the developing removability of the uncured curable composition (particularly titanium black) in the formation of the cured film.
Titanium black is excellent in light-shielding properties for light in a wide wavelength range from ultraviolet light to infrared light, and therefore titanium black and the dispersed material containing Si atoms (preferably having a content ratio (Si / Ti) of 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 and Ti atoms in the dispersed material is, for example, the method (1-1) or the method (1-2) described in paragraph 0033 of JP2013-249417A. ) Can be used for measurement.
Regarding the substance to be dispersed contained in the cured film obtained by curing the curable composition, whether the content ratio (Si / Ti) of Si atoms and Ti atoms in the substance to be dispersed is 0.05 or more. In order to judge that, the method (2) described in paragraph No. 0035 of JP2013-249417A can be used.

In the dispersed material containing titanium black and Si atoms, the above-mentioned titanium black can be used.
In this dispersed material, a composite oxide of Cu, Fe, Mn, V, Ni, etc., cobalt oxide, iron oxide, carbon black, and Black pigments such as aniline black may be used alone or in combination of two or more. In this case, it is preferable that titanium black occupies 50% by mass or more of the whole dispersed material.
In this substance to be dispersed, other colorants (organic pigment and / or dye, etc.) may be optionally used together with titanium black 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 when introducing Si atoms into the substance to be dispersed will be described. When introducing Si atoms into the substance to be dispersed, a Si-containing substance such as silica may be used.
Examples of silica that can be used include precipitated silica, fumed silica, colloidal silica, and synthetic silica, and these may be appropriately selected and used.
Further, when the particle size 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. In addition, as an example of the fine particle type silica, for example, silica described in JP-A-2013-249417, paragraph 0039 can be mentioned, 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.
Hereinafter, the tungsten compound and the metal boride will be described in detail.
Tungsten compounds and metal borides have high absorption with respect to infrared rays (light having a wavelength of about 800 to 1200 nm) (that is, high light-shielding properties (shielding properties) against infrared rays) and low absorption with respect to visible light. It is an infrared shielding material. Therefore, the curable composition contains a tungsten compound and / or a metal boride, and thus can form a pattern having a high light-shielding property in the infrared region and a high light-transmitting property in the visible light region.
Tungsten compounds and metal borides have small absorption even for light having a wavelength shorter than the visible range, which is used for exposure of high-pressure mercury lamps, KrF, ArF, etc. used for image formation. Therefore, by combining with a polymerizable compound and an alkali-soluble resin described later, an excellent pattern can be obtained and a development residue can be further suppressed in the pattern formation.

Examples of the tungsten compound include a tungsten oxide-based compound, a tungsten boride-based compound, and a tungsten sulfide-based compound, and a tungsten oxide-based compound represented by the following formula (compositional 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

  Examples of the metal of M include alkali metal, alkaline earth metal, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Examples thereof include Al, Ga, In, Tl, Sn, Pb, Ti, Nb, V, Mo, Ta, Re, Be, Hf, Os, and Bi, but an alkali metal is preferable. The metal of M may be one kind or two or more kinds.

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

When x / y is 0.001 or more, infrared rays can be sufficiently shielded, and when it is 1.1 or less, it is possible to more surely avoid generation of an impurity phase in the tungsten compound. it can.
When z / y is 2.2 or more, the 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 , and Ba _0.33 WO _3. Among them, 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 further 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 due to light scattering, so that the light transmittance in the visible light region can be further ensured. From the viewpoint of avoiding light scattering, the smaller the average primary particle diameter is, the more preferable, but the average primary particle diameter of the tungsten fine particles is usually 1 nm or more for reasons such as ease of handling during production.

  Two or more kinds of tungsten compounds can be used.

Although a tungsten compound is commercially available, for example, a tungsten oxide compound 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.

Examples of the metal boride include lanthanum boride (LaB ₆ ), praseodymium boride (PrB ₆ ), neodymium boride (NdB ₆ ), cerium boride (CeB ₆ ), yttrium boride (YB ₆ ), and titanium boride ( TiB _2), zirconium boride _(ZrB 2), hafnium boride _(HfB 2), vanadium boride _(VB 2), tantalum boride _(TaB 2), chromium borides _(CrB, CrB 2), molybdenum borides ( MoB ₂ , Mo ₂ B ₅ , MoB), and one or more kinds of tungsten boride (W ₂ B ₅ ) and the like are mentioned, and lanthanum boride (LaB ₆ ) is preferable.

  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, it becomes difficult for the metal boride fine particles to block visible light due to light scattering, so that the light transmittance in the visible light region can be more ensured. From the viewpoint of avoiding light scattering, the smaller the average primary particle diameter is, the more preferable, but the average primary particle diameter of the metal boride fine particles is usually 1 nm or more for reasons such as ease of handling during production.

  Two or more kinds of 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. A gas phase reaction method is usually used for producing the titanium nitride-containing particles, and specific examples thereof include an electric furnace method and a thermal plasma method. Among these manufacturing methods, the thermal plasma method is preferable because it is less contaminated with impurities, has a uniform particle size, and has high productivity.
Examples of the method for generating thermal plasma include direct current arc discharge, multi-phase arc discharge, radio frequency (RF) plasma, and hybrid plasma, and high frequency plasma in which impurities from the electrodes are less mixed 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 device as a carrier gas, and the titanium powder is nitrided in the cooling process. , A method of synthesizing titanium nitride-containing particles, and the like. The thermal plasma method is not limited to the above.

  The method for producing the 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 WO 2010/147098, a component containing Fe and / or a component containing Si described below is used, and a mixture of this and a titanium powder material (titanium particles) is used as a raw material. The titanium nitride-containing particles contained in the curable composition can be manufactured.

  The titanium powder material (titanium particles) used for producing the titanium nitride-containing particles is preferably highly pure. The titanium powder material is not particularly limited, but a titanium element having a purity of titanium of 99.99% or more is preferable, and a material having a purity of 99.999% or more is more preferable.

The titanium powder material (titanium particles) used for producing the titanium nitride-containing particles may contain atoms other than titanium atoms. Other atoms that can be contained in the titanium powder material include, for example, Fe atoms and Si atoms.
When the titanium powder material contains Fe atoms, the content of Fe atoms is preferably more than 0.001 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 mass% and less than 0.3 mass% with respect to the total mass of the titanium powder material, and 0.01 ˜0.15% by mass, more preferably 0.02 to 0.1% by mass. When the content of Si atoms exceeds 0.002 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 surface layer of the obtained titanium nitride-containing particles becomes more stable. This improves the adsorptivity of the dispersant to the titanium nitride-containing particles when the titanium nitride-containing particles are dispersed, and reduces the undispersed titanium nitride-containing particles.
The water content in the titanium powder material (titanium particles) used for producing the titanium nitride-containing particles is preferably less than 1% by mass, and less than 0.1% by mass, based on the total mass of the titanium powder material. It is more preferable, and it is further preferable that it is not substantially contained.

  By obtaining the titanium nitride-containing particles by using the thermal plasma method, the diffraction angle 2θ (details will be described later) of the peak derived from the (200) plane when the CuKα ray is used as the X-ray source is 42.6. It becomes easy to adjust in the range of more than 43.5 ° and below.

The method for incorporating Fe atoms into the titanium nitride-containing particles is not particularly limited, and for example, Fe atoms are introduced at the stage of obtaining the titanium particles (titanium powder) used as the raw material of the titanium nitride-containing particles described above. Method etc. are mentioned. More specifically, when producing titanium by the Kroll method or the like, a reaction vessel made of a material containing Fe atoms such as stainless steel is used as a reaction vessel, and a press or crusher for crushing titanium is 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, by adding components such as Fe particles and Fe oxide in addition to titanium particles as a raw material and nitriding them by the thermal plasma method. The Fe-atoms can be contained in the titanium nitride-containing particles.
Fe atoms contained in the titanium nitride-containing particles are ions, metal compounds (including complex compounds), intermetallic compounds, alloys, oxides, complex oxides, nitrides, oxynitrides, sulfides and oxysulfides. Etc., and may be included in any form. The Fe atom contained in the titanium nitride-containing particles may exist as an impurity at a crystal lattice position, or may exist as an impurity in a crystal grain boundary in an amorphous state.

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

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

The method of incorporating Si atoms into the titanium nitride-containing particles is not particularly limited, and for example, introducing Si atoms in the step of obtaining the titanium particles (titanium powder) used as the raw material of the titanium nitride-containing particles described above. Method etc. are mentioned. More specifically, when producing titanium by the Kroll method or the like, a reaction vessel made of a material containing Si atoms is used, or a Si atom is used as a material for a press and a crusher when crushing titanium. Si atoms can be attached to the surface of the titanium particles by using a material containing.
When the thermal plasma method is used in the production of titanium nitride-containing particles, by adding components such as Si particles and Si oxide in addition to titanium particles as a raw material and nitriding them by the thermal plasma method. The titanium nitride-containing particles can contain Si atoms.
Si atoms contained in the titanium nitride-containing particles are ions, metal compounds (including complex compounds), intermetallic compounds, alloys, oxides, complex oxides, nitrides, oxynitrides, sulfides and oxysulfides. Etc., and may be included in any form. The Si atom contained in the titanium nitride-containing particles may be present as an impurity at the position between crystal lattices, or may be present as an impurity in the crystal grain boundary in an amorphous state.

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, based on the total mass of the titanium nitride-containing particles. More preferably, it is more preferably 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, based on the total mass of the titanium nitride-containing particles. More preferably, it is more preferably 10 to 40% by mass. The content of nitrogen atoms 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 more prominent when oxygen is mixed in during its synthesis and when the particle size is small, but due to oxidation of the particle surface, etc. You may contain a part oxygen atom.
The content of oxygen atoms in the titanium nitride-containing particles is preferably 1 to 40 mass%, more preferably 1 to 35 mass%, and more preferably 5 to 5 mass% with respect to the total mass of the titanium nitride containing particles. It is more preferable that the content is ˜30% by mass. The content of oxygen atoms 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, 10~60m 2 /} g is more preferable. 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.
The composite fine particles refer to particles in which titanium nitride particles and metal fine particles are combined or are highly dispersed. Here, "composite" means that particles are composed of both components of titanium nitride and metal, and "highly dispersed state" means titanium nitride particles and metal particles. And exist individually and mean that the particles of the minor component are not aggregated but are uniformly and uniformly dispersed.
The metal fine particles are not particularly limited and include, 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 More preferably, it is at least one selected from the above alloys. From the viewpoint of being more excellent in moisture resistance, silver is preferable.
The content of the metal fine particles in the titanium nitride-containing particles is preferably 5 to 50 mass% and more preferably 10 to 30 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 of more than 42.6 ° and 43.5 ° or less when a CuKα ray is used as an X-ray source. 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 was measured using CuKα ray as an X-ray source, TiN had a peak of (200) plane in the vicinity of 2θ = 42.5 ° and TiO (200 ) A peak derived from the plane is seen near 2θ = 43.4 °. On the other hand, most peaks not strength strong peak is anatase TiO ₂ is derived from the (200) plane in the vicinity 2 [Theta] = 48.1 °, rutile TiO ₂ and a peak derived from (200) plane is 2 [Theta] = 39 Observed near 2 °. Therefore, the peak position shifts to a higher angle side with respect to 42.5 ° as the crystalline state contains more oxygen atoms.

