JPWO2017221620A1 - Curable composition, cured film, color filter, light shielding film, solid-state imaging device, image display device, method of producing cured film, and polyfunctional thiol compound - Google Patents

Abstract

A curable composition, a cured film, a color filter, a light shielding film, a solid-state imaging device, an image display device, and a cured film having excellent exposure sensitivity and capable of obtaining a cured film having excellent adhesion to a support. A method of producing a membrane, and a multifunctional thiol compound are provided. The curable composition contains a polyfunctional thiol compound, a polymerizable compound, and a photopolymerization initiator, and the polyfunctional thiol compound has two or more thiol groups and an interactive group different from the thiol group. Contains

Description

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

A color filter used in an image display apparatus is provided with a light shielding film called a black matrix for the purpose of shielding light between colored pixels and improving contrast.
Also in the solid-state imaging device, a light shielding film is provided for the purpose of preventing noise generation and improving the image quality. At present, small and thin imaging units are mounted on portable terminals of electronic devices such as mobile phones and PDAs (Personal Digital Assistants). Such an imaging unit generally includes a solid-state imaging device such as a charge coupled device (CCD) image sensor and a complementary metal-oxide semiconductor (CMOS) image sensor, and a lens for forming an object image on the solid-state imaging device. Is equipped.

  Patent Document 1 describes “A photosensitive resin composition for forming a partition separating pixels in an image display device, wherein the photosensitive resin composition has a carboxyl group in the molecule as the component (A). Photosensitivity comprising a binder polymer, a photopolymerizable compound as component (B), a photopolymerization initiator as component (C), a compound having a mercapto group as component (D), and a black pigment as component (E) Resin composition. "Is described.

JP, 2014-41188, A

The present inventor applies the photosensitive resin composition described in Patent Document 1 onto a support, exposes the obtained photosensitive resin composition layer to produce a cured film, and further improves the exposure sensitivity. I found that there is room for Specifically, it has been found that the photosensitive resin composition described in Patent Document 1 has a problem that the energy required for exposure becomes large when attempting to obtain a finer pattern shape.
Moreover, when the present inventor examined the cured film obtained by said method, it also discovered that there exists room for the further improvement in adhesiveness with a support body (henceforth a "board | substrate").

Then, this invention makes it a subject to provide the curable composition which can obtain the cured film which has the outstanding exposure sensitivity and the outstanding adhesiveness with a support body.
Moreover, this invention makes it a subject to provide a cured film, a color filter, a light shielding film, a solid-state image sensor, an image display apparatus, the manufacturing method of a cured film, and a polyfunctional thiol compound.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining in order to achieve the said subject, this inventor discovered that the curable composition containing a predetermined | prescribed polyfunctional thiol compound could solve the said subject, and completed this invention.
That is, it discovered that the above-mentioned subject could be achieved by the following composition.

[1] A curable composition comprising a multifunctional thiol compound, a polymerizable compound, and a photopolymerization initiator, wherein the multifunctional thiol compound has two or more thiol groups and a mutually different thiol group. Curable composition containing an active group.
[2] The curable composition according to [1], wherein the polyfunctional thiol compound is a compound represented by Formula (1).
[3] The curable composition according to [1] or [2], wherein the polyfunctional thiol compound is a compound represented by Formula (2).
[4] The curable composition as described in [2] or [3] whose m is an integer of 3-14.
[5] An interaction group different from a thiol group is a hydroxyl group, an amino group, a pyridinyl group, a pyridinium group, an ammonium group, a phosphonium group, a carboxylic acid group or a salt thereof, a phosphoric acid group or a salt thereof, a sulfonic acid group or [1] to [1] which is at least one selected from the group consisting of a salt thereof, an aryl group, -Si (R ^X ) _p (R ^Y ) _3-p , and-(OR ^A ) _q -R ^Z The curable composition in any one of 4].
Here, p represents an integer of 1 to 3, R ^X represents a hydrolysable group, R ^Y represents a monovalent organic group other than a hydrolysable group, and p R ^X and 3-p Each R ^Y may be the same or different. Further, R ^Z represents a hydrogen atom, an alkyl group or an alkoxy group, q represents an integer of 1 to 4, and R ^A represents an alkylene group having 1 to 15 carbon atoms.
[6] An interaction group different from a thiol group is a hydroxyl group, an amino group, a pyridinyl group, a pyridinium group, an ammonium group, a phosphonium group, a carboxylic acid group or a salt thereof, a phosphoric acid group or a salt thereof, and a sulfonic acid group Or the curable composition in any one of [1]-[5] which is at least 1 sort (s) selected from the group which consists of its salt.
[7] An interactive group different from a thiol group is selected from the group consisting of a hydroxyl group, an amino group, a pyridinyl group, a carboxylic acid group or a salt thereof, a phosphoric acid group or a salt thereof, and a sulfonic acid group or a salt thereof The curable composition in any one of [1]-[6] which is at least 1 sort (s).
[8] The curable composition according to any one of [1] to [7], further containing a colorant.
[9] The curable composition according to [8], wherein the colorant contains a black pigment.
[10] The curable composition according to any one of [1] to [9], wherein the photopolymerization initiator is an oxime compound.
[11] A cured film obtained by curing the curable composition according to any one of [1] to [10].
[12] A color filter comprising the cured film according to [11].
[13] A light shielding film containing the cured film according to [11].
[14] A solid-state imaging device containing the cured film according to [11].
[15] An image display device containing the cured film according to [11].
[16] 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 [10], and a curable composition layer Exposing the substrate, and an exposure process.
[17] The cured film according to [16], wherein the step of forming a curable composition layer includes the step of directly applying the curable composition on a support to form a curable composition layer on a support Manufacturing method.
[18] The curing according to [16] or [17], further comprising a developing step of developing the exposed curable composition layer, and a washing step of washing the developed curable composition layer. Method of producing a membrane
[19] A multifunctional thiol compound containing two or more thiol groups and an interactive group different from the thiol group.
[20] The polyfunctional thiol compound according to [19], which is a compound represented by the formula (1).
[21] The polyfunctional thiol compound according to [19] or [20], which is a compound represented by the formula (2).
[22] The polyfunctional thiol compound according to [20] or [21], wherein m is an integer of 3 to 14.
[23] The interaction group different from the thiol group is a hydroxyl group, an amino group, a pyridinyl group, a pyridinium group, an ammonium group, a phosphonium group, a carboxylic acid group or a salt thereof, a phosphoric acid group or a salt thereof, a sulfonic acid group or At least one selected from the group consisting of salts thereof, aryl groups, -Si (R ^X ) _p (R ^Y ) _{3 -p} , and-(OR ^A ) _q -R ^Z , [19] to [[19] 22. The polyfunctional thiol compound as described in any one of 22.
Here, p represents an integer of 1 to 3, R ^X represents a hydrolysable group, R ^Y represents a monovalent organic group other than a hydrolysable group, and p R ^X and 3-p Each R ^Y may be the same or different. Further, R ^Z represents a hydrogen atom, an alkyl group or an alkoxy group, q represents an integer of 1 to 4, and R ^A represents an alkylene group having 1 to 15 carbon atoms.
[24] An interaction group different from a thiol group is a hydroxyl group, an amino group, a pyridinyl group, a pyridinium group, an ammonium group, a phosphonium group, a carboxylic acid group or a salt thereof, a phosphoric acid group or a salt thereof, and a sulfonic acid group Or the polyfunctional thiol compound in any one of [19]-[23] which is at least 1 sort (s) selected from the group which consists of its salt.

According to the present invention, it is possible to provide a curable composition capable of obtaining a cured film having excellent exposure sensitivity and excellent adhesion to a support.
In addition, the present invention can provide a cured film, a color filter, a light shielding film, a solid-state imaging device, an image display device, a method for producing a cured film, and a multifunctional thiol compound.