The diffraction angle 2θ of the peak derived from the (200) plane of the titanium nitride-containing particles is preferably more than 42.6 ° and less than 43.5 ° from the viewpoint of the temporal stability of the particles. From the viewpoint of excellent process margin, it is more preferably 42.7 ° or more and less than 43.5 °, and further preferably 42.7 ° or more and less than 43.4 ° from the viewpoint of excellent reproducibility of particle performance. When titanium oxide TiO ₂ is contained as a sub-component, the peak derived from anatase type TiO ₂ (101) is the strongest peak in the vicinity of 2θ = 25.3 ° and the peak derived from rutile TiO ₂ (110). Is seen near 2θ = 27.4 °. However, since TiO ₂ is white and becomes a factor that reduces the light-shielding property of the black matrix, it is preferable that the TiO ₂ is reduced to the 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 light transmitted through the cured film exhibits a blue to violet color with a peak wavelength of 475 nm or less, and high light-shielding properties. It is possible to obtain a black matrix that also has ultraviolet sensitivity. When the crystallite size is 20 nm or more, the ratio of the active particle surface to the particle volume is small and the balance is good, and the titanium nitride-containing particles are more excellent in heat resistance and / or durability. Becomes

.. Metal Nitride-Containing Particles Containing Atom A Further, as the inorganic pigment, metal nitride-containing particles that are a metal nitride-containing particle containing a predetermined atom A can 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 effects of the present invention in which the curable composition is more excellent. Nb or V is more preferable in that it has
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 thereof is not particularly limited, but the content of the atom A in the metal nitride-containing particles is preferably 0.00005 to 10 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.
A gas phase reaction method is usually used for producing the metal nitride-containing particles, and specific examples thereof 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 size, 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 the “black composite fine particle production apparatus” described later) can be mentioned. The apparatus for producing metal fine particles includes, for example, a plasma torch for generating thermal plasma, a material supply device for supplying metal raw material powder into the plasma torch, a chamber containing a cooling function, a cyclone for classifying the produced metal fine particles, and metal fine particles. It is composed of a recovery unit for recovering.
In the present specification, the term “fine metal particles” means particles containing a metal element and having a primary particle diameter of 20 nm to 40 μm.

-Organic pigment As an organic pigment, 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, and C.I. 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. The pigments may be used alone or in combination of two or more.

(dye)
As the dye, for example, JP-A-64-90403, JP-A-64-91102, JP-A-1-94301, JP-A-6-11614, Japanese Patent No. 2592207, and US Pat. No. 4,808,501. U.S. Pat. No. 5,667,920, U.S. Pat. No. 5,050,950, JP-A-5-333207, JP-A-6-35183, JP-A-6-51115, and JP-A-6-194828. Dyes can be used. When classified as a chemical structure, a pyrazole azo compound, a pyrromethene compound, an anilino azo compound, a triphenyl methane compound, an anthraquinone compound, a benzylidene compound, an oxonol compound, a pyrazolotriazole azo compound, a pyridone azo compound, a cyanine compound, a phenothiazine compound, and a pyrrolopyrazole azomethine compound. A compound etc. are mentioned. As the dye, a dye multimer may be used. 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 a wavelength region of an infrared region (preferably a wavelength of 650 to 1300 nm). The infrared absorber is preferably a compound having a maximum absorption wavelength in the wavelength range of 675 to 900 nm.
Examples of the colorant having such spectral characteristics include, for example, pyrrolopyrrole compounds, copper compounds, cyanine compounds, phthalocyanine compounds, iminium compounds, thiol complex compounds, transition metal oxide compounds, squarylium compounds, naphthalocyanine compounds, quaterrylene. Examples thereof include compounds, dithiol metal complex compounds, and croconium compounds.
As the phthalocyanine compound, the naphthalocyanine compound, the iminium compound, the cyanine compound, the squarylium compound and the croconium compound, the compounds disclosed in paragraphs 0010 to 0081 of JP 2010-111750 A may be used, and the contents thereof are described herein. Incorporated. For the cyanine compound, for example, “functional dye, Shin Okawara / Ken Matsuoka / Teijiro Kitao / Tsunaki Hirashima, Kodansha Scientific” can be referred to, and the contents thereof are incorporated herein.

  As the colorant having the above-mentioned spectral characteristics, the compounds disclosed in paragraphs 0004 to 0016 of JP-A-07-164729 and / or the compounds disclosed in paragraphs 0027 to 0062 of JP-A-2002-146254, JP-A-2011-164583. It is also possible to use near-infrared absorbing particles composed of crystallites of oxides 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.

As the compound having the maximum absorption wavelength in the wavelength range of 675 to 900 nm, 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 is preferable.
The infrared absorber is preferably a compound that is soluble in water at 25 ° C. in an amount of 1% by mass or more, and more preferably a compound that is dissolved in water at 25 ° C. in an amount of 10% by mass or more. By using such a compound, the solvent resistance is improved.
The pyrrolopyrrole compound can refer to paragraphs 0049 to 0062 of JP 2010-222557 A, the contents of which are incorporated herein. Cyanine compounds and squarylium compounds are described in WO 2014/088063, paragraphs 0022 to 0063, WO 2014/030628, paragraphs 0053 to 0118, and JP 2014-59550, paragraphs 0028 to 0074, WO 2012/0074. Paragraphs 0013 to 0091 of Japanese Patent Laid-Open No. 169447, Paragraphs 0019 to 0033 of Japanese Patent Laid-Open No. 2015-176046, Paragraphs 0053 to 0099 of Japanese Patent Laid-Open No. 2014-63144, Paragraphs 0085 to 0150 of Japanese Patent Laid-Open No. 2014-52431, Paragraphs 0076 to 0124 of 2014-44301, paragraphs 0045 to 0078 of JP2012-8532A, paragraphs 0027 to 0067 of JP2015-172102A, and paragraphs 002 of JP2005-172004A. 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 JP2014-095007A, Paragraphs 0013 to 0047 of JP2014-80487A, and Paragraphs 0007 to 0028 of JP2013-227403A can be referred to. The content is 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.
Equation 1

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

In Formula 1-A, Z ^1A represents a non-metallic atomic group forming a nitrogen-containing heterocycle, R ^2A represents an alkyl group, an alkenyl group, or an aralkyl group, d represents 0 or 1, and The wavy line represents the connecting hand.
Equation 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 represent 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 represent 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 a substituent,
R ⁶ may be covalently bonded or coordinated to R ^1a or R ^3, and R ⁷ may be covalently or coordinately bonded to R ^1b or R ⁵ .
Formula 3

In Formula 3, Z ¹ and Z ² are each independently a non-metal atomic group forming a 5-membered or 6-membered nitrogen-containing heterocycle which may be condensed.
R ¹⁰¹ and R ¹⁰² each independently represent 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 part, X ¹ represents an anion, c represents a number necessary for balancing charges, and the site represented by Cy in the formula is an anion part. X ¹ represents a cation, c represents a number necessary for balancing charges, and when the charge at the site represented by Cy in the formula is neutralized in the molecule, c represents It 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 the organic pigment is substituted with an acidic group, a basic group or a phthalimidomethyl group. From the viewpoint of dispersibility and dispersion stability of the colorant A, the pigment derivative is preferably a pigment derivative having an acidic group or a basic group. Particularly preferred is a pigment derivative 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.

The organic pigment for constituting the pigment derivative, diketopyrrolopyrrole pigment, azo pigment, phthalocyanine pigment, anthraquinone pigment, quinacridone pigment, dioxazine pigment, perinone pigment, perylene pigment, thioindigo pigment , Isoindolin-based pigments, isoindolinone-based pigments, quinophthalone-based pigments, slene-based pigments, and metal complex-based pigments.
As the acidic group contained in the pigment derivative, a sulfonic acid group or a salt thereof, or a carboxylic acid group or a salt thereof is preferable, a carboxylic acid group or a sulfonic acid group is more preferable, and a sulfonic acid group is further preferable. As the basic group contained in the pigment derivative, 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 based on the mass of the pigment. As the pigment derivative, only one kind may be used, or two or more kinds may be used in combination.

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

  Although the content of the polymerizable compound in the curable composition is not particularly limited, it is generally preferably 5 to 30 mass% with respect to the total solid content of the curable composition. The polymerizable compounds may be used alone or in combination of two or more. When two or more polymerizable compounds are used in combination, the total content is preferably within the above range.

  The polymerizable compound is preferably a compound containing one or more groups containing an ethylenically unsaturated bond, more preferably a compound containing two or more groups, still more preferably three or more groups, and five or more groups. Is particularly preferable. The upper limit is, for example, 15 or less. 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, the compounds described in JP-A-2008-260927, paragraph 0050, and JP-A-2005-68893, paragraph 0040 can be used, and the above contents are described in the present specification. Incorporated into.

The polymerizable compound may be in any of chemical forms such as a monomer, a prepolymer, an oligomer, a mixture thereof and a polymer thereof.
The polymerizable compound is preferably a 3- to 15-functional (meth) acrylate compound, and more preferably a 3- to 6-functional (meth) acrylate compound.

  As the polymerizable compound, a compound having one or more groups 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, and the contents thereof are incorporated in the present specification.

  Examples of the polymerizable compound include dipentaerythritol triacrylate (commercially available KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (commercially available KAYARAD D-320; manufactured by Nippon Kayaku Co., Ltd.). ), Dipentaerythritol penta (meth) acrylate (commercially available KAYARAD D-310; manufactured by Nippon Kayaku), dipentaerythritol hexa (meth) acrylate (commercially available KAYARAD DPHA; manufactured by Nippon Kayaku, A) -DPH-12E; manufactured by Shin-Nakamura Chemical Co., Ltd.) and a structure in which these (meth) acryloyl groups are mediated by an ethylene glycol residue or a propylene glycol residue (for example, commercially available from Sartomer, SR454, SR499). Is preferred. These oligomer types can also be used. In addition, NK ester A-TMMT (pentaerythritol tetraacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.), KAYARAD RP-1040 (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 the unreacted hydroxyl group of the aliphatic polyhydroxy compound is reacted with a non-aromatic carboxylic acid anhydride to form an acid. 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 products of the polymerizable compound include Aronix TO-2349, M-305, M-510, and M-520 manufactured by Toagosei Co., Ltd.

  The acid value of the polymerizable compound containing an acid group is preferably 0.1 to 40 mgKOH / g, more preferably 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 (the property of being easily dissolved in an alkali developing solution) and is 40 mgKOH / g or less, It is advantageous in terms of production and / or handling of the polymerizable compound, and has more excellent 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 with (meth) acrylic acid and ε-caprolactone. Among them, compounds containing a caprolactone structure represented by the following formula (Z-1) are preferable.

  In the formula (Z-1), all six Rs are groups represented by the following formula (Z-2), or 1 to 5 of the six Rs are 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.

The polymerizable compound containing a caprolactone structure is commercially available, for example, from Nippon Kayaku as KAYARAD DPCA series, and DPCA-20 (m in formulas (Z-1) to (Z-3) above is 1; -2), the number of groups represented by 2 and R ¹ are all hydrogen atoms), DPCA-30 (in the formula, m is 1, and the number of groups represented by formula (Z-2) is 3, a 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 R ¹ are all hydrogen atoms) and the like.

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

Wherein (Z-4) and (Z-5), E are each _{independently, - ((CH 2) y} CH 2 O) -, _{or, ((CH 2) y CH} (CH 3) O) - Represents y represents the integer of 0-10 each independently. X's each independently represent a (meth) acryloyl group, a hydrogen atom, or a carboxylic acid group.
In formula (Z-4), the total of (meth) acryloyl groups is 3 or 4, m each independently represents an integer of 0 to 10, and the sum 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, n each independently represents an integer of 0 to 10, and the sum of each n is an integer of 0 to 60.

In formula (Z-4), m is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4.
The sum of each m is preferably an integer of 2 to 40, more preferably an integer of 2 to 16, and even more preferably an integer of 4 to 8.
In formula (Z-5), n is preferably an integer of 0 to 6, more preferably an integer of 0 to 4.
The sum of each n is preferably an integer of 3 to 60, more preferably an integer of 3 to 24, and even more preferably an integer of 6 to 12.
Formula (Z-4) or formula (Z-5) in the _{- ((CH 2) y CH} 2 O) -, _{or, ((CH 2) y CH} (CH 3) O) - , the oxygen atom side A form in which the end is bonded to X is preferable.

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

The total content of the compounds 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.
Among the compounds represented by formula (Z-4) or formula (Z-5), a pentaerythritol derivative and / or a dipentaerythritol derivative are more preferable.

The polymerizable compound may contain a cardo skeleton.
The polymerizable compound having a cardo skeleton is preferably a polymerizable compound having a 9,9-bisarylfluorene skeleton.
The polymerizable compound containing a cardo skeleton is not particularly limited, and examples thereof include Oncoat EX series (manufactured by Nagase & Co., Ltd.) and Ogsol (manufactured by Osaka Gas Chemicals).

[Arbitrary ingredients]
The curable composition may contain other components as long as the effects of the present invention are exhibited. Examples of other components include resins, polymerization inhibitors, solvents, surfactants, ultraviolet absorbers, and silane coupling agents. Hereinafter, the optional components contained in the curable composition will be described in 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 mass% with respect to the total solid content of the curable composition. The other polymerization initiators may be used alone or in combination of two or more. When two or more 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, azobismalenonitrile, and dimethyl- (2,2 ′)-azobis (2 -Methyl propionate) [V-601] and the like, and benzoyl peroxide, lauroyl peroxide, and organic peroxides such as potassium persulfate.
Examples of the thermal polymerization initiator include the compounds described on pages 65 to 148 of “Ultraviolet Curing System” by Kiyomi Kato (published by Sogo Gijutsu 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, hexaarylbiimidazole, and the like. Examples include oxime compounds such as oxime derivatives (excluding specific oxime compounds), organic peroxides, thio compounds, ketone compounds, aromatic onium salts, aminoacetophenone compounds, and hydroxyacetophenone.
As the photopolymerization initiator, for example, paragraphs 0265 to 0268 of JP2013-29760A can be referred to, and the contents thereof are incorporated in the present specification.

As the photopolymerization initiator, more specifically, for example, an aminoacetophenone-based initiator described in JP-A-10-291969 or an acylphosphine-based initiator described in Japanese Patent No. 4225898 can be used. Yes, and 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 name: all manufactured by BASF) can be used, but the aminoacetophenone compound is not limited thereto. As the aminoacetophenone compound, the compound described in Japanese Patent Application Laid-Open No. 2009-191179 in which the absorption wavelength is matched with a long-wave light source such as 365 nm or 405 nm can also be used, and the above contents are incorporated herein.
As the acylphosphine compound, IRGACURE-819 or IRGACURE-TPO (trade name: all manufactured by BASF) 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 mass% with respect to the total solid content of the curable composition. The resins may be used alone or in combination of two or more. When two or more resins are used in combination, the total content is preferably within the above range.

(Dispersant)
The curable composition preferably contains a dispersant (corresponding to a resin). In the present specification, the dispersant means a compound different from the alkali-soluble resin described below.
Although the content of the dispersant in the curable composition is not particularly limited, it is generally preferably 5 to 40 mass% with respect to the total solid content of the curable composition.
The dispersants may be used alone or in combination of two or more. 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 polymer dispersants. 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 and the like.
As the dispersant, polyoxyethylene alkyl phosphate ester, polyoxyethylene alkyl amine, pigment derivative, or the like can be used.
Among them, polymer compounds are preferable as the dispersant. The polymer compound can be further classified into a linear polymer, a terminal modified polymer, a graft polymer, and a block polymer based on its structure.

-Polymer compound The polymer compound is adsorbed on the surface of a colorant (hereinafter, may be referred to as a "pigment"), and acts to prevent re-aggregation of the substance to be dispersed. Therefore, a terminal-modified polymer, a graft-type (containing a polymer chain) polymer, and a block-type polymer, which contain an anchor site to the pigment surface, are preferable.

The polymer compound may contain a curable group.
As the curable group, for example, an ethylenically unsaturated group (eg, (meth) acryloyl group, vinyl group, styryl group, etc.), and cyclic ether group (eg, epoxy group, oxetanyl group, etc.), etc. However, the present invention is not limited to these.
Among them, the ethylenically unsaturated group is preferable as the curable group because 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. As described later, when the resin contains a structural unit containing a graft chain, the above-mentioned graft chain May contain a polyester structure and / or a polyether structure.
In the resin, it is more preferable that the graft chain has a polyester structure.

The polymer compound preferably contains a structural unit containing a graft chain. In the present specification, “structural unit” has the same meaning as “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 a better affinity with a solvent, so that it is easier to disperse a pigment or the like, and even after a lapse of time after dispersing the pigment or the like. The initial dispersion state is less likely to change (has better stability over time). Further, the polymer compound containing a structural unit containing a graft chain, because it contains the graft chain, has a better affinity with the polymerizable compound and / or other components described below. As a result, the polymer compound containing the structural unit containing the graft chain is less likely to produce a residue due to the unreacted polymerizable compound or the like during the alkali development described later.
When the graft chain is long (the formula weight 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 adsorptivity to the pigment or the like will decrease, and the dispersibility of the pigment or the like will tend to decrease. Therefore, the number of atoms in the graft chain (excluding hydrogen atoms) is preferably 40 to 10000, more preferably 50 to 2000, and even more preferably 60 to 500.
Here, the graft chain is intended to extend from the root of the main chain of the polymer compound (atoms bonded to the main chain in the 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, a poly (meth) acrylic structure), a polyester structure, a polyurethane structure, a polyurea structure, a polyamide structure, and a poly structure. An ether structure etc. are mentioned.
The polymer chain has a polyester structure, a polyether structure, and a poly (meth) acrylate structure because the polymer chain has a better affinity with the solvent and the polymer compound more easily disperses the pigment and the like. It is preferable to contain at least one selected from the group consisting of, and it is 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 containing a polymer structure and binding 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.

  Examples of commercially available macromonomers corresponding to the structural unit containing a polymer chain contained in the polymer compound and which can be used in 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 of the above are trade names, manufactured by Toagosei 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 of 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 polyester, and polymethyl acrylate and polymethyl methacrylate. And more preferably contains at least one structure selected from the group consisting of chain-like polyesters, and comprises a polymethyl acrylate structure, a polymethyl methacrylate structure, a polycaprolactone structure, and a polyvalerolactone structure. It is more preferable to contain at least one structure selected from the group consisting of
The dispersant may contain one kind of the above structure in the molecule, or may contain a plurality of kinds of the structure in the molecule.
Here, the polycaprolactone structure means a structure containing a ring-opening structure of ε-caprolactone as a repeating unit. The polyvalerolactone structure means a structure containing a ring-opening structure of δ-valerolactone as a repeating unit.
Examples of the dispersant containing a polycaprolactone structure include those having j or k of 5 in the following formula (1) or formula (2). Examples of the dispersant containing a polyvalerolactone structure include those in which j or k is 4 in the following formula (1) or formula (2).
Examples of the dispersant containing a polymethyl acrylate structure include those represented by the following formula (4) in which X ⁵ is a hydrogen atom and R ⁴ is a methyl group.
Examples of the dispersant containing a polymethylmethacrylate structure include those represented by the following formula (4) in which X ⁵ is a methyl group and R ⁴ is a methyl group.

-Structural Unit Containing Graft Chain The polymer compound contains, as a structural unit containing a graft chain, at least one polymer chain selected from the group consisting of the following formulas (1) to (4). 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): It is more preferable to contain a structural unit containing a polymer chain.

In 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 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. From the viewpoint of synthetic constraints, X ¹ , X ² , X ³ , X ⁴ , and X ⁵ are each independently a hydrogen atom or an alkyl group having 1 to 12 carbon atoms (number of carbon atoms). , Each independently, a hydrogen atom or a methyl group is more preferable, and a methyl group is further 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 mean a binding site. Among the structures shown below, (Y-2) or (Y-13) is more preferable because of the ease of synthesis.

In 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 the pigment and the like can be more easily dispersed. More preferably, it is an alkyl group or alkoxy group having 5 to 24 carbon atoms, 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 formulas (1) to (4), n, m, p, and q each independently represent an integer of 1 to 500.
In formula (1) and formula (2), j and k each independently represent an integer of 2 to 8.
In formulas (1) and (2), j and k are integers of 4 to 6 in that the curable composition has more excellent stability over time and more excellent developability. Preferably, 5 is more preferable.
In the formulas (1) and (2), n and m are preferably integers of 10 or more, and more preferably 20 or more. When the dispersant contains a polycaprolactone structure and a polyvalerolactone structure, the sum of the polycaprolactone structure repeating number and the polyvalerolactone repeating number is preferably an integer of 10 or more, and 20 or more. An integer is more preferable.

In formula (3), R ³ represents a branched or linear alkylene group, preferably an alkylene group having 1 to 10 carbon atoms, and more preferably an alkylene group having 2 or 3 carbon atoms. When p is 2 to 500, a plurality of R ^3's may be the same or different.
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. 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 further 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 the graft chain may be the same or different from each other.

The polymer compound may contain a structural unit containing two or more kinds 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 n and m in the formulas (1) to (4) may be contained. , P, and q each represent an integer of 2 or more, in formula (1) and formula (2), j and k may have different structures in the side chains, 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 more excellent stability over time and developability. More preferable.
As the structural unit represented by the formula (2), the structural unit represented by the following formula (2A) is more preferable because the curable composition has more excellent stability over time 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 stability over time and better developability. Structural units are more preferred.

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

  The polymer compound more preferably contains a structural unit represented by the formula (1A) as a structural unit containing a graft chain, especially 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, in terms of mass, based on the total mass of the polymer compound. 2-90 mass% is preferable, and the range of 5-30% is more preferable. When the content of the structural unit containing the graft chain in the polymer compound is within the above range, the dispersant more easily disperses the pigment and the like, and the curable composition has more excellent developability.

-Hydrophobic Structural Unit The polymer compound preferably contains a hydrophobic structural unit that is different from the structural unit containing the graft chain (that is, does not correspond to the structural unit containing the graft chain). However, in the present 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, and a phenolic hydroxyl group).

  The hydrophobic structural unit is preferably a (corresponding) structural unit derived from 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 preferable.

The ClogP value is measured by Daylight Chemical Information System, Inc. It is a value calculated by the program "CLOGP" available from This program provides the value of "computational logP" calculated by the Hansch, Leo fragment approach (see below). The fragment approach is based on the chemical structure of the compound and estimates the compound's logP value by dividing the chemical structure into substructures (fragments) and summing the logP contributions assigned to that fragment. The details are described in the following documents. As used herein, ClogP value is intended to be the value calculated by the program CLOGP v4.82.
A. J. Leo, Comprehensive Medicinal Chemistry, Vol. 4, C.I. Hansch, P .; G. Sammmens, J.M. B. Taylor and C.I. A. Ramsden, Eds. , P. 295, Pergamon Press, 1990 C.I. Hansch & A. J. Leo. Substituent Constants For Correlation Analysis in Chemistry and Biology. John Wiley & Sons. A. J. Leo. Calculating logPoint from structure. Chem. Rev. , 93, 1281-1306, 1993.

logP means a common logarithm of partition coefficient P (Partition Coefficient), and quantitatively shows how an organic compound is distributed in the equilibrium of two-phase system of oil (generally 1-octanol) and water. 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.
It means that the oil solubility increases when the value of logP increases to a positive value across 0, and the water solubility increases when the absolute value increases to a negative value, and there is a negative correlation with the water solubility of organic compounds. It is widely used as a parameter for estimating the water content.

  The polymer compound may contain, as the hydrophobic structural unit, at least one structural unit selected from the group consisting of structural units derived from the monomers represented by the following formulas (i) to (iii). 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 or the like), or a carbon number. Represents an alkyl group of 1 to 6 (eg, methyl group, ethyl group, 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, and more preferably a hydrogen atom or a methyl group. R ² and R ³ are more preferably hydrogen atoms.
X represents an oxygen atom (-O-) or an imino group (-NH-), and an oxygen atom is preferable.