Hereinafter, the present invention will be described in detail.
The following description may be made based on representative embodiments of the present invention, but the present invention is not limited to such embodiments.
In the present specification, a numerical range represented using “to” means a range including numerical values described before and after “to” as the lower limit value and the upper limit value.
In the notation of the group (atomic group) in the present specification, the notation not describing substitution and non-substitution includes those containing no substituent as well as those containing a substituent. For example, the "alkyl group" includes not only an alkyl group containing no substituent (unsubstituted alkyl group) but also an alkyl group containing a substituent (substituted alkyl group).
In the present specification, the term "actinic ray" or "radiation" refers to, for example, the emission line spectrum of a mercury lamp, far ultraviolet light represented by an excimer laser, extreme ultraviolet (EUV) light, X-rays, and electron beams. Means etc. In the present specification, "light" means actinic rays and radiation. Unless otherwise specified, the "exposure" in the present specification refers not only to the emission line spectrum of a mercury lamp, exposure to far ultraviolet rays represented by an excimer laser, X-rays, EUV light, etc., but also electron beams and ion beams Also includes particle beam drawing of.
As used herein, "(meth) acrylate" refers to acrylate and methacrylate. In the present specification, "(meth) acrylic" represents acrylic and methacrylic. As used herein, "(meth) acryloyl" represents acryloyl and methacryloyl. As used herein, "(meth) acrylamide" refers to acrylamide and methacrylamide.
In the present specification, "monomer" and "monomer" are synonymous. A monomer is distinguished from an oligomer and a polymer and refers to a compound having a weight average molecular weight of 2,000 or less. In the present specification, a polymerizable compound refers to a compound containing a polymerizable group, and may be a monomer or a polymer. The polymerizable group refers to a group involved in the polymerization reaction.

[Curable composition]
The curable composition is a curable composition containing a polyfunctional thiol compound, a polymerizable compound, and a photopolymerization initiator, and the polyfunctional thiol compound has two or more thiol groups, a thiol group, and Contains different interactive groups.

The inventor of the present invention forms a curable composition layer on a support using a curable composition containing a thiol compound described in Patent Document 1, and exposes the curable composition layer to form fine particles. In order to produce a cured film having a proper pattern shape, it has been found that the amount of exposure must be increased.
It is presumed that this is because when the pattern shape is to be miniaturized, the opening of the photomask is narrowed, and as a result, the amount of light irradiated to the curable composition layer is further reduced. That is, it is presumed that the bottom of the curable composition layer becomes difficult to cure because the amount of light reaching the bottom of the curable composition decreases.
In such a case, the amount of light reaching the bottom of the curable composition layer can be increased by increasing the amount of exposure.
On the other hand, when the exposure amount is increased, light diffracted at the mask opening, so-called "leakage light" is also likely to be increased, and should be masked originally at the upper part of the curable composition layer (that is, a part closer to the photomask). The part was exposed and the pattern shape might be deteriorated.

  In general, a curable composition containing a photopolymerization initiator is used to form a curable composition layer on a support, and when the curable composition layer is exposed, the photopolymerization initiator initiates a radical reaction. . At this time, radicals generated by the photopolymerization initiator and oxygen in the curable composition layer may be generated to generate peroxy radicals. Since the peroxy radical does not have the function of promoting the reaction, the polymerization reaction may be stopped there.

In one aspect of the present invention, the curable composition contains a multifunctional thiol compound containing two or more thiol groups. Since the thiol group generates a thiyl radical which is less susceptible to polymerization deactivation by donating hydrogen to a peroxy radical, the polymerization reaction continues.
Furthermore, the multifunctional thiol compound contains an interactive group different from the thiol group. The interactive group interacts with the support (or, if the support is provided with an overcoat, with the molecules that constitute the overcoat). Therefore, it is presumed that the polyfunctional thiol compound is likely to be unevenly distributed in a portion (that is, the bottom) closer to the support in the curable composition layer formed using the above-mentioned curable composition. In the above curable composition layer, when the polyfunctional thiol compound is unevenly distributed at the bottom of the curable composition layer in which the amount of light reaching at the time of exposure is relatively small, the action of the above thiol group is more effectively exhibited. It is guessed.
That is, although the amount of light reaching the bottom of the curable composition layer is small if the exposure amount is smaller, the multifunctional thiol compound is easily distributed unevenly in the bottom, so that thiyl radicals are easily generated at the bottom of the curable composition layer. It is estimated that even a small amount of light cures sufficiently to the bottom.
Furthermore, in the cured film, since the interactive group is unevenly distributed in a portion closer to the support (that is, the bottom), the interaction with the support becomes stronger, and it has excellent adhesion to the support. It is guessed.
The components contained in the curable composition according to one aspect of the present invention will be described below.

[Multifunctional thiol compound]
The curable composition contains a predetermined polyfunctional thiol compound.
The polyfunctional thiol compound is not particularly limited as long as it contains two or more thiol groups (a group represented by -SH) and an interactive group different from the thiol group, and known polyfunctional thiols Compounds can be used.

The number of thiol groups contained in the polyfunctional thiol compound is two or more, preferably three or more, and more preferably four or more.
The upper limit of the number of thiol groups contained in the polyfunctional thiol compound is not particularly limited, but generally 30 or less is preferable, 20 or less is more preferable, and 14 or less is still more preferable.

The number of interactive groups different from the thiol group contained in the multifunctional thiol compound is one or more, preferably two or more.
The upper limit of the interaction group different from the thiol group contained in the polyfunctional thiol compound is not particularly limited, but generally 30 or less is preferable, 20 or less is more preferable, and 15 or less is still more preferable.

In the present specification, the term "interacting group" means a group capable of interacting with another molecule. The interaction includes groups that can interact in any manner such as intermolecular force, molecular association, electrostatic attraction, ionic bonding, and / or hydrogen bonding.
Among them, as the interactive group, a group capable of interacting with the support described later and / or the molecule forming the undercoat layer is preferable. Specific examples of the interactive group will be described in detail later.

As content of a polyfunctional thiol compound, 0.5-10 mass% is preferable with respect to the total solid of a curable composition.
When the content of the polyfunctional thiol compound is 0.5 to 10% by mass, the exposure sensitivity is more excellent.
The polyfunctional thiol compounds may be used alone or in combination of two or more. When two or more polyfunctional thiol compounds are used in combination, the total amount thereof is preferably in the above range.

<Preferred Embodiment 1 of Polyfunctional Thiol Compound>
As a polyfunctional thiol compound, the compound represented by the following formula (1) is preferable.

In Formula (1), L ¹ and L ² each independently represent a divalent linking group. m represents an integer of 2 to 14, preferably an integer of 3 to 14, and more preferably 3 to 6. When m is an integer of 3 or more, the curable composition has better exposure sensitivity. n represents an integer of 1 to 15; L ³ represents an m + n valent linking group, and R ¹ represents an interactive group different from a thiol group.
L ¹ and L ² may be the same or different from each other, and m L ^{1 's} , n L ^{2' s} , and n R ^{1 's} may be the same or different, respectively. Good.

Examples of the divalent linking group of L ¹ include, for example, a divalent aliphatic hydrocarbon group (preferably having a carbon number of 1 to 8), a divalent aromatic hydrocarbon group (preferably having a carbon number of 6 to 12), O-, -S-, -N (R ⁴ )-(R ⁴ : monovalent organic group), -C (= O)-, -C (= O) -O-, -O-C (= O ) -O-, -C (= O) -NH-, -O-C (= O) -NH-, -S (= O)-, -S (= O) -O-, -S (= O) ) _2- , -S (= O) ₂ -O-, -CH = N-, -N (R)-(R: alkyl group), or a combination thereof (eg, alkyleneoxy group, alkyleneoxy) And the like, and the like.

The divalent linking group of L ² is the same as that of L ¹ above. L ¹ and L ² may be identical to or different from each other. In addition, m L ¹ and n L ² in one molecule of the polyfunctional thiol compound may be the same or different.

The m + n-valent linking group for L ³ is, for example, a trivalent group such as a trimethylolpropane residue or an isocyanuric ring having three — (CH ₂ ) _k — (k represents an integer of 2 to 6) And a tetravalent linking group such as pentaerythritol residue or a pentavalent linking group, a hexavalent linking group such as dipentaerythritol residue, and combinations thereof.
m + n is 3 or more, and 4 or more is preferable.
m + n is 29 or less, preferably 10 or less.

The linking group of m + n valent L ^3, for example, the following formula (A) ~ group represented by any one of (D), or, a group combining thereof.