L is a single bond or a divalent linking group. Examples of the divalent linking group include a divalent aliphatic group (eg, alkylene group, substituted alkylene group, alkenylene group, substituted alkenylene group, alkynylene group, and substituted alkynylene group), divalent aromatic group (eg, , An arylene group, and a substituted arylene group), a divalent heterocyclic group, an oxygen atom (—O—), a sulfur atom (—S—), an imino group (—NH—), a substituted imino group (—NR ³¹ -, Where 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. 1-20 are preferable, as for carbon number of an aliphatic group, 1-15 are more preferable, and 1-10 are more preferable. The aliphatic group may be an unsaturated aliphatic group or a saturated aliphatic group, and the saturated aliphatic group is preferable. The aliphatic group may contain a substituent. The substituent is not particularly limited, but examples thereof include a halogen atom, an aromatic group, and a heterocyclic group.

  6-20 are preferable, as for carbon number of a bivalent aromatic group, 6-15 are more preferable, and 6-10 are more preferable. The aromatic group may contain a substituent. The substituent is not particularly limited, but examples thereof include a halogen atom, an aliphatic group, an aromatic group, and a heterocyclic group.

The divalent heterocyclic group preferably contains a 5-membered ring or a 6-membered ring as the heterocycle. Another heterocycle, an aliphatic ring or an aromatic ring may be condensed with the heterocycle. The heterocyclic group may contain a substituent. The substituent is not particularly limited, and examples thereof 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 includes an aliphatic group, an aromatic group or a heterocyclic group), an aliphatic group, an aromatic group, and a heterocyclic group.

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. Polyoxyethylene _{structure, - (OCH 2 CH 2)} n - it is represented, n is preferably an integer of 2 or more, and more preferably an integer of from 2 to 10.

Z is an aliphatic group (for example, an alkyl group, a substituted alkyl group, an unsaturated alkyl group, a substituted unsaturated alkyl group, etc.), an aromatic group (for example, an aryl group, a substituted aryl group, an arylene group, and A substituted arylene group), a heterocyclic group, or a combination thereof. These groups an oxygen atom (-O-), sulfur atom (-S-), an imino group (-NH-), a substituted imino group ^{(-NR 31} -, wherein ^{R 31} is an aliphatic group, 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. 1-20 are preferable, as for carbon number of an aliphatic group, 1-15 are more preferable, and 1-10 are more preferable. The aliphatic group further contains a ring-assembled hydrocarbon group, or a cross-linked cyclic hydrocarbon group, and examples of the ring-assembled hydrocarbon group include bicyclohexyl group, perhydronaphthalenyl group, biphenyl group, and 4-cyclohexylphenyl group and the like can be mentioned. Examples of the crosslinked cyclic hydrocarbon ring include pinane, bornane, norpinane, norbornane, and bicyclooctane ring (bicyclo [2.2.2] octane ring, bicyclo [3.2.1] octane ring, etc.) and the like. A bicyclic hydrocarbon ring of adamantane, tricyclo [5.2.1.0 ^2,6 ] decane, and tricyclo [4.3.1.1 ^2,5 ] undecane ring, etc. Tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodecane, and a tetracyclic hydrocarbon ring such as a perhydro-1,4-methano-5,8-methanonaphthalene ring; and the like. The bridged cyclic hydrocarbon ring includes a condensed cyclic hydrocarbon ring such as perhydronaphthalene (decalin), perhydroanthracene, perhydrophenanthrene, perhydroacenaphthene, perhydrofluorene, perhydroindene, and perhydroindene. A condensed ring in which a plurality of 5- to 8-membered cycloalkane rings such as a phenalene ring are condensed 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.

  6-20 are preferable, as for carbon number of an aromatic group, 6-15 are more preferable, and 6-10 are more preferable. 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.

The heterocyclic group preferably contains a 5-membered ring or a 6-membered ring as the heterocycle. Another heterocycle, an aliphatic ring or an aromatic ring may be condensed with the heterocycle. 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 an aliphatic group). Group, aromatic group or heterocyclic group), aliphatic group, aromatic group, and heterocyclic group. 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, or the like) and a carbon number of 1 to 6. Represents an alkyl group (for example, a methyl group, an ethyl group, a propyl group, etc.), Z, or LZ. Here, L and Z have the same meanings as described above. As R ⁴ , R ⁵ and R ⁶ , a hydrogen atom or an alkyl group having 1 to 3 carbon atoms is preferable, and a hydrogen atom is more preferable.

As the monomer represented by the above formula (i), R ¹ , R ² , and R ³ are hydrogen atoms or methyl groups, and L contains a single bond, or an alkylene group, or an oxyalkylene structure. A compound having a divalent linking group, wherein 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. As the monomer represented by the above formula (iii), a compound in which R ⁴ , R ⁵ and R ⁶ are hydrogen atoms or a methyl group and Z is an aliphatic group, a heterocyclic group or an aromatic group is preferable.

Examples of typical compounds represented by the formulas (i) to (iii) include acrylic acid esters, methacrylic acid esters, and radically polymerizable compounds such as styrenes.
As examples of representative compounds represented by formulas (i) to (iii), the 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, more preferably 20 to 80% by mass, based on the total mass of the polymer compound. When the content of the hydrophobic structural unit is within the above range, the curable composition has more excellent effects of the present invention.

-Structural unit containing functional group capable of forming interaction with pigment etc. A functional group capable of forming interaction with pigment etc. 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 or the like include an acid group, a basic group, a coordinating group, and a reactive functional group.
When the polymer compound contains an acid group, a basic group, a coordinating group, or a reactive functional group, a structural unit containing an acid group, a structural unit containing a basic group, and a It is preferable to contain a structural unit containing a coordination group or a structural unit having reactivity.
In particular, when the polymer compound further contains, as an acid group, an alkali-soluble group such as a carboxylic acid group, the polymer compound can be imparted with developability for pattern formation by alkali development.
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 the pigment and the like is simultaneously alkali-soluble. The curable composition containing such a polymer compound has a better alkali developability (the unexposed portion is more easily dissolved by alkali development), and the obtained cured film has a better light shielding property. Have sex.

The polymer compound containing an acid group has higher affinity with the solvent described later. Therefore, the curable composition containing the polymer compound containing an acid group has more excellent coatability.
This is because the acid group in the structural unit containing an acid group easily interacts with the pigment or the like, the polymer compound stably disperses the pigment or the like, and the viscosity of the polymer compound in which the pigment or the like is dispersed further decreases. It is presumed that this is because the polymer compound itself is likely to be stably dispersed.

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

Among the functional groups capable of forming an interaction with a pigment and the like, examples of the acid group include a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, and a phenolic hydroxyl group, and a carboxylic acid group, a sulfonic acid group. , And at least one selected from the group consisting of a phosphoric acid group are preferable, and a carboxylic acid group is more preferable in that it has more excellent adsorptivity to pigments and the like and has more excellent 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 type or two or more types of 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 mass% with respect to the total mass of the polymer compound, and the image strength damage due to alkali development is further suppressed, 10 to 60 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 , Amide groups and the like. Among them, the tertiary amino group is preferable in that it has a better adsorptivity to pigments and the like and a better dispersibility. The polymer compound may contain one basic group 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 exhibits more excellent developability. From the point shown, 0.01 to 30 mass% is more preferable.

Among the functional groups capable of forming an interaction with the pigment and the like, a coordinating group, and as the reactive functional group, for example, acetylacetoxy group, trialkoxysilyl group, isocyanate group, acid anhydride group, and , Acid chloride groups and the like. Among them, an acetylacetoxy group is preferable because it has a better adsorptive power to the pigment and the like and is more likely to disperse the pigment and the like. The polymer compound may contain one kind of a coordinating group and one kind of a reactive functional group, or may contain two kinds or more. The polymer compound may or may not contain both 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 functional group having reactivity in the polymer compound is preferably 10 to 80 mass% with respect to the total mass of the polymer compound, and is curable. 20 to 60 mass% is more preferable in that the composition exhibits more excellent developability.

  When the polymer compound contains a functional group capable of forming an interaction with the pigment or the like in addition to the graft chain, it may have a functional group capable of forming an interaction with the pigment or the like. Although it is not particularly limited how it 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 are each independently a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom, and a bromine atom), or a carbon number. Represents an alkyl group of 1 to 6 (eg, methyl group, ethyl group, 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, each independently being a hydrogen atom. Or a methyl group is more preferable. In formula (iv), each of R ¹² and R ¹³ is more preferably a hydrogen atom.

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

L _{1 in} 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 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. The polyoxyalkylene structure is preferably a polyoxyethylene structure or a polyoxypropylene structure. Polyoxyethylene structure, - _(OCH 2 _CH 2) represented by n-, n is preferably an integer of 2 or more, and more preferably an integer of from 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 in addition to the graft chain, and is preferably a carboxylic acid group or a tertiary amino group, and a carboxylic acid group. Is more preferable.

In formula (vi), R ¹⁴ , R ¹⁵ , and R ¹⁶ are each independently a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom, and a bromine atom) or an alkyl group having 1 to 6 carbon atoms. group (e.g., methyl group, ethyl group, and propyl group), - _{Z 1,} or an _L 1 -Z _1. Here, L ₁ and Z ₁ have the same meanings as L ₁ and Z ₁ described above, and preferred examples are also the same. R ¹⁴ , R ¹⁵ , and R ¹⁶ are each independently preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and 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 is a divalent group containing an alkylene group or an oxyalkylene structure. 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 each independently represent a hydrogen atom or a methyl group, L ₁ represents a single bond or an alkylene group, and Z ₁ Compounds in which is a carboxylic acid group are preferred.

Below, the typical example of the monomer (compound) represented by Formula (iv) -Formula (vi) is shown.
As the monomer, for example, a reaction of succinic anhydride with 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) Substance, 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 , A reaction product of a compound containing an addition polymerizable double bond and a hydroxyl group in the molecule with trimellitic anhydride, a compound containing an addition polymerizable double bond and a hydroxyl group in the molecule and pyromellitic dianhydride Reaction product 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 the pigment or the like is high from the viewpoint of interaction with the pigment or the like, stability over time, and penetrability into a developer. 0.05-90 mass% is preferable with respect to the total mass of a molecular compound, 1.0-80 mass% is more preferable, 10-70 mass% is still more preferable.

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

-Physical properties of 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 further 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 developing 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, sedimentation of the pigment and the like in the curable composition is further suppressed, and the number of coarse particles is smaller. As a result, the curable composition has better stability over time. 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, a polymer compound having a desired acid value can be obtained by changing the content of the structural unit containing an acid group in the polymer compound.

The weight average molecular weight of the polymer compound is such that the curable composition has better developability, and the resulting cured film is less likely to peel off in the development step, and thus GPC (Gel Permeation Chromatography: gel permeation chromatography) is used. The polystyrene conversion value by the (graphography) method is preferably 4,000 to 300,000, more preferably 5,000 to 200,000, further preferably 6,000 to 100,000, and particularly preferably 10,000 to 50,000. preferable.
The GPC method is based on a method in which HLC-8020GPC (manufactured by Tosoh Corporation) is used, TSKgel SuperHZM-H, TSKgel SuperHZ4000, TSKgel SuperHZ2000 (manufactured by Tosoh Corporation, 4.6 mm ID × 15 cm) are used as columns, and THF (tetrahydrofuran) is used as an eluent. . The polymer compound can be synthesized by a known method.

Specific examples of the polymer compound include "DA-7301" manufactured by Kusumoto Kasei Co., Ltd., "Disperbyk-101 (polyamidoamine phosphate)" manufactured by BYK Chemie, 107 (carboxylic acid ester), 110 (copolymer containing an acid group). ), 111 (phosphoric acid-based dispersant), 130 (polyamide), 161, 162, 163, 164, 165, 166, 170, 190 (polymer), “BYK-P104, P105 (high molecular weight). "Saturated polycarboxylic acid)", "EFKA 4047, 4050-4010-4165 (polyurethane type), EFKA 4330-4340 (block copolymer), 4400-4402 (modified polyacrylate), 5010 (polyester amide), 5765 (manufactured by EFKA). High molecular weight polycarboxylic acid salt), 6220 (fatty acid polyester) ), 6745 (phthalocyanine derivative), 6750 (azo pigment derivative) "," Ajinomoto Fine-Techno Co., Ltd. "" Adisper PB821, PB822, PB880, PB881 ", Kyoeisha Chemical Co., Ltd." Floren TG-710 (urethane oligomer) "," Polyflow " No. 50E, No. 300 (acrylic copolymer), Kusumoto Kasei's "Disparlon KS-860, 873SN, 874, # 2150 (aliphatic polycarboxylic acid), # 7004 (polyether ester), DA -703-50, DA-705, DA-725 ", Kaosha's" Demol RN, N (naphthalene sulfonic acid formalin polycondensate), MS, C, SN-B (aromatic sulfonic acid formalin polycondensate) " , "Homogenol L-18 (polymeric polycarboxylic acid)", "Emulgen 920" 930, 935, 985 (polyoxyethylene nonylphenyl ether) "," acetamine 86 (stearylamine acetate) ", Nippon Lubrizol" Solsperse 5000 (phthalocyanine derivative), 22000 (azo pigment derivative), 13240 (polyester amine), 3000, 12000, 17000, 20000, 27000 (polymer containing a functional part at the end), 24000, 28000, 32000, 38500 (graft copolymer) ", Nikko Chemicals' Nikkor T106 (polyoxyethylene sorbitan mono) OLE ART), MYS-IEX (polyoxyethylene monostearate) ", Kawaken Fine Chemicals Hinoact T-8000E, Shin-Etsu Chemical Organosiloxane Polymer KP341, Yusho W001: Cationic surfactant ", polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate , Nonionic surfactants such as sorbitan fatty acid ester, 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 ", San Nopco's" Disperse Aid 6, Disperse Aid 8, Disperse Aid 15, Dispa " Polymer dispersants such as Suede 9100, "ADEKA Pluronic L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, P" manufactured by ADEKA. -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.
In addition, DISCERBYK-130, DISPERBYK-140, DISPERBYK-142, DISPERBYK-145, DISPERBYK-180, DISPERBYK-187, DISPERBYK-191, DISPERBYK-2001, DISPERBYK-2010, 20K, 20K, 20K, DISPERBYK manufactured by BIC Chemie. BYK-9076, Ajinomoto Fine Techno Co., Ltd. Ajisper PB821, Ajisper PB822, and Ajisper PB881 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 also be used, and the contents thereof are incorporated in the present specification.

As the dispersant, the graft copolymers of paragraphs 0037 to 0115 of JP 2010-106268 A (corresponding paragraphs 0075 to 0133 of US2011 / 0124824) can also be used, the contents of which are incorporated herein. Be done.
As the dispersant, a constituent component containing a side chain structure in which the acidic groups of paragraphs 0028 to 0084 of JP 2011-153283 A (corresponding to paragraphs 0075 to 0133 of US 2011/0279759) are bonded via a linking group. It is also possible to use polymer compounds containing, the contents of which are incorporated herein.
As the dispersant, the resins described in paragraphs 0033 to 0049 of JP-A-2016-109763 can also be used, and the contents thereof are incorporated in the present specification.

(Binder resin)
The curable composition preferably contains a binder resin.
The content of the binder resin is preferably 0.1 to 30 mass% with respect to the total solid content of the curable composition.
The binder resins may be used alone or in combination of two or more. When two or more binder resins are used in combination, the total amount thereof is preferably within the above range.

  A linear organic polymer is preferably used as the binder resin. As such a linear organic polymer, any known one can be used. Preferably, a linear organic polymer that is soluble or swellable in water or weak alkaline water is selected to allow water development or weak alkaline water development. Among them, as the binder resin, an alkali-soluble resin (a resin containing a group that promotes alkali-solubility) is particularly preferable.

The alkali-soluble resin is intended to be a resin containing a group that promotes alkali-solubility (alkali-soluble group), and is intended to be a resin different from the dispersant described above.
Examples of the alkali-soluble resin include resins containing at least one alkali-soluble group in the molecule, and examples thereof include polyhydroxystyrene resin, polysiloxane resin, (meth) acrylic resin, (meth) acrylamide resin, (meth) acrylic. Examples include / (meth) acrylamide copolymers, epoxy resins, and polyimide resins.

Specific examples of the alkali-soluble resin include copolymers of unsaturated carboxylic acid and ethylenically unsaturated compound.
The unsaturated carboxylic acid is not particularly limited, but includes monocarboxylic acids such as (meth) acrylic acid, crotonic acid, and vinylacetic acid; dicarboxylic acids such as itaconic acid, maleic acid, and fumaric acid, or an acid anhydride thereof. And the like; polyvalent carboxylic acid monoesters such as phthalic acid mono (2- (meth) acryloyloxyethyl); and the like.

  Examples of the copolymerizable ethylenically unsaturated compound include methyl (meth) acrylate. The compounds described in paragraphs 0027 of JP-A-2010-97210 and paragraphs 0036 to 0037 of JP-A-2015-68893 can also be used, and the above contents are incorporated herein.

  Further, a copolymerizable ethylenically unsaturated compound having a side chain containing an ethylenically unsaturated group 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, the carboxylic acid group of the acrylic resin containing a carboxylic acid group, an addition reaction of an ethylenically unsaturated compound containing a glycidyl group or an alicyclic epoxy group You can get it.

  Examples of the alkali-soluble resin include, for example, JP-A-59-44615, JP-B-54-34327, JP-B-58-12577, JP-B-54-25957, JP-A-54-92723, and JP-A-59-. 53836, and radical polymers containing a carboxylic acid group in the side chain described in JP-A-59-71048; EP993966, EP1204000, and JP2001-318463. And an acetal-modified polyvinyl alcohol-based binder resin containing an alkali-soluble group, polyvinylpyrrolidone, polyethylene oxide, alcohol-soluble nylon, and 2,2-bis- (4-hydroxyphenyl) -propane. Polyether, which is a reaction product with epichlorohydrin; International Publication No. 2 And the like can be used; polyimide resin described in JP 08/123097.

  As the alkali-soluble resin, for example, the 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 is intended to be 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.
Examples of the polyimide precursor include a resin containing a repeating unit represented by the formula (1). Examples of the structure of the polyimide precursor include, for example, an amic acid structure represented by the following formula (2) and the following formula (3) in which the amic acid structure is partially imide-closed, and / or the following formula in which all imide rings are imide-closed. The thing containing the imide structure shown by (4) is mentioned.
In addition, in this specification, the polyimide precursor which has an amic acid structure may be called 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 2008-106250 A, compounds described in paragraphs 0022 to 0039 of JP 2016-122101 A, and JP 2016-68401 A. Examples thereof include the compounds described in paragraphs 0061 to 0092 of the publication, 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 resins described in paragraph 0050 of JP-A-2014-137523, resins described in paragraph 0058 of JP-A-2015-187676, and JP-A-2014-106326. Examples thereof 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. The polymerization inhibitor is not particularly limited, and known polymerization inhibitors 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-t-butylphenol), 2,2'-methylenebis (4-methyl-6-t-butylphenol), 4-methoxynaphthol, etc.); hydroquinone polymerization inhibition Agents (for example, hydroquinone and 2,6-di-tert-butylhydroloquinone and the like); quinone-based polymerization inhibitors (for example, benzoquinone and the like); free-radical-based polymerization inhibitors (for example, 2, 2, 6, and so on) 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 them, the phenol-based polymerization inhibitor or the free radical-based polymerization inhibitor is preferable in that the curable composition has the more excellent effect 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 at the time of synthesizing 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 curable composition has better stability over time, and in that it has better curability, the total solid content of the curable composition. 0.0001 to 1 mass% is preferable with respect to the minute.
The polymerization inhibitors may be used alone or in combination of two or more. 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 production of the dispersion composition; after the production of the dispersion composition; during the production of the curable composition; after the production of the curable composition; etc., the temperature of the dispersion composition and / or the curable composition becomes high. Even when there is a concern that the resin containing a curable group may 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 it is generally preferable that the solid content of the curable composition is adjusted to 20 to 90% by mass, and adjusted to 30 to 90% by mass. More preferably.
The solvent may be used alone or in combination of two or more. When two or more kinds of solvents are used in combination, it is preferable that the total solid content of the curable composition is adjusted to fall within the above range.

Examples of the solvent include water and organic solvents.
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 include, but are not limited to, butyl acetate, methyl lactate, N-methyl-2-pyrrolidone, ethyl lactate, and the like.

<Surfactant>
The curable composition preferably contains a surfactant. The curable composition containing a surfactant has more excellent coatability.
The content of the surfactant in the curable composition is not particularly limited, but it is preferably 0.001 to 2.0 mass% with respect to the total solid content of the curable composition.
As the surfactant, one type may be used alone, or two or more types may be used in combination. 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 characteristics (particularly the 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 lowering the interfacial tension between the support and the curable composition. The wettability of the composition to the support is improved, and the coatability of the curable composition is improved. Therefore, even when a curable composition layer having a thickness of about several μm is formed with a small amount of liquid, it is possible to form a curable composition layer having a less uniform thickness and a more uniform thickness.

  The fluorine content in the fluorine-based surfactant 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, curing The composition has more excellent liquid saving property. Further, when it is within the above range, the fluorine-based surfactant is more easily dissolved in the curable composition.

Examples of the fluorinated surfactant include Megafac F171, F172, F173, F176, F177, F141, F142, F143, F144, R30, F437, F475 and F479. F482, F554, F780 (above, manufactured by DIC Corporation), Florard FC430, FC431, FC171 (above, manufactured by Sumitomo 3M Ltd.), Surflon S-382, SC-101, SC-101. 103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, KH-40 (above Asahi Glass Co., Ltd.), PF636, PF656, Examples thereof include PF6320, PF6520, and PF7002 (manufactured by OMNOVA).
A block polymer may be used as the fluorine-based surfactant, for example, the compound described in JP 2011-89090 A may be used, and the above contents are incorporated in the present specification.

<Ultraviolet absorber>
The curable composition may contain an ultraviolet absorber. The cured film obtained from the curable composition containing the ultraviolet absorber has a more excellent pattern shape (finer pattern shape).
As the ultraviolet absorber, salicylate-based, benzophenone-based, benzotriazole-based, substituted acrylonitrile-based, and triazine-based ultraviolet absorbers can be used.
As the ultraviolet absorber, for example, the compounds described in JP 2012-068418 A, paragraphs 0137 to 0142 (corresponding paragraphs 0251 to 0254 of US2012 / 0068292) can be used, and the above contents are incorporated in the present specification. Be done.
As the ultraviolet absorber, a diethylamino-phenylsulfonyl-based ultraviolet absorber (manufactured by Daito Chemical Co., Ltd., trade name: UV-503) and 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 in the present specification.
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 based on the total solid content of the curable composition. More preferably, 0.1-5 mass% is still more preferable.

<Silane coupling agent>
The curable composition may contain a silane coupling agent.
In the present specification, the silane coupling agent means a compound containing the following hydrolyzable group and a functional group other than that in the molecule. The above-mentioned hydrolyzable group means a substituent which is directly bonded to a silicon atom and can form 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 bonded to a silicon atom. When the hydrolyzable group contains a carbon atom, the carbon number thereof is preferably 6 or less, and more preferably 4 or less. Particularly, an alkoxy group having 4 or less carbon atoms or an alkenyloxy group having 4 or less carbon atoms is preferable.

  The silane coupling agent preferably contains neither a silicon atom other than the silicon atom to which the hydrolyzable group is bonded, nor a 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, based on the total solid content in the curable composition. 0.0 to 6 mass% is more preferable.
The silane coupling agent may be used alone or in combination of two or more. When two or more silane coupling agents are used in combination, the total content is preferably within the above range.

[Method for producing curable composition]
The curable composition may 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, etc.). it can.
Upon preparation of the curable composition, the respective components may be blended together, or the respective components may be dissolved or dispersed in a solvent and then sequentially blended. In addition, the order of addition and the working conditions at the time of compounding are not particularly limited.