In formulas (A) to (D),
L ⁴ represents a trivalent group. T ³ represents a single bond or a divalent linking group, three of T ³ may be the being the same or different.
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 as or different from one another.
L ⁶ represents a pentavalent group. T ⁵ represents a single bond or a divalent linking group, five T ⁵ may be the being the same or different.
L ⁷ represents a hexavalent group. T ⁶ represents a single bond or a divalent linking group, and the six T ⁶ may be the same as or different from one another.
^The definition of the divalent linking group represented by ^{T 3,} T ^4, T ⁵ and ^{T 6} are the same as those defined divalent linking group represented by ^{L 1} described above.

As the m + n valent linking group of L ³ , for example, groups represented by the following formulas (E) to (J) or a group obtained by combining them are preferable.

In formulas (E) to (J),
R represents a hydrogen atom or a monovalent organic group. As a monovalent organic group, an alkyl group is preferable. * Indicates a bonding position. t represents an integer of 2 to 11.

L ³ may be a group represented by the following formulas (K) to (O), or a group obtained by combining them. In the formulae, * represents a bonding position.

In Formula (1), R ¹ is the same as in the embodiment of the interactive group different from the thiol group described above.
Among them, as the interactive group different from the thiol group in that the cured film has more excellent adhesion to the support, there are a hydroxyl group, an amino group, a pyridinyl group, a pyridinium group, an ammonium group and a phosphonium group. , Carboxylic acid group or salt thereof, phosphoric acid group or salt thereof, sulfonic acid group or salt thereof, aryl group, -Si (R ^X ) _p (R ^Y ) _3-p (hereinafter referred to as "Si group" in the present specification) And at least one selected from the group consisting of-(OR ^A ) _q -R ^Z, and is preferably a hydroxyl group, an amino group, a pyridinyl group, a pyridinium group, an ammonium group, a phosphonium group, a carboxylic acid group Or at least one selected from the group consisting of salts thereof, phosphoric acid groups or salts thereof, and sulfonic acid groups or salts thereof, more preferably hydroxyl groups, amino Further preferred is at least one selected from the group consisting of groups, pyridinyl groups, carboxylic acid groups or salts thereof, phosphoric acid groups or salts thereof, and sulfonic acid groups or salts thereof.
Although the mechanism by which the cured film has a better adhesion to the support is not necessarily clear by the interaction group different from the thiol group being the above functional group, the inventor of the present invention is as follows: I guess. That is, interactions (non-bonding intermolecular forces) are broadly classified into van der Waals interactions, π-π stacking, hydrogen-π bonds, electrostatic interactions, or hydrogen bonds, and in general become stronger in this order It is inferred that "hydrogen bonding" is the strongest and then "electrostatic interaction" is the strongest. Here, for example, hydrogen-π bond, which is a bond of π electron of phenyl group and hydrogen of O—H, is considered to be weak as compared with the above two, and it is presumed that the above effect is obtained. The mechanism by which the effects of the present invention can be obtained is not limited to the above estimation.
Incidentally, the above-mentioned amino group, primary amino group _(NH 2 -), secondary amino group _(NR a H-), and tertiary amino group _{(NR a R} a -) are included. R _a contained in the secondary amino group and the tertiary amino group is not particularly limited as long as it is a monovalent organic group, and examples thereof include a hydrocarbon group (for example, an alkyl group).

In the above -Si (R ^x ) _p (R ^Y ) _3-p , R ^x represents a hydrolyzable group.
In the present specification, a hydrolyzable group is a group which is directly linked to a silicon atom (Si) and is capable of advancing a hydrolysis reaction. And the like.

R ^Y represents a monovalent organic group. However, the said hydrolyzable group is remove | excluded from the said organic group.
The monovalent organic group may be an organic group other than a hydrolyzable group, and examples thereof include an alkyl group, an alkenyl group, an aryl group, an alkylcarbonyl group, a cycloalkylcarbonyl group, an arylcarbonyl group and an alkyloxycarbonyl group. And a cycloalkyloxycarbonyl group, an aryloxycarbonyl group, an alkylaminocarbonyl group, a cycloalkylaminocarbonyl group, an arylaminocarbonyl group, a group obtained by combining these, and the like. Among them, an alkyl group, an aryl group, an alkenyl group, or a group combining these is preferable.

  The number of carbon atoms contained in the alkyl group is preferably 1 to 6, and may be linear, branched or cyclic. The number of carbon atoms contained in the aryl group is preferably 6 to 10. Moreover, 2-12 are preferable carbon number contained in the said alkenyl group.

p is an integer of 1 to 3; Among them, p is preferably 3 in that the cured film has better adhesion to the support.
Moreover, p R ^X and 3-p R ^Y may be identical to or different from each other.

In the above-(OR ^A ) _q -R ^Z , R ^Z represents a hydrogen atom, an alkyl group or an alkoxy group, and the alkyl group and the alkyl group in the alkoxy group preferably have 1 to 6 carbon atoms, It may be linear, branched or cyclic.

R ^A represents an alkylene group having 1 to 15 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 1 to 6 carbon atoms. q represents an integer of 1 to 4, an integer of 2 to 4 is more preferable, and an integer of 3 to 4 is still more preferable.

<Preferred Embodiment 2 of Multifunctional Thiol Compound>
As the above-mentioned polyfunctional thiol compound, a compound represented by the following formula (2) is more preferable.

In formula (2), R ² and R ³ each independently represent a divalent linking group having one or more carbon atoms.
The divalent linking group having one or more carbon atoms is not particularly limited, and, for example, a divalent aliphatic hydrocarbon group (preferably having a carbon number of 1 to 8), a divalent aromatic hydrocarbon group (preferably having a carbon number of 6 to 12), -C (= O)-, -C (= O) -O-, -O-C (= O) -O-, -C (= O) -NH-, -O-C ( OO), —CH = N—, —N (R) — (R: alkyl group), or a group in which these are combined with the group described as L ¹ in the above formula (1), and the like.
R ² and R ³ may be the same or different from each other, and m R ^{2 's} , n R ^{2' s} and n R ³ 's may be the same or different from each other. .

In formula (2), m represents the integer of 2-14, the integer of 3-14 is preferable and 3-6 are more preferable. When m is an integer of 3 or more, the curable composition has better exposure sensitivity.
n represents an integer of 1 to 15, preferably 1 to 4.
The value of m for n (m / n) is not particularly limited, but is preferably 0.13 to 14, more preferably 1 to 5, and still more preferably 2 to 5.
If m / n is in the range of 1 to 5, the adhesion between the support and the cured film formed on the support using the curable composition is more excellent.
When m + n is the same, the smaller the m / n, the better the pattern shape obtained by curing the curable composition, and the cured film formed on the support using the curable composition. And adhesion to the support are more excellent.

In the above formula (2), each M ¹ independently represents a single bond, -O-, -S-, -N (R ⁴ )-(R ⁴ : monovalent organic group), -C (= O) -, -C (= O) -O-, -O-C (= O) -O-, -C (= O) -NH-, -O-C (= O) -NH-, -S (= O)-, -S (= O) -O-, -S (= O) _2- , -S (= O) _2- O-, or -CH = N-.
The m M ^{1 s} and the n M ^{1 s} may be the same or different.

L ³ represents an m + n valent linking group and the aspect is as described above. Further, R ¹ represents an interactive group different from the thiol group, and the mode is the same as that in the above-mentioned formula (1).
The n R ^{1 s} may be the same or different.

The synthesis method of the polyfunctional thiol compound is not particularly limited, and can be synthesized by combining known methods.
For example, a desired polyfunctional thiol compound can be synthesized by reacting a raw material compound having a plurality of thiol groups and a compound having a predetermined interactive group and having a group capable of reacting with the thiol group. it can. In addition, carbon-carbon double bond group, carbon-carbon triple bond group, an epoxy group, a carboxyl group, a halogen atom, an alkyl sulfonate group, an aryl sulfonate group etc. are mentioned as group which can be reacted with a thiol group.
More specifically, a desired polyfunctional thiol compound can be synthesized by reacting a (meth) acrylate compound having a predetermined interactive group by Michael addition with a raw material compound having a plurality of thiol groups.

  Specific examples of polyfunctional thiol compounds are shown in Table 1 below. However, polyfunctional thiol compounds are not limited to these.

In Table 1-1 to 1-6, "Me" is intended methyl group (-CH _3). "OTs" represents a tosyl group.
In Tables 1-1 to 1-6, R ^{1 to} R ³ , L ³ , and M ¹ are groups corresponding to respective parts in Formula (2), and m and n are m and n in Formula (2). It is a corresponding number.

The symbols in Tables 1-1 to 1-6 intend the following contents.
*: It shows the connection points of ^{L 3} and ^{M 1.}
●: ^{M 1,} and in the column of ^{R 2,} showing the coupling portion of the ^{M 1} and ^{R 2.} Further, in the column of ^{R 3,} showing the connection portion between ^{R 3} and -S- group.
○: indicates a point of connection to a thiol (-SH) group or -S- group.
R ³ and R ¹ wavy lines: indicate points of connection between R ³ and R ¹ .
Up arrow: Indicates the same as the field immediately above.

[Photopolymerization initiator]
The curable composition contains a photopolymerization initiator.
The photopolymerization initiator is not particularly limited as long as it can initiate the polymerization of the polymerizable compound, and a known photopolymerization initiator can be used. As the photopolymerization initiator, for example, one having photosensitivity to an ultraviolet light region to a visible light region is preferable. The photopolymerization initiator may be an activator that produces an action with the photoexcited sensitizer and generates active radicals, and is an initiator that initiates cationic polymerization according to the type of the polymerizable compound. May be
The photopolymerization initiator preferably contains at least one compound having a molar absorption coefficient of at least about 50 in a wavelength range of about 300 nm to 800 nm (330 nm to 500 nm is more preferable).

As content of a photoinitiator, 1-9 mass% is preferable with respect to the total solid of a curable composition.
When the content of the photopolymerization initiator is 1 to 9% by mass with respect to the total solid content of the curable composition, the pattern shape of the cured film obtained by curing the curable composition is more excellent.
The photopolymerization initiator may be used singly or in combination of two or more. When two or more photopolymerization initiators are used in combination, the total amount thereof is preferably in the above range.

As the photopolymerization initiator, for example, a halogenated hydrocarbon derivative (for example, one containing a triazine skeleton, one containing an oxadiazole skeleton, etc.), an acylphosphine compound such as an acylphosphine oxide, hexaarylbiimidazole, Examples include oxime compounds such as oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, and hydroxyacetophenone.
Examples of the halogenated hydrocarbon compound containing a triazine skeleton described above include Wakabayashi et al., Bull. Chem. Soc. Japan, 42, 2924 (1969), a compound described in British Patent 1388492, a compound described in JP-A-53-133428, a compound described in German Patent 3337024, an F. compound. C. Schaefer et al. Org. Chem. 29, 1527 (1964), compounds described in JP-A-62-58241, compounds described in JP-A-5-281728, compounds described in JP-A-5-34920, US Patent No. 4212976 The compounds described in the specification, and the like can be mentioned.

  From the viewpoint of exposure sensitivity, trihalomethyl triazine compounds, benzyl dimethyl ketal compounds, α-hydroxy ketone compounds, α-amino ketone compounds, acyl phosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triallyl imidazole dimers, onium compounds, Compounds selected from the group consisting of benzothiazole compounds, benzophenone compounds, acetophenone compounds and their derivatives, cyclopentadiene-benzene-iron complexes and their salts, halomethyl oxadiazole compounds, and 3-aryl substituted coumarin compounds are preferred.

  Among them, trihalomethyl triazine compounds, α-amino ketone compounds, acyl phosphine compounds, phosphine oxide compounds, oxime compounds, triallyl imidazole dimers, onium compounds, benzophenone compounds, or acetophenone compounds are more preferable, and trihalomethyl triazine compounds, α- More preferred is at least one compound selected from the group consisting of amino ketone compounds, oxime compounds, triallylimidazole dimers, and benzophenone compounds.

In particular, when the curable composition is used to form a light shielding film, it is necessary to form a fine pattern in a sharp shape, and therefore it is important that the image be developed with no residue in the unexposed area together with the curability. is there. From such a viewpoint, it is particularly preferable to use an oxime compound as the photopolymerization initiator. In particular, in the case of forming a fine pattern, a stepper exposure is used for the curing exposure, but this exposure machine may be damaged by halogen, and the addition amount of the photopolymerization initiator also needs to be suppressed low. In consideration of these points, it is particularly preferable to use an oxime compound as the photopolymerization initiator in order to form a fine pattern.
As a specific example of a photoinitiator, the paragraph 0265 to 0268 of Unexamined-Japanese-Patent No. 2013-29760 can be considered, for example, and this content is integrated in this specification.

As the photopolymerization initiator, a hydroxyacetophenone compound, an aminoacetophenone compound, and an acyl phosphine compound can also be suitably used. More specifically, for example, an aminoacetophenone-based initiator described in JP-A-10-291969 and an acylphosphine-based initiator described in Japanese Patent No. 4225898 can also be used.
Examples of the hydroxyacetophenone compound include IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, and IRGACURE-127 (trade names, all manufactured by BASF Corp.).
Examples of the aminoacetophenone compound include IRGACURE-907, IRGACURE-369, and IRGACURE-379EG (trade names, all manufactured by BASF Corp.) which are commercially available products. As an amino acetophenone compound, the compound of Unexamined-Japanese-Patent No. 2009-191179 whose absorption wavelength was matched by long-wave light source, such as 365 nm or 405 nm, is also mentioned.
As an acyl phosphine compound, IRGACURE-819 which is a commercial item, and DAROCUR-TPO (a brand name, all are BASF Corporation make) are mentioned.

<Oxime compound>
More preferably, an oxime compound (oxime type initiator) is mentioned as a photoinitiator.
The said curable composition whose photoinitiator is an oxime compound has more excellent exposure sensitivity. Further, the oxime compound is preferable because it has high sensitivity and high polymerization efficiency, can cure the curable composition layer regardless of the concentration of the colorant, and can easily design the concentration of the colorant high.
As a specific example of an oxime compound, the compound of Unexamined-Japanese-Patent No. 2001-233842, the compound of Unexamined-Japanese-Patent No. 2000-80068, and the compound of Unexamined-Japanese-Patent No. 2006-342166 are mentioned.
As an oxime compound, 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, 2-acetoxyiminopentan-3-one, 2- Acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3- (4-toluenesulfonyloxy) iminobutan-2-one, and 2-ethoxycarbonyloxyimino -1-phenylpropan-1-one and the like.
Also, J.J. C. S. Perkin II (1979) pp. 1653-1660), J.F. C. S. Perkin II (1979) pp. 156-162, Journal of Photopolymer Science and Technology (1995) pp. Compound described in JP-A-2000-66385; and compounds described in JP-A-2000-80068, JP-A-2004-534797, and JP-A-2006-342166. Etc.
Among commercially available products, IRGACURE-OXE01 (manufactured by BASF), IRGACURE-OXE02 (manufactured by BASF), IRGACURE-OXE03 (manufactured by BASF), or IRGACURE-OXE04 (manufactured by BASF) are also suitably used. In addition, TR-PBG-304 (made by Changzhou High Power Electronic New Material Co., Ltd.), Adeka Akurus NCI-831 and Adeka Akurus NCI-930 (made by ADEKA), or N-1919 (carbazole oxime ester skeleton containing photo initiation) An agent (made by Adeka) can also be used.

Compounds described in JP-T-2009-519904, in which an oxime is linked to the carbazole N-position, as oxime compounds other than those described above; compounds described in US Pat. Compounds described in JP-A-2010-15025 and US Patent Publication 2009-292039 in which a nitro group is introduced at the site; Ketooxime compounds described in International Publication 2009-131189; The compound described in US Pat. No. 7,556,910, which is contained therein; the compound described in JP2009-221114A having an absorption maximum at 405 nm and good sensitivity to a g-line light source; .
Preferably, for example, paragraphs 0274 to 0275 of JP-A-2013-29760 can be referred to, and the contents thereof are incorporated herein.
Specifically, as the oxime compound, a compound represented by the following formula (OX-1) is preferable. Whether the N-O bond of the oxime compound is an oxime compound of (E) form, an oxime compound of (Z) form, or a mixture of (E) form and (Z) form Good.