The curable composition is preferably filtered with a filter for the purpose of removing foreign matters 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, but examples thereof include fluororesins such as PTFE (polytetrafluoroethylene), polyamide resins such as nylon, and polyolefin resins such as polyethylene and polypropylene (PP) (high density, super Examples of the filter include a polymer having a high molecular weight) and the like. 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, further preferably 0.2 to 1.5 μm, and 0.3 to 0. 0.7 μm is particularly preferable. Within this range, it is possible to reliably remove fine foreign matters such as impurities and agglomerates contained in the pigment while suppressing the filter clogging of the pigment.
When using the 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 different filters are combined to perform filtering two or more times, the pore size of the filter used for the second filtering is preferably the same as or larger than the pore size of the filter used for the first filtering. Further, filters having the same material but different pore sizes may be combined. For the pore size here, the nominal value of the filter manufacturer can be referred to.
Examples of commercially available filters include filters manufactured by Nippon Pole, Advantech Toyo, Japan Entegris (formerly Japan Microlith), and Kits Microfilter.

The second filter may be made of the same material as the first filter. 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, and further preferably 0.3 to 6.0 μm.
The curable composition preferably contains substantially no impurities such as metals (particles and ions), metal salts containing halogen, acids, and alkalis. In the present specification, “substantially free from” means that it cannot be detected by the following measuring method.
The content of impurities contained in the curable composition, the above components, and the filter and the like is not particularly limited, but is preferably 1 mass ppm or less, more preferably 1 mass ppb or less, and more preferably 100 mass ppm or less with respect to the total mass. A mass ppt or less is more preferable, and a mass ppt or less is particularly preferable, and it is most preferable not to contain substantially.
The content of the above impurities can be measured by an inductively coupled plasma mass spectrometer (Yokogawa Analytical Systems, Agilent 7500cs type).
It should be noted that ppm represents parts per million, ppb represents parts per billion, and ppt represents parts per million.

〔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, one having a high cleanliness inside the container and less elution of impurities is preferable. For example, a commercially available product for semiconductor use may be used.
Specific examples of usable containers 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 multi-layer bottle in which the inner wall of the container is made of 6 kinds of resins in a 6-layer structure, or a multi-layer bottle in which the inner wall of the container is made of 6 kinds of resin in a 7-layer structure. Examples of these containers include the containers described in JP-A-2015-123351.

[Cured film and method for producing cured film]
The cured film according to the embodiment of the present invention is a cured film obtained by curing the curable composition. Although the thickness of the cured film is not particularly limited, it is generally preferably 0.2 to 7 μm, more preferably 0.4 to 5 μm.
The above-mentioned thickness is an average thickness, and is a value obtained by measuring the thicknesses of arbitrary 5 or more points of the cured film and arithmetically averaging them.

The method for producing the cured film is not particularly limited, and examples thereof include a method in which the curable composition is applied on a support to form a coating film, and the coating film is subjected to a curing treatment to produce a cured film.
The method of curing treatment is not particularly limited, and examples thereof include light curing treatment or heat curing treatment. From the viewpoint of easy pattern formation, photocuring treatment (particularly, curing treatment by irradiation with actinic rays or radiation) is preferable. ..

The cured film according to the embodiment of the present invention is a cured film obtained by curing a curable composition layer formed using a curable composition.
The method for producing the cured film is not particularly limited, but it is preferable to include the following steps.
-Curable composition layer forming step-exposure step-developing step Hereinafter, each step will be described.

<Curable composition layer forming step>
The curable composition layer forming step is a step of forming a curable composition layer using the curable composition. Examples of the step of forming a curable composition layer using the curable composition include a step of applying a curable composition on a support to form a curable composition layer (application step). Can be mentioned.
The type of support is not particularly limited, but when a cured film is applied to a solid-state image sensor, for example, a silicon substrate is used, and when the cured film is used as a color filter (including a solid-state image sensor color filter), , Glass substrates (glass wafers), and the like.
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 method. To be
The curable composition applied 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 actinic rays or radiation through a photomask having a patterned opening, and was exposed to light. Only the curable composition layer is cured.
The exposure is preferably performed by irradiation with radiation, and ultraviolet rays such as g-rays, h-rays and i-rays are preferably used. A high pressure mercury lamp is preferable as the light source. The irradiation intensity is not particularly limited, but generally 5 to 1500 mJ / cm ² is preferable.

<Developing process>
After the exposure step, a development process (development step) is performed to elute the unexposed portion in the exposure step with the developer. This leaves only the photo-cured part on the support.
The developing solution is not particularly limited, but examples thereof include an alkaline developing solution, and among them, an organic alkaline developing solution is preferable.
The developing conditions are not particularly limited, but the developing temperature is generally preferably 20 to 40 ° C., and the developing time is generally preferably 20 to 180 seconds.
The alkaline aqueous solution (alkali 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 hydrogen carbonate, sodium silicate, and , Sodium metasilicate and the like.
The content of the above compound in the alkaline aqueous solution is not particularly limited, but generally 0.001 to 10% by mass, and more preferably 0.005 to 0.5% by mass, based on the total mass of the alkaline aqueous solution.
The alkaline compound contained in the organic alkaline developer includes ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxy. And choline, pyrrole, piperidine, and 1,8-diazabicyclo- [5,4,0] -7-undecene.
The content of the above compound in the alkaline aqueous solution is not particularly limited, but generally 0.001 to 10% by mass, and more preferably 0.005 to 0.5% by mass, based on the total mass of the alkaline aqueous solution.

The alkaline aqueous solution may contain 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 developing solution, it is preferable to wash the developed curable composition layer with pure water or the like. In this specification, this step is referred to as a cleaning step, and the method for producing a cured film preferably includes a cleaning step.

The method for producing a cured film may include other steps.
The other steps are not particularly limited and can be appropriately selected depending on the purpose.
Examples of the other steps include a surface treatment step of the base material, a pre-heating step (pre-baking step), and a post-heating step (post-baking step).
The heating temperature in the pre-heating step and the post-heating 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 reflectance of the cured film can be reduced. Even if the cured film itself has an uneven structure on its surface, a coat film may be arranged on the cured film to provide the uneven structure. The shape of the surface uneven 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, still more preferably 2% or less.
The method of producing the surface uneven structure is not particularly limited, but a method of incorporating an organic filler and / or an inorganic filler into a cured film or a coat film; a lithography method, an etching method, a sputtering method, a nanoimprint method, etc. And the like, a method of roughening the surface of the cured film and / or the coat film, and the like.
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 on the low refractive index film (for example, a high refractive index film) And a method of forming a low optical density layer and a high optical density layer, which are described in JP-A-2015-1654.

  The above-mentioned cured film is a portable device such as a personal computer, a tablet, a mobile phone, a smartphone, and a digital camera; an OA (Office Automation) device such as a printer multifunction peripheral and a scanner; a surveillance camera, a bar code reader, and an automatic cash deposit. Industrial equipment such as ATM (automated teller machine), high-speed camera, and equipment having a personal authentication function using face image authentication; vehicle-mounted camera equipment; endoscope, capsule endoscope, and Medical camera equipment such as catheters; biological sensors, biosensors, military reconnaissance cameras, stereoscopic map cameras, weather and ocean observation cameras, land resource exploration cameras, and exploration cameras for space astronomical and deep space targets Optics used for space equipment, etc. Filter 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 be used for applications such as a micro LED (Light Emitting Diode) and a micro OLED (Organic Light Emitting Diode). The above-mentioned cured film is suitable not only for optical filters and optical films used for micro LEDs and micro OLEDs, but also for members that impart a light shielding function or an antireflection function.
Examples of the micro LED and the micro OLED include those described in JP-T-2015-500562 and JP-T-2014-533890.

The cured film is suitable as an optical filter and an optical film used in a quantum dot display. Further, it is suitable as a member that imparts a light shielding function and an antireflection function.
Examples of quantum dot displays are 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. The ones mentioned are mentioned.

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

Configuration examples of the solid-state imaging device and the solid-state imaging device will be described with reference to FIGS. 7 to 8. Note that, in FIGS. 7 to 8, in order to clarify each part, the ratio of the thickness and / or the width of each configuration is partially exaggerated regardless of the actual condition.
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 held above the solid-state imaging element 701 and sealing the solid-state imaging element 701. There is. Further, a lens layer 711 is provided on the cover glass 703 with a spacer 704 interposed therebetween. The lens layer 711 includes a support body 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 molded. When stray light is incident on the peripheral area of the lens layer 711, the effect of light collection on the lens material 712 is weakened due to the diffusion of light, and the light reaching the imaging unit 702 is reduced. Also, noise is generated due to stray light. Therefore, a light shielding film 714 is provided in the peripheral area of the lens layer 711 to shield the light. The cured film according to the embodiment of the present invention (in particular, 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 the optical image formed in the imaging unit 702, which is the light receiving surface, and outputs it as an image signal. The solid-state image sensor 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 known materials 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 image capturing unit 702, dark current (noise) is generated from the circuits in the peripheral area. Therefore, the peripheral area is shielded by 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 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) (a bonding wire is also possible) provided on the surface of the chip substrate 706.

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

  As shown in FIG. 8, the image pickup unit 702 is configured of each unit provided on the substrate 804 such as the light receiving element 801, the color filter 802, and the microlens 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 a black pigment is contained as a colorant) can be used as the black matrix 805bm.

  As the material of the substrate 804, the same material as that of the chip substrate 706 described above 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 which are n-type layers and which generate and store signal charges by photoelectric conversion are arranged in a square lattice.

  A vertical transfer path 808 composed of an n-type layer is formed on one side of the light receiving element 801 via a read gate portion 807 on the surface layer of the p well layer 806. Further, on the other side of the light receiving element 801, a vertical transfer path 808 belonging to an adjacent pixel is formed via an element isolation region 809 made of a p-type layer. The read gate portion 807 is a channel region for reading out the signal charges 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. A vertical transfer electrode 811 made of polysilicon or amorphous silicon is formed on the gate insulating film 810 so as to cover the vertical transfer path 808, the read gate portion 807, and the element isolation region 809 substantially immediately above. The vertical transfer electrode 811 functions as a drive electrode that drives the vertical transfer path 808 to perform charge transfer, and a read electrode that drives the read gate unit 807 to perform signal charge read. 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 directly above the light receiving element 801, and shields the other area. 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 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 flattening film 815 made of a transparent resin or the like are provided. ing. The color filter 802 is formed on the intermediate layer.

[Black matrix]
The black matrix contains the cured film according to the embodiment of the present invention. The black matrix may be contained in a color filter, a solid-state image sensor, and a liquid crystal display device.
The black matrix has already been described above; a black edge provided on the peripheral portion of a display device such as a liquid crystal display device; a grid pattern and / or stripe pattern between red, blue and green pixels. Black portions; dot-like and / or line-like black patterns for light shielding of TFTs (thin film transistors); and the like. For the definition of this black matrix, refer to, for example, Taihei Sugano, “Dictionary for Liquid Crystal Display Manufacturing Equipment,” Second 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 driving type liquid crystal display device using a thin film transistor (TFT), to prevent deterioration of image quality due to current leakage of light. .

  The method for producing the black matrix is not particularly limited, but the black matrix can be produced by the same method as the method for producing the cured film. Specifically, a curable composition is applied onto a support to form a curable composition layer, which is then 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 glasses such as soda lime glass, alkali-free glass, quartz glass, and borosilicate glass; polyester-based resins and plastics such as polyolefin-based resins; and the like. From the viewpoint of chemical resistance and heat resistance, non-alkali glass, quartz glass and the like are 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 openings of the black matrix formed on the support can be exemplified.

The color filter containing the black matrix (cured film) can be manufactured, 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 the color filter is formed in the opening of the patterned black matrix formed on the support. The resin composition for each color is not particularly limited, and a known resin composition can be used, but it is preferable to use the curable composition according to the embodiment of the present invention.
Next, the resin composition layer is exposed through a photomask having a pattern corresponding to the openings of the black matrix. Next, after removing the unexposed portion by a developing process, baking is performed to form a colored pixel in the opening portion of the black matrix. Producing a color filter having red pixels, green pixels, and blue pixels by performing a series of operations using a resin composition for each color containing a red pigment, a green pigment, and a blue pigment, for example. You can

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

  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 to face each other and a liquid crystal compound enclosed between the supports. And a form including. The support is as described above for the black matrix support.