In formula (OX-1), R and B each independently represent a monovalent substituent, A represents a divalent organic group, and Ar represents an aryl group.
In Formula (OX-1), the monovalent substituent represented by R is preferably a monovalent nonmetal atomic group.
Examples of the monovalent nonmetal atom group include an alkyl group, an aryl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a heterocyclic group, an alkylthiocarbonyl group, and an arylthiocarbonyl group. These groups may have one or more substituents. Moreover, the substituent mentioned above may be further substituted by the other substituent.
Examples of the substituent include a halogen atom, an aryloxy group, an alkoxycarbonyl group or an aryloxycarbonyl group, an acyloxy group, an acyl group, an alkyl group, an aryl group and the like.
In the formula (OX-1), the monovalent substituent represented by B is preferably an aryl group, a heterocyclic group, an arylcarbonyl group or a heterocyclic carbonyl group. These groups may have one or more substituents. Examples of the substituent include the substituents described above.
As a bivalent organic group represented by A in Formula (OX-1), a C1-C12 alkylene group, a cycloalkylene group, or an alkynylene group is preferable. These groups may have one or more substituents. Examples of the substituent include the substituents described above.

  As a photoinitiator, the oxime compound containing a fluorine atom can also be used. As a specific example of the oxime compound containing a fluorine atom, a compound described in JP-A-2010-262028; a compound 24, 36-40 described in JP-A-2014-500852; a compound described in JP-A-2013-164471 (C-3); and the like. This content is incorporated herein.

  As a photoinitiator, the compound represented by following General formula (1)-(4) can also be used.

In Formula (1), R ¹ and R ² each independently represent an alkyl group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group having 4 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or R ⁷ represents an arylalkyl group having 7 to 30 carbon atoms, and when R ¹ and R ² are phenyl groups, the phenyl groups may be bonded to form a fluorene group, and R ³ and R ⁴ are each independently Represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms or a heterocyclic group having 4 to 20 carbon atoms, and X represents a direct bond or carbonyl Indicates a group.

In the formula ^(2), R ^1, R 2, ^{R 3} and ^{R 4} have the same meanings as ^{R 1,} R 2, ^{R 3} and ^{R 4} in Formula (1), ^{R 5 is} -R 6, -OR ^{6, -SR 6, -COR 6,} -CONR 6 R 6, -NR 6 COR 6, -OCOR 6, -COOR 6, -SCOR 6, -OCSR 6, -COSR 6, -CSOR 6, -CN, halogen R ⁶ represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 4 to 20 carbon atoms , X represents a direct bond or a carbonyl group, and a represents an integer of 0 to 4.

In Formula (3), R ¹ is an alkyl group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group having 4 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an aryl having 7 to 30 carbon atoms R ³ and R ⁴ each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or 4 carbon atoms And a heterocyclic group of 20 to 20, and X represents a direct bond or a carbonyl group.

In the formula ^(4), R 1, ^{R 3} and ^{R 4} have the same meanings as ^R 1, ^{R 3} and ^{R 4} in the formula ^(3), R ^{5 is, -R 6, -OR 6, -SR} 6, ^{-COR 6, -CONR 6 R 6,} -NR 6 COR 6, -OCOR 6, -COOR 6, -SCOR 6, -OCSR 6, -COSR 6, -CSOR 6, -CN, a halogen atom or a hydroxyl group R ⁶ represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms or a heterocyclic group having 4 to 20 carbon atoms, and X represents a direct bond Or a carbonyl group, a represents an integer of 0 to 4;

In the above formulas (1) and (2), R ¹ and R ² are each independently preferably a methyl group, an ethyl group, an n-propyl group, an i-propyl group, a cyclohexyl group or a phenyl group. R ³ is preferably a methyl group, an ethyl group, a phenyl group, a tolyl group or a xylyl group. R ⁴ is preferably an alkyl group having 1 to 6 carbon atoms or a phenyl group. R ⁵ is preferably a methyl group, an ethyl group, a phenyl group, a tolyl group or a naphthyl group. X is preferably a direct bond.
In the above formulas (3) and (4), R ¹ is preferably each independently a methyl group, an ethyl group, an n-propyl group, an i-propyl group, a cyclohexyl group or a phenyl group. R ³ is preferably a methyl group, an ethyl group, a phenyl group, a tolyl group or a xylyl group. R ⁴ is preferably an alkyl group having 1 to 6 carbon atoms or a phenyl group. R ⁵ is preferably a methyl group, an ethyl group, a phenyl group, a tolyl group or a naphthyl group. X is preferably a direct bond.
As a specific example of a compound represented by Formula (1) and Formula (2), the compound described in stage number 0076-0079 of Unexamined-Japanese-Patent No. 2014-137466 is mentioned, for example. This content is incorporated herein by reference.

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

The oxime compound preferably has a maximum absorption wavelength in a wavelength range of 350 nm to 500 nm, more preferably a maximum absorption wavelength in a wavelength range of 360 nm to 480 nm, and still more preferably a 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, 5,000 to 200, More preferably, it is 000.
The molar absorption coefficient of the compound can be determined according to a known method, for example, using an ethyl acetate solvent in a UV-visible spectrophotometer (Cary-5 spctrophotometer manufactured by Varian), at a concentration of 0.01 g / L. It is preferable to measure.
You may use a photoinitiator in combination of 2 or more types as needed.

[Polymerizable compound]
The curable composition contains a polymerizable compound.
1-40 mass% is preferable with respect to the total solid of a curable composition, and, as for content of a polymeric compound, 10-40 mass% is more preferable.
When the content of the polymerizable compound is 10 to 40% by mass based on the total solid content of the curable composition, the curable composition has more excellent exposure sensitivity. In addition, a polymeric compound may be used individually by 1 type, or may use 2 or more types together. When using 2 or more types of polymeric compounds together, it is preferable that the total amount is in the said 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, still more preferably three or more, and five or more Is particularly preferred. The upper limit is, for example, 15 or less. As a group containing an ethylenically unsaturated bond, a vinyl group, a (meth) allyl group, and a (meth) acryloyl group etc. are mentioned, for example.

The polymerizable compound may be, for example, any of chemical forms such as monomers, prepolymers, oligomers, and mixtures thereof, and multimers thereof, and the like, and monomers are preferable.
100-3,000 are preferable and, as for the molecular weight of a polymeric compound, 250-1,500 are more preferable.
The polymerizable compound is preferably a 3 to 15 functional (meth) acrylate compound, and more preferably a 3 to 6 functional (meth) acrylate compound.
Examples of monomers and prepolymers include unsaturated carboxylic acids (eg, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid etc.) or esters thereof, amides, and multimers thereof. Preferred are esters of unsaturated carboxylic acids and aliphatic polyhydric alcohol compounds, and amides of unsaturated carboxylic acids and aliphatic polyhydric amine compounds, and multimers thereof. Also, addition reaction products of unsaturated carboxylic acid esters or amides containing nucleophilic substituent such as hydroxy group, amino group, mercapto group etc. with monofunctional or polyfunctional isocyanates or epoxies; A dehydration condensation product of a saturated carboxylic acid ester or amide and a monofunctional or polyfunctional carboxylic acid is preferably used. In addition, a reaction product of unsaturated carboxylic acid ester or amide containing an electrophilic substituent such as isocyanate group and epoxy group with monofunctional or polyfunctional alcohol, amines or thiol, halogen group Alternatively, a reaction product of unsaturated carboxylic acid ester or amide containing a leaving substituent such as tosyloxy group with monofunctional or polyfunctional alcohol, amines or thiols is also suitable. Further, instead of the above unsaturated carboxylic acid, it is also possible to use a compound group substituted by unsaturated phosphonic acid, vinyl benzene derivatives such as styrene, vinyl ether, allyl ether and the like.
As these specific compounds, the compounds described in paragraphs 0095 to 0108 of JP 2009-288705 A can be suitably used in the present invention.

  The polymerizable compound is also preferably a compound having one or more groups containing an ethylenically unsaturated bond and having a boiling point of 100 ° C. or more under normal pressure. For example, the compounds described in paragraph 0227 of JP-A-2013-29760 and paragraphs 0254 to 0257 of JP-A-2008-292970 can be referred to, and the contents thereof are incorporated herein.