  As a concrete 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) A laminated body containing the element / support / polarizing plate / backlight unit in this order can be mentioned.

  The liquid crystal display device is not limited to the above, and includes, for example, "Electronic display device (Akio Sasaki, published by Industrial Research Institute Co., Ltd., 1990)", "Display device (Junsho Ibuki, Sangyo Tosho Co., Ltd.) Liquid crystal display device described in "Issued annually" and the like. Further, for example, a liquid crystal display device described in “Next-generation liquid crystal display technology (edited by Tatsuo Uchida, published by Industrial Research Institute Co., Ltd., 1994)” can be mentioned.

[Infrared sensor]
The infrared sensor which concerns on embodiment of this invention contains the said cured film.
The infrared sensor according to the above embodiment will be described with reference to FIG. In the infrared sensor 900 shown in FIG. 9, reference numeral 910 indicates 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). A film that shields light having a wavelength of 900 to 1000 nm) is preferable, and a cured film containing an infrared absorbing agent (the form of the infrared absorbing agent is as described above) 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 are provided. The formed color filter or the like is used, and the form thereof is as described above.
A resin film 914 (for example, a transparent resin film) capable of transmitting light having a wavelength that has passed through the infrared transmission filter 913 is disposed between the infrared transmission filter 913 and the solid-state image sensor 910.
The infrared transmission filter 913 is a filter that has a visible light shielding property and transmits infrared rays having a specific wavelength, and is a colorant that absorbs light in the visible light region (for example, a perylene compound and / or bisbenzo). 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, a polymethine compound, or the like) can be used. The infrared transmission filter 913 preferably blocks, for example, light having a wavelength of 400 to 830 nm and transmits light having a wavelength of 900 to 1300 nm.
A microlens 915 is arranged on the incident light hν side of the color filter 912 and the infrared transmission filter 913. A flattening film 916 is formed so as to cover the microlens 915.
Although the resin film 914 is arranged in the embodiment shown in FIG. 9, 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 they may be different.
In the embodiment shown in FIG. 9, the color filter 912 is provided on the incident light hν side of the infrared absorption filter 911. However, the order of the infrared absorption filter 911 and the color filter 912 is exchanged to change the infrared absorption filter 911. May be provided on the incident light hν side of the color filter 912.
In the embodiment shown in FIG. 9, the infrared absorption filter 911 and the color filter 912 are laminated adjacent to each other, but the filters do not necessarily have to be adjacent to each other, and another layer may be provided therebetween. . The cured film according to the embodiment of the present invention can be used as a light-shielding film on the end portion or side surface of the surface of the infrared absorption filter 911, and can also be used for the inner wall of the device of the infrared sensor to provide internal reflection or light reception It is possible to prevent unintended incidence of light and improve the sensitivity.
According to this infrared sensor, image information can be captured at the same time, so that it is possible to perform motion sensing in which an object whose motion is to be detected is recognized. Furthermore, since the distance information can be acquired, it is possible to capture an image including 3D information.

Next, a solid-state imaging device to which the above 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. Note that paragraphs 0032 to 0036 of JP 2011-233983 A can be referred to for each structure of the solid-state imaging device, and the contents thereof are incorporated in the present specification.

  Hereinafter, the present invention will be described in more detail based on examples. The materials, usage amounts, ratios, treatment contents, treatment procedures, and the like shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be limitedly interpreted by the following examples.

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

The precursor A in the above formula was synthesized using the method described in paragraph 0026 of Japanese Patent No. 4223071. Next, to a DMAc (N, N dimethylacetamide, 160 g) solution in which the precursor A (6.00 g, 12.6 mmol) was cooled in an ice bath, myristic acid chloride (15.6 g, 63.2 mmol) was added. ) Was added dropwise and after stirring for 1 hour under the same temperature conditions, it was further stirred at 20 ° C. for 3 hours to obtain a reaction solution. Next, to the reaction solution, 400 mL of ethyl acetate and 200 mL of a 4% by mass aqueous sodium bicarbonate solution were added and stirred for 1 hour to generate a solid substance in the reaction solution. Next, the generated solid matter was removed by Celite filtration, the filtrate was further washed twice with 200 mL of an aqueous solution of sodium hydrogen carbonate, then separated, 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 for the oily liquid, a developing solvent was made a mixture of hexane and ethyl acetate, and the mixture ratio (volume ratio) was 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): 1.15-1.38 (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 2009-191061 A, and then cooled in an ice bath, and precursor B (6.00 g, 11.3 mmol). To a THF (tetrahydrofuran, 60 g) solution in which triethylamine (1.62 g, 16.0 mmol) was dissolved, myristic acid chloride (3.34 g, 13.5 mmol) was added dropwise, and after the addition, the mixture was stirred at the same temperature for 1 hour. After that, the mixture was further stirred at 20 ° C. for 3 hours to obtain a reaction solution. Next, to the reaction solution, 400 mL of ethyl acetate and 200 mL of a 4% by mass aqueous sodium bicarbonate solution were added, and the layers were separated to obtain an organic phase. Next, the obtained organic phase was washed twice with 200 mL of a sodium bicarbonate aqueous 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 for the oily liquid, a developing solvent was made a mixture of hexane and ethyl acetate, and the mixture ratio (volume ratio) was changed from hexane / ethyl acetate = 4/1 to hexane / acetic acid. Purification by changing to ethyl = 1/1 to obtain 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 0.75 to 7.85 (m, 4H), 8.02 (d, 2H)

[Synthesis of INT-17]

The precursor C in the above formula was synthesized by using the method described in paragraph 0355 of JP-T-2016-531926. Next, the same as the synthesis of INT-31 described above, except that "precursor C (5.01 g, 11.3 mmol)" was used in place of "precursor B (6.00 g, 11.3 mmol)". The oxime compound INT-17 (4.94 g, 7.56 mmol) was obtained. 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 to 8.08 (m, 13H)

[Synthesis of INT-26]

The precursor D in the above formula was synthesized using the method described in paragraph 0368 of JP2009-191061A. Next, in place of "precursor B (6.00 g, 11.3 mmol)", "precursor D (6.27 g, 11.3 mmol)" was used, and the synthesis of INT-31 described above was performed. Similarly, an 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 to 3.25 (m, 4H), 4.43 (q, 2H), 7.22 to 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 compound.

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

<Intermediate 1 synthesis process>
Pentaerythritol (PE) (13.5 g, 99.2 mmol) and N, N-dimethylacetamide (DMAc) (200 g) were 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 mixed solution so that the temperature of the mixed solution did not exceed 30 ° C., and the mixture was 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 aqueous sodium hydrogen carbonate (250 g), water (250 g) and saturated saline (150 g), respectively. Next, sodium sulfate was added to the washed organic phase, followed by filtration 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 process>
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 mixed solution was obtained. Next, potassium thioacetate (51.0 g, 446 mmol) was added to the mixed solution in 4 portions, and the mixture was 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 organic layer 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 saline (350 g) to wash the organic phase. Next, sodium sulfate was added to the washed organic phase and the mixture was 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 the mixture was stirred at 15 ° C under a nitrogen atmosphere to obtain a mixed liquid. Next, hydrazine hydrochloride (35.2 g, 514 mmol) and sodium acetate (84.4 g, 1.03 mol) were added to the mixed solution, and the mixture was 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 solution was separated twice with 1 mol / L hydrochloric acid (280 g) and then twice with saturated saline (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).

  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, polyfunctional thiol compound, colorant, and other components described in each column of Table 5 were mixed to prepare curable compositions of Examples and Comparative Examples. The content of each component is shown in Table 3.

  The final solid content of each curable composition was adjusted with an organic solvent so as to be 28% by mass. The organic solvent was used in combination so that the mass ratio in each curable composition was PGMEA (propylene glycol monomethyl ether acetate) / butyl acetate / cyclohexanone = 27/18/27.

  In the curable compositions of Comparative Examples, compounds used in place of the specific oxime compound (Comparative Compound 1 and Comparative Compound 2 are referred to as "CINT-1" and "CINT-2" in Table 5-2, respectively. ).) Is shown below.

[Preparation of colorant]
Each colorant used for the preparation of the curable composition was prepared by the following method.

(Titanium nitride-containing particles (TiN-1))
First, Ti particles (TC-200, manufactured by Toho Tech Co., Ltd.) were plasma-treated in Ar gas to form Ti nanoparticles. The Ti nanoparticles after the plasma treatment were allowed to stand in an Ar gas atmosphere at an O ₂ concentration of 50 ppm or less at 30 ° C. for 24 hours, and then O ₂ gas was introduced into the Ar atmosphere so that the O ₂ concentration became 100 ppm. In this state, it was left standing at 30 ° C. for 24 hours (pretreatment of Ti particles).
Then, the obtained Ti nanoparticles were classified by using a TTSP separator manufactured by Hosokawa Micron under the condition that the yield was 10% to obtain powder of Ti particles. The primary particle diameter of the obtained powder was 120 nm when the average particle diameter of 100 particles was obtained by arithmetical averaging by TEM observation.
The titanium nitride-containing particles TiN-1 were produced by using an apparatus similar to the apparatus for producing black composite fine particles shown in FIG. 1 of WO 2010/147098.
Specifically, in the black composite fine particle producing 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 of 50 L / min and nitrogen is supplied as plasma gas 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. Further, 10 L / min of carrier gas was supplied from the atomizing gas supply source of the material supply device.
Then, with respect to the Ti particles obtained as described above, Fe powder (JIP270M, manufactured by JFE Steel Co., Ltd.) and Si powder (Silicon powder SI006031) were used in a mass ratio of Ti / Fe / Si = balance. /0.05/0.05 and mixed with argon gas which is a carrier gas into a thermal plasma flame in a plasma torch, vaporized in the thermal plasma flame, and highly dispersed in a gas phase state. It was
Further, nitrogen was used as the 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 rate was 1000 L / min. The pressure inside the cyclone was 50 kPa, and the feed 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 content of titanium (Ti) atoms, iron (Fe) atoms, and silicon (Si) atoms in the obtained titanium nitride-containing particles TiN-1 was measured by ICP (Inductively Coupled Plasma) emission spectroscopy. For the ICP emission spectroscopic analysis method, an ICP emission spectroscopic analyzer “SPS3000” (trade name) manufactured by Seiko Instruments Inc. was used.
Further, the content of nitrogen atoms 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 particles TiN was Ti / N / Fe / Si = 57/34 / 0.0030 / 0.0020.

The X-ray diffraction of titanium nitride-containing particles TiN-1 was measured by packing a powder sample in an aluminum standard sample holder and using a wide-angle X-ray diffraction method (manufactured by Rigaku Denki Co., Ltd., trade name “RU-200R”). As the measurement conditions, the X-ray source was CuKα ray, the output was 50 kV / 200 mA, the slit system was 1 ° -1 ° -0.15 mm-0.45 mm, the measurement step (2θ) was 0.02 °, and the scan speed was 2 ° / min.
Then, the diffraction angle of the peak derived from the TiN (200) plane observed near the diffraction angle 2θ (42.6 °) was measured. Further, from the half width of the peak derived from this (200) plane, the crystallite size constituting the particles was obtained using Scherrer's formula. As a result, the diffraction angle of the peak was 42.62 °, and the crystallite size was 10 nm. No X-ray diffraction peak due to TiO ₂ was found.

(Titanium nitride-containing particles TiN-2)
As the Ti particles, "578-347" manufactured by Sigma-Aldrich Co., Ltd. was used instead of "TC-200" manufactured by Toho Tech Co., and each of the Fe powder and the Si powder had a mass ratio of Ti / Fe / Si = residual / Titanium nitride-containing particles TiN-2 were obtained in the same manner as TiN-1 except that the mixture was adjusted 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 were obtained in the same manner as TiN-1 except that Fe powder and Si powder were mixed so that the mass ratio of each was Ti / Fe / Si = residual / 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 (NbN) Containing Fe Atoms)
Niobium nitride-containing particles containing Fe atoms were produced by the following method.
First, niobium (powder) <100-325 mesh> manufactured by Mitsuwa Chemical Co., Ltd. was prepared as a raw material (hereinafter, also referred to as “metal raw material powder”).
Next, the above metal raw material powder was subjected to a plasma treatment in Ar gas (the treatment condition was the following plasma treatment (1)) to form Nb nanoparticles.