The polymerizable compound is dipentaerythritol triacrylate (commercially available as KAYARAD D-330, PET-30, manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (commercially available as KAYARAD D-320, Nippon Kayaku Co., Ltd.) Product, dipentaerythritol penta (meth) acrylate (commercially available as KAYARAD D-310, manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (meth) acrylate (commercially available as KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd.) A-DPH-12E (manufactured by Shin-Nakamura Chemical Co., Ltd.), and structures in which these (meth) acryloyl groups are mediated by 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.), and KAYARAD RP-1040 (manufactured by Nippon Kayaku Co., Ltd.) can also be used.
The aspect of a preferable polymeric compound is shown below.

  The polymerizable compound may have an acid group such as a carboxylic acid group, a sulfonic acid group, or a phosphoric acid group. As the polymerizable compound containing an acid group, an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid is preferable, and a nonaromatic carboxylic acid anhydride is reacted with an unreacted hydroxy group of the aliphatic polyhydroxy compound. A polymerizable compound having an acid group is more preferable, and in this ester, one in which the aliphatic polyhydroxy compound is pentaerythritol and / or dipentaerythritol is more preferable. Examples of commercially available products include ALONIX TO-2349, M-305, M-510, and M-520 manufactured by Toagosei Co., Ltd.

  As a preferable acid value of the polymeric compound containing an acidic radical, it is 0.1-40 mgKOH / g, More preferably, it is 5-30 mgKOH / g. When the acid value of the polymerizable compound is 0.1 mg KOH / g or more, the developing dissolution property is good, and when it is 40 mg KOH / g or less, it is advantageous in production and / or handling. Furthermore, when it is in the above range, the photopolymerization performance is good and the curability is excellent.

As the polymerizable compound, a compound having a caprolactone structure is also a preferred embodiment.
The compound having a caprolactone structure is not particularly limited as long as it contains a caprolactone structure in the molecule, and examples thereof include trimethylolethane, ditrimethylolethane, trimethylolpropane, ditrimethylolpropane, pentaerythritol, and dipentacene. Ε-caprolactone modified polyfunctional (meth) acrylate obtained by esterifying polyhydric alcohol such as erythritol, tripentaerythritol, glycerin, diglycerol, trimethylolmelamine and (meth) acrylic acid and ε-caprolactone Can be mentioned. Among them, compounds containing a caprolactone structure represented by the following formula (Z-1) are preferable.

  In the formula (Z-1), all six R's are a group represented by the following formula (Z-2), or 1 to 5 of the six R's 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 represents a number of 1 or 2, and * represents a bond.

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

The polymerizable compound containing a caprolactone structure is commercially available, for example, as KAYARAD DPCA series from Nippon Kayaku Co., Ltd., and m is 1 in DPCA-20 (formula (Z-1) to (Z-3), formula (Z-) 2) a compound in which the number of groups represented by 2 is 2 and all R ¹ are hydrogen atoms; DPCA-30 (in the formula, m is 1; 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 and a compound in which the number of groups represented by formula (Z-2) is 6, and all R ¹ are hydrogen atoms) DPCA-120 (in the formula, m is 2, the number of groups represented by formula (Z-2) is 6, and compounds wherein all R ¹ are hydrogen atoms), and the like.

  The compound represented by following formula (Z-4) or (Z-5) can also be used for a polymeric compound.

In formulas (Z-4) and (Z-5), each E independently represents-((CH ₂ ) _y CH ₂ O)-or ((CH ₂ ) _y CH (CH ₃ ) O)- And y each independently represents an integer of 0 to 10,
Each X independently represents 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 m is an integer of 0 to 40.
In formula (Z-5), the total of (meth) acryloyl groups is 5 or 6, n independently represents an integer of 0 to 10, and the sum of 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 still more preferably an integer of 4 to 8.
In formula (Z-5), n is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4.
The total of each n is preferably an integer of 3 to 60, more preferably an integer of 3 to 24, and still more preferably an integer of 6 to 12.
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 terminal Preferred is a form binding to X.

  The compounds represented by formula (Z-4) or formula (Z-5) may be used alone or in combination of two or more. In particular, in a form in which all six X's are an acryloyl group in formula (Z-5), a compound in which all six X's are an acryloyl group in formula (Z-5), and A preferred embodiment is a mixture with a compound in which at least one hydrogen atom is present. With such a configuration, developability can be further improved.

  20 mass% or more is preferable, and, as for the total content in the polymeric compound of a compound represented by Formula (Z-4) or Formula (Z-5), 50 mass% or more is more preferable.

  The compounds represented by the formula (Z-4) or the formula (Z-5) are obtained by ring-opening addition reaction of ethylene oxide or propylene oxide to pentaerythritol or dipentaerythritol which is a conventionally known step. A ring-opened skeleton can be synthesized from the step of bonding a ring-opened skeleton and the step of introducing a (meth) acryloyl group by, for example, reacting (meth) acryloyl chloride with the terminal hydroxy group of the ring-opened skeleton. Each step is a well-known step, and those skilled in the art can easily synthesize a compound represented by general formula (Z-4) or (Z-5).

Among the compounds represented by Formula (Z-4) or Formula (Z-5), pentaerythritol derivatives and / or dipentaerythritol derivatives are more preferable.
Specific examples thereof include compounds represented by the following formulas (a) to (f) (hereinafter also referred to as “exemplified compounds (a) to (f)”), and among them, exemplified compounds (a) and (f) b), (e) and (f) are preferred.

  Commercially available products of the polymerizable compounds represented by the formulas (Z-4) and (Z-5) include, for example, SR-494 which is a tetrafunctional acrylate containing four ethyleneoxy chains manufactured by Sartmar, Nippon Kayaku Co., Ltd. Examples thereof include DPCA-60, which is a hexafunctional acrylate containing 6 pentylene oxy chains manufactured by Co., and TPA-330, which is a trifunctional acrylate containing 3 isobutylene oxy chains.

As polymerizable compounds, urethane acrylates described in JP-B-48-41708, JP-A-51-37193, JP-B-2-32293 and JP-B-2-16765; JP-B-58- The urethane compounds having an ethylene oxide-based skeleton described in JP-A-49860, JP-B-56-17654, JP-B-62-39417, and JP-B-62-39418 are also suitable. Also, addition polymerizable compounds containing an amino structure and / or a sulfide structure in the molecule, as described in JP-A-63-277653, JP-A-63-260909, and JP-A-1-105238. By using the same kind, it is possible to obtain a curable composition excellent in photospeed.
As commercially available products, urethane oligomers UAS-10, UAB-140 (manufactured by Sanyo Kokusaku Pulp Co., Ltd.), UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA- 306T, UA-306I, AH-600, T-600, AI-600 (made by Kyoeisha), etc. are mentioned.

The SP (Solubility Parameter) value of the polymerizable compound is preferably 9.50 or more, more preferably 10.40 or more, and still more preferably 10.60 or more.
In the present specification, unless otherwise specified, the SP value is determined by the Hoy method (HL Hoy Journal of Painting, 1970, Vol. 42, 76-118). Although the unit is omitted and shown about SP value, the unit is cal1 ^{/ 2cm-3 /} 2.

It is also preferable that the curable composition contains a polymerizable compound containing a cardo skeleton from the viewpoint of improving the development residue.
As the polymerizable compound containing a cardo skeleton, a polymerizable compound containing a 9,9-bisarylfluorene skeleton is preferable, and a compound represented by the following formula (Q3) is more preferable.

Formula (Q3)

In the formula (Q3), each of Ar ^{11 to} Ar ¹⁴ independently represents an aryl group containing a benzene ring surrounded by a dashed line. Each of X ^{1 to} X ⁴ independently represents a substituent containing a polymerizable group, and a carbon atom in the above substituent may be substituted by a hetero atom. a and b each independently represent an integer of 1 to 5; c and d each independently represent an integer of 0 to 5; R ^{1 to} R ⁴ each independently represent a substituent, e, f, g and h each independently represent an integer of 0 or more, and the upper limits of e, f, g and h are Ar ^{11 to} Ar ¹⁴ respectively It is a value obtained by subtracting a, b, c or d from the number of substituents that can be contained. However, when Ar ^{11 to} Ar ¹⁴ each independently represent a polycyclic aromatic hydrocarbon group containing a benzene ring surrounded by a broken line as one of the condensed rings, X ^{1 to} X ⁴ and R ^{1 to} R ⁴ are Each may be substituted to a benzene ring surrounded by a broken line independently, or may be substituted to a ring other than the benzene ring surrounded by a broken line.

In the formula (Q3), the aryl group containing a benzene ring surrounded by a broken line represented by Ar ^{11 to} Ar ¹⁴ is preferably an aryl group having 6 to 14 carbon atoms, and an aryl group having 6 to 10 carbon atoms For example, a phenyl group and a naphthyl group are more preferable, and a phenyl group (only a benzene ring surrounded by a broken line) is more preferable.

In formula (Q3), X ^{1 to} X ⁴ each independently represent a substituent containing a polymerizable group, and a carbon atom in the above substituent may be substituted by a hetero atom. There are no particular limitations on the substituent containing a polymerizable group X ¹ to X ⁴ represents preferably an aliphatic group containing a polymerizable group.
The aliphatic group containing a polymerizable group represented by X ^{1 to} X ⁴ is not particularly limited, but is preferably an alkylene group having 1 to 12 carbon atoms other than the polymerizable group, and having 2 to 10 carbon atoms. It is more preferable that it is the alkylene group of, and it is still more preferable that it is a C2-C5 alkylene group.
In the aliphatic group containing a polymerizable group represented by X ^{1 to} X ⁴ , when the aliphatic group is substituted by a hetero atom, it is substituted by —NR— (R is a substituent), an oxygen atom or a sulfur atom The non-adjacent -CH _{2-in the} aliphatic group is more preferably substituted with an oxygen atom or a sulfur atom, and the non-adjacent -CH _2- in the aliphatic group is an oxygen More preferably, it is substituted by an atom. The aliphatic group containing a polymerizable group represented by X ^{1 to} X ⁴ is preferably substituted at one or two places by a hetero atom, more preferably at one place by a hetero atom, and Ar ¹¹ to It is further preferable that one place adjacent to the aryl group containing a benzene ring surrounded by a dashed line represented by Ar ¹⁴ is substituted by a hetero atom.
The polymerizable group contained in the aliphatic group containing a polymerizable group represented by X ^{1 to} X ⁴ is a polymerizable group capable of radical polymerization or cationic polymerization (hereinafter also referred to as a radical polymerizable group and a cationic polymerizable group, respectively) Is preferred.
As a radically polymerizable group, a generally known radically polymerizable group can be used, and as a preferable group, a polymerizable group containing an ethylenically unsaturated bond capable of radical polymerization can be mentioned, and specifically, And examples thereof include a vinyl group and a (meth) acryloyloxy group. Among them, a (meth) acryloyloxy group is preferable, and an acryloyloxy group is more preferable.
As the cationically polymerizable group, generally known cationic polymerizability can be used, and specifically, alicyclic ether group, cyclic acetal group, cyclic lactone group, cyclic thioether group, spiroorthoester group, vinyloxy And the like. Among them, alicyclic ether group and vinyloxy group are preferable, and epoxy group, oxetanyl group and vinyloxy group are particularly preferable.
The polymerizable groups Ar ¹¹ to Ar ¹⁴ contains a substituted group containing is preferably a radical polymerizable group.
Two or more of the Ar ¹¹ to Ar ¹⁴ comprises a substituent containing a polymerizable ^group, preferably contains a substituent 2-4 of Ar 11 ^{to Ar 14} contains a polymerizable group, Ar More preferably, 2 or 3 out of ^{11 to} Ar ¹⁴ contain a substituent containing a polymerizable group, and 2 out of Ar ^{11 to} Ar ¹⁴ contain a substituent containing a polymerizable group More preferable.
When Ar ^{11 to} Ar ¹⁴ each independently represent a polycyclic aromatic hydrocarbon group containing a benzene ring surrounded by a broken line as one of the condensed rings, X ^{1 to} X ⁴ are each independently surrounded by a broken line The benzene ring may be substituted or a ring other than the benzene ring surrounded by a broken line may be substituted.

In formula (Q3), a and b each independently represent an integer of 1 to 5, preferably 1 or 2, and it is more preferable that both a and b be 1.
In formula (Q3), c and d each independently represent an integer of 0 to 5, preferably 0 or 1, and it is more preferable that both c and d be 0.

In formula (Q3), R ^{1 to} R ⁴ each independently represent a substituent. The substituent represented by R ^{1 to} R ⁴ is not particularly limited, and examples thereof include a halogen atom, a halogenated alkyl group, an alkyl group, an alkenyl group, an acyl group, a hydroxy group, a hydroxyalkyl group, an alkoxy group, an aryl group and a hetero An aryl group, an alicyclic group, etc. can be mentioned. The substituent represented by R ^{1 to} R ⁴ is preferably an alkyl group, an alkoxy group or an aryl group, and more preferably an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms or a phenyl group More preferably, it is a methyl group, a methoxy group or a phenyl group.
In the formula (Q3), when Ar ^{11 to} Ar ¹⁴ each independently represent a polycyclic aromatic hydrocarbon group containing a benzene ring surrounded by a broken line as one of the condensed rings, R ^{1 to} R ⁴ are each independently The benzene ring may be substituted by a dashed line or a ring other than the benzene ring surrounded by a dashed line.

In formula (Q3), e, f, g and h each independently represent an integer of 0 or more, and the upper limit values of e, f, g and h are each a substituent which Ar ^{11 to} Ar ¹⁴ can contain. It is a value obtained by subtracting a, b, c or d from the number.
Each of e, f, g and h is preferably independently 0 to 8, more preferably 0 to 2, and still more preferably 0.
When Ar ^{11 to} Ar ¹⁴ each independently represent a polycyclic aromatic hydrocarbon group containing a benzene ring surrounded by a broken line as one of the condensed rings, e, f, g and h are 0 or 1 Preferably, it is 0.

  Examples of the compound represented by the formula (Q3) include 9,9-bis [4- (2-acryloyloxyethoxy) phenyl] fluorene and the like. As the polymerizable compound containing a 9,9-bisarylfluorene skeleton, compounds described in JP-A-2010-254732 can also be suitably used.

  As a polymerizable compound containing such a cardo frame, although not limited, for example, On Coat EX series (manufactured by Nagase & Co., Ltd.) and ogsol (manufactured by Osaka Gas Chemical Co., Ltd.) can be mentioned.

[Optional component]
<Colorant>
The curable composition preferably contains a colorant. The colorant is at least one selected from the group consisting of a pigment and a dye, and may be a chromatic colorant or a black colorant, but preferably contains a black pigment.
Although the content of the coloring agent in the curable composition is not particularly limited, when the cured film obtained by the above-mentioned curable composition is used as a light shielding film, the curable composition of the curable composition is more excellent in light shielding property 50 mass% or more is preferable with respect to a total solid content.
The upper limit value of the content of the colorant is not particularly limited, but in general, 70% by mass or less is preferable with respect to the total solid content of the curable composition. When the content of the colorant is less than or equal to the upper limit value, the curable composition has more excellent coatability.

(Pigment)
The pigment is not particularly limited, and known inorganic pigments and / or organic pigments can be used.

-Inorganic pigment It does not restrict | limit especially as said inorganic pigment, A well-known inorganic pigment can be used.
Examples of inorganic pigments include zinc flower, lead white, lithopone, titanium oxide, chromium oxide, iron oxide, precipitated barium sulfate and barite powder, red lead, iron oxide red, yellow lead, zinc yellow (zinc yellow 1 type, Zinc yellow 2), ultramarine blue, Prussian blue (ferrous iron potassium) zircon gray, praseodymium yellow, chromium titanium yellow, chromium green, peacock, Victoria green, bitumen blue (independent of Prussian blue), vanadium zirconium blue, Chrome tin pink, pottery test pink, and salmon pink etc. are mentioned. In addition, as a black inorganic pigment, metal oxides containing one or more metal elements selected from the group consisting of Co, Cr, Cu, Mn, Ru, Fe, Ni, Sn, Ti, and Ag , Metal nitrides, and metal oxynitrides.

As an inorganic pigment, carbon black, titanium black, metal pigments, etc. (hereinafter, “black pigment”) in that a curable composition capable of forming a cured film having a high optical density at least is contained. It is also preferred). The metal pigment includes, for example, metal oxides containing one or more metal elements selected from the group consisting of Nb, V, Co, Cr, Cu, Mn, Ru, Fe, Ni, Sn, Ti, and Ag. And metal nitrogens.
The inorganic pigment includes at least one selected from the group consisting of titanium nitride, titanium oxynitride, niobium nitride, vanadium nitride, silver, or metal pigments containing silver, and metal pigments containing silver and tin. It is preferable to contain 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.
In addition, carbon black can also be used as an inorganic pigment. Specific examples of carbon black include C.I. I. Organic pigments such as C.I. I. Inorganic pigments such as C.I. Pigment Black 7 may be mentioned, but not limited thereto.

In the curable composition, pigments having infrared absorptivity other than the pigments described as the black pigment can also be used.
As the pigment having infrared absorptivity, tungsten compounds, metal borides and the like are preferable, and in particular, tungsten compounds are preferable from the viewpoint of being excellent in the light shielding property at the wavelength in the infrared region. In particular, a tungsten compound is preferable from the viewpoint of being excellent in the light absorption wavelength region of the photopolymerization initiator related to the curing efficiency by exposure and the light transmittance of the visible light region.

These pigments may be used in combination of two or more, and may be used in combination with the dyes described later. For example, a black pigment or a pigment having an infrared ray shielding property has red, green, yellow, orange, purple, blue and the like in order to adjust the color tone and to enhance the light shielding property in a desired wavelength range. The aspect which mixes a coloring pigment or the dye mentioned later is mentioned. It is preferable to mix a red pigment or dye, or a violet pigment or dye with a black pigment or a pigment having infrared light shielding properties, and more preferable to mix a red pigment with a black pigment or a pigment having infrared light shielding properties .
Furthermore, near infrared absorbers and infrared absorbers described later may be added.

The black pigment preferably contains titanium black and / or niobium oxynitride. Titanium black is a black particle containing a titanium atom. Preferred is low-order titanium oxide, titanium oxynitride or titanium nitride. The surface of the titanium black particles can be modified as needed for the purpose of improving dispersibility, suppressing aggregation, and the like. It is possible to coat with silicon oxide, titanium oxide, germanium oxide, aluminum oxide, magnesium oxide or zirconium oxide, and also treatment with a water repellent substance as shown in JP-A-2007-302836. It is possible.
Titanium black is typically titanium black particles, and it is preferable that both the primary particle size and the average primary particle size of the individual particles be small. The same applies to niobium oxynitride.
Specifically, those having an average primary particle diameter in the range of 10 nm to 45 nm are preferable.

The average primary particle size of the pigment can be measured using a transmission electron microscope (TEM). As a 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 size of the pigment is the maximum length of the particle image obtained using a transmission electron microscope (Dmax: the maximum length at two points on the outline of the particle image), and the maximum length perpendicular length (D DV-max: When the image is sandwiched by two straight lines parallel to the maximum length, the shortest length connecting the two straight lines is measured, and the geometric mean value (Dmax × DV-max) 1 / 2 was made into the particle diameter. The average primary particle size of the pigment measures the particle size of 100 particles by this method, and the arithmetic mean value is intended.

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

  It is preferable to use titanium oxynitride, titanium nitride or niobium oxynitride as the colorant, and titanium nitride or niobium oxynitride is more preferable, and niobium oxynitride is further preferable because moisture resistance of the obtained cured film is more excellent. preferable. It is believed that this is because these colorants are hydrophobic.

Furthermore, it is also preferable to contain titanium black as a dispersion containing titanium black and Si atoms.
In this embodiment, titanium black is contained as a substance to be dispersed in the curable composition, and the content ratio (Si / Ti) of Si atoms to Ti atoms in the substance to be dispersed is 0. 0 in mass conversion. 05 or more are preferable, 0.05-0.5 are more preferable, and 0.07-0.4 are still more preferable.
Here, the above-mentioned to-be-dispersed body includes both those in which titanium black is in the state of primary particles and those in the state of aggregates (secondary particles).
In order to change the content ratio (Si / Ti) of the material to be dispersed (for example, to 0.05 or more), the following means can be used.
First, a dispersion is obtained by dispersing titanium oxide and silica particles using a disperser, and the dispersion is subjected to reduction treatment at a high temperature (for example, 850 to 1,000 ° C.) to obtain titanium black particles. It is possible to obtain a to-be-dispersed material containing Si and Ti as main components. The reduction treatment can also be performed in the atmosphere of a reducing gas such as ammonia.
Examples of titanium oxide include TTO-51N (trade name, manufactured by Ishihara Sangyo).
Commercially available silica particles include AEROSIL (registered trademark) 90, 130, 150, 200, 255, 300, 380 (trade name, manufactured by Evonik) and the like.
Dispersion of titanium oxide and silica particles may use a dispersant. As a dispersing agent, what is demonstrated by the column of the dispersing agent mentioned later is mentioned.
The above dispersion may be carried out in a solvent. Examples of the solvent include water and organic solvents. What is demonstrated by the column of the organic solvent mentioned later is mentioned.
The titanium black whose content ratio (Si / Ti) is adjusted to, for example, 0.05 or more is described in, for example, paragraph [0005] and paragraphs [0016] to [0021] of JP-A-2008-266045. It can be produced by the method of

Curing including the material to be dispersed by adjusting the content ratio (Si / Ti) of Si atoms to Ti atoms in a material to be dispersed containing titanium black and Si atoms to a suitable range (for example, 0.05 or more) When a cured film is formed using the sexing composition, the residue derived from the curable composition outside the formation region of the cured film is reduced. In addition, a residue contains the component derived from curable compositions, such as a titanium black particle | grain and a resin component.
The reason why the residue is reduced is still unclear, but the above-mentioned material to be dispersed tends to have a smaller particle size (for example, particle size of 30 nm or less), and further contains Si atoms of this material to be dispersed. By increasing the content of components, the adsorptivity of the entire film to the substrate is reduced. It is speculated that this contributes to the improvement of the development removability of the uncured curable composition (particularly titanium black) in the formation of the cured film.
Since titanium black is excellent in the light shielding property to light in a wide wavelength range from ultraviolet light to infrared light, a dispersion containing the above-described titanium black and Si atoms (preferably, the content ratio (Si / Ti) is The cured film formed using the one having a mass conversion of 0.05 or more) exhibits excellent light shielding properties.
The content ratio (Si / Ti) of Si atoms to Ti atoms in the material to be dispersed is, for example, the method (1-1) or the method (1-2) described in paragraph 0033 of JP-A-2013-249417. ) Can be used.
Regarding the material to be dispersed contained in the cured film obtained by curing the curable composition, whether the content ratio (Si / Ti) of Si atom to Ti atom in the material to be dispersed is 0.05 or more In order to judge, the method (2) as described in Paragraph 0035 of Unexamined-Japanese-Patent No. 2013-249417 can be used.

In the dispersion containing titanium black and Si atoms, titanium black can be used as described above.
In this material to be dispersed, together with titanium black, for the purpose of adjusting the dispersibility, colorability, etc., complex oxides such as Cu, Fe, Mn, V, Ni, cobalt oxide, iron oxide, carbon black, aniline black etc. The black pigment consisting of these may be used 1 type or in combination of 2 or more types. In this case, it is preferable that the to-be-dispersed body which consists of titanium black occupies 50 mass% or more in all the to-be-dispersed bodies.
In this material to be dispersed, other colorants (such as organic pigments and / or dyes) 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 material to be dispersed will be described. When introducing Si atoms into the material to be dispersed, a Si-containing substance such as silica may be used.
Examples of the silica that can be used include precipitated silica, fumed silica, colloidal silica, synthetic silica and the like, and these may be appropriately selected and used.
Furthermore, fine particles of silica are preferably used because the light shielding properties are more excellent when the particle size of the silica particles is smaller than the film thickness when the cured film is formed. In addition, as an example of silica of a fine particle type, the silica of Unexamined-Japanese-Patent No. 2013-249417, Paragraph is mentioned, for example, and these content is integrated in this specification.

The curable composition can use a tungsten compound and / or a metal boride as a pigment.
Tungsten compounds and metal borides have high absorption for infrared rays (light with a wavelength of about 800 to 1,200 nm) (that is, high light shielding properties (shielding properties for infrared rays)) and visible lights. It is an infrared