・ Plasma treatment (1)
Plasma treatment (1) was performed by the following method. Plasma processing (1) was performed under the following conditions using an apparatus similar to the above-mentioned black composite fine particle manufacturing apparatus.
-High frequency voltage applied to the high frequency oscillation coil: frequency, about 4 MHz, voltage, about 80 kVA
・ Plasma gas: Argon gas (supply rate 100 L / min)
・ Carrier gas: Argon gas (supply rate 10 L / min)
・ Chamber atmosphere: Argon gas (supply rate 1000 L / min, chamber flow rate 5 m / sec)
・ Atmosphere in cyclone: Argon gas, internal pressure: 50 kPa
・ Material supply rate from the chamber to the 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 above plasma treatment (1) to form Fe nanoparticles.

  Next, the Nb nanoparticles and the Fe nanoparticles obtained above were mixed to obtain a raw material metal powder. This raw metal powder was subjected to plasma treatment in nitrogen gas (treatment conditions were 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 was the same as in the plasma treatment (1).
-High frequency voltage applied to the high frequency oscillation coil: frequency, about 4 MHz, voltage, about 80 kVA
・ Plasma gas: Argon gas and nitrogen gas (supply amount of 50 L / min each)
・ Carrier gas: Nitrogen gas (supply rate 10 L / min)
・ Atmosphere in chamber: Nitrogen gas (supply rate 1000 L / min, chamber flow rate 5 m / sec)
・ Atmosphere in cyclone: Nitrogen gas, internal pressure 50kPa
・ Material supply rate from the chamber to the cyclone: 10 m / s (average value)

Nitrogen gas at 20 ° C. was introduced into the particles after the plasma treatment (2) with Ar gas using a split flow type humidity supply device SRH manufactured by Nippon Shintech Co., Ltd. under the condition that the relative humidity was 95% in the atmosphere. Let stand for hours. Then, the obtained particles were classified using a TTSP separator manufactured by Hosokawa Micron under the condition that the yield was 10% to obtain niobium nitride-containing particles (NbN). In addition, nitrogen gas was supplied to the separator.
When the content of iron (Fe) atoms in the obtained niobium nitride-containing particles was measured by ICP emission spectroscopy, it was 50 mass ppm.

(Preparation of Fe-Atom-Containing Vanadium Nitride-Containing Particles (VN))
In the production of the niobium nitride-containing particles containing Fe atoms, Fe atoms were similarly prepared, except that Niobium metal powder vanadium powder VHO manufactured by Taiyo Mining Co., Ltd. was used instead of niobium (powder) manufactured by Mitsuwa Chemical Co., Ltd. <100-325 mesh>. A vanadium nitride-containing particle (VN) containing was produced. When the content of iron (Fe) atoms in the obtained vanadium nitride-containing particles was measured by ICP emission spectroscopy, it was 50 mass ppm.

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

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

-Compound A-52 (In the formula, Ph represents a phenyl group.)

[Dispersant]
As the dispersant, Dispersant A having the following structure was used. The numerical value described in each structural unit means the mass% of each structural unit based on all structural units.

(Binder resin)
As the binder resin, 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 means the mass% of each structural unit based on all structural units. The resin A corresponds to an alkali-soluble resin.
・ BzMA: benzyl methacrylate ・ MMA: methyl methacrylate

[Polymerizable compound]
As the polymerizable compound, the polymerizable compound M1 and the polymerizable compound M2 were used.
The structure of the polymerizable compound M1 (dipentaerythritol hexaacrylate) is as shown in the following formula (Nippon Kayaku Co., Ltd., trade name "KAYARAD").

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 (A) and (B) in the formula 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 sealed in a Bloom bottle having a capacity of 100 mL and stored in a thermostat bath at 60 ° C. for 7 days (forced heating). Next, each curable composition after the aging by heating was rotated on a Si substrate (corresponding to a support) whose surface was treated with SiO ₂ so that the film thickness after drying was 1.5 μm. After adjusting the number, 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 (FPA3000i5 + manufactured by Canon Inc.) for the substrate with the coating film (curable composition layer) after prebaking, the above coating film was passed through a photomask on which a 200 μm long × 20 μm wide line pattern was formed. Was exposed (negative). Next, the coating film after exposure was paddle-developed for 30 seconds using tetramethylammonium hydroxide as a developing solution using a coater developer ACT8 manufactured by Tokyo Electron, and then shower rinse was performed for 20 seconds using pure water. 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 end of the pattern / film thickness at the center) was calculated and evaluated according to the following criteria. The evaluation range of "2" or higher is the practical range. The results are shown in Table 5.
* 7: The ratio is more than 0.98 and not more than 1.00, and there is no difference in the film thickness between the central portion and the end portion of the pattern by observation with SEM.
* 6: The ratio is more than 0.96 and 0.98 or less, 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 0.96 or less, and there is a difference in the film thickness between the central portion and the end portion of the pattern.
* 4: The ratio is more than 0.92 and 0.94 or less, and the film thickness at the end is thin and slightly distorted, but there is no practical problem.
* 3: The ratio is more than 0.90 and 0.92 or less, and the film thickness at the end is thin and distorted, but there is no problem in practical use.
-2: The ratio is more than 0.80 and 0.90 or less, and the film thickness at the end is thin, but it is a level that can be practically used.
-1: The ratio is 0.80 or less, and the film thickness at the end is thin, which is not acceptable.

[Development residue suppression performance]
A substrate with a coating film was produced using each constituent composition in the same manner as above. After that, development was performed in the same manner as 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 area not exposed to light (unexposed portion) was observed by 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 in the unexposed area.
B: One or more and three or less residues were observed in 1.0 μm square on the unexposed area.
C: 4 or more and 7 or less residues were observed in 1.0 μm square on the unexposed area.
D: 8 or more and 10 or less residues were observed in 1.0 μm square on the unexposed area.
E: 11 or more residues were observed in 1.0 μm square in the unexposed area.
Practically preferred is "D" or more, 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) means the specific oxime compound (A) and the total solid content of the curable composition as 100% by mass. It is each content (mass%) of the polyfunctional thiol compound (B).
-In Table 5, "A / B" represents the content mass ratio of the content of the specific oxime compound (A) to the content of the polyfunctional thiol compound (B) in the curable composition.
In Table 5, the types of colorants CP-1 to CP-8 represent the chromatic pigments 1 to 8 in Table 4, respectively.

From the results shown in Table 5, the curable composition according to each example had the effect of the present invention. On the other hand, the curable composition according to the comparative example did not have the effect of the present invention.
The curable composition of Example 1 containing the specific oxime compound in which R ¹ of Formula (1) has 13 or more carbon atoms has a pattern of a cured film obtained as compared with the curable composition of Example 8. The shape was better.
The curable composition of Example 3 containing a polyfunctional thiol compound (secondary thiol compound) in which R ^{24 of the} formula (2) is other than a hydrogen atom is the curable composition of Example 4 (R ²⁴ , and As compared with a primary thiol compound in which both R ^{25 s} are hydrogen atoms, it had a more excellent development residue suppression performance. Further, 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 hydrogen atoms has further excellent development residue suppression performance. Was there.
In addition, the curable compositions of Examples 43 and 47 in which n in the formula (2) is 3 to 10 are obtained by comparison with the curable composition of Example 46 (n is 2). The pattern shape of the film was better.
The curable composition of Example 12 in which the content mass ratio of the content of the oxime compound to the content of the polyfunctional thiol compound was 4 to 10, was compared with the curable compositions of Example 10 and Example 13. The resulting cured film had a more excellent pattern shape.
Curing of Examples 15 to 19 and Examples 21 to 22 in which R ^{1 of the} formula (1) is a linear alkyl group having 13 or more carbon atoms, or a group represented by * -L ¹¹ -R ^11. As for the functional composition, the cured film obtained had a more excellent pattern shape as compared with the curable composition of Example 20.

Example 71
Instead of TiN-1, TiN-1 and carbon black (trade name “Color Black S170”, manufactured by Degussa Co., average primary particle diameter 17 nm, BET specific surface area 200 m ² / g, carbon black produced by gas black method) Was evaluated in the same manner as in Example 43 except that the solid content mass ratio was 7: 3, and 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, and the same results as in Example 43 were obtained.

Example 73
When a curable composition was prepared and evaluated in the same manner as in Example 43 except that the polymerization inhibitor was not used, the same results as in Example 43 were obtained.

101 ... Support 102, 401 ... Curable composition layer 103 ... Photomask 201, 501 ... Cured film 301, 601 ... Cured film 700 after post-baking ... Solid-state imaging device 701 ... Solid-state imaging device 702 ... Imaging unit 703 ... Cover glass 704 ... Spacer 705 ... Laminated substrate 706 ... Chip substrate 707 ... Circuit board 708 ... Electrode pad 709 ... .. External connection terminal 710 ... Through electrode 711 ... Lens layer 712 ... Lens material 713 ... Supports 714, 715 ... Cured film 801 ... Light receiving element 802 ... Color filter 803 Microlens 804 Substrate 805b Blue pixel 805r Red pixel 805g Green pixel 805bm Black matrix 806 p-well layer 807 ... reading gate portion 808 ... vertical transfer path 809 ... element isolation region 810 ... gate insulating film 811 ... vertical transfer electrode 812 ... cured films 813,814. Insulating film 815 ... Flattening film 900 ... Infrared sensor 910 ... Solid-state image sensor 911 ... Infrared absorption filter 912 ... Color filter 913 ... Infrared transmission filter 914 ... Resin film 915 ... ..Micro lens 916 ... Flattening film

Claims (16)

A photopolymerization initiator, a polyfunctional thiol compound, a polymerizable compound, and a curable composition containing a colorant,
A curable composition in which the photopolymerization initiator is an oxime compound represented by the following formula (1).

In formula (1), R ¹ represents a hydrocarbon group having 8 or more carbon atoms which may contain a hetero atom, R ² represents an alkyl group or an aryl group, X ² represents a single bond, or It 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 according to claim 1, wherein R ¹ in the formula (1) has 13 or more carbon atoms.   The curable composition according to claim 1 or 2, wherein the content mass 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 mass ratio of the content of the oxime compound to the content of the polyfunctional thiol compound in the curable composition is 4 to 10. Stuff. The curable composition according to claim 1, wherein the polyfunctional thiol compound is a compound represented by the following formula (2).

In formula (2), R ²⁴ and R ²⁵ are each independently a hydrogen atom, an alkyl group, an aryl group, —C (═O) —R ²³ , —C (═O) —O—R ²³ , or Represents —C (═O) —NH—R ²³ , L ²¹ represents an n-valent organic linking group, n represents an integer of 2 to 10, M ²¹ represents a single bond, or —O—, —S. -, -N (R < ²³ >)-, -C (= O) -O-, -OC (= O) -O-, -C (= O) -NH-, -C (= O)-, An alkylene group or a group in which two or more thereof 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—. And the curable composition according to claim 5, wherein n is an integer of 3 to 10.   The curable composition according to claim 1, wherein the colorant is an organic pigment.   The curable composition according to claim 1, wherein the colorant is an inorganic pigment.   A cured film obtained by curing the curable composition according to claim 1.   A color filter comprising the cured film according to claim 9.   A light-shielding film containing the cured film according to claim 9.   A solid-state imaging device, comprising 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 claim 1.
A method for producing a cured film, which comprises the step of exposing the curable composition layer to light.   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. Membrane manufacturing method. The method for producing a cured film according to claim 14 or 15, further comprising a developing step of developing the exposed curable composition layer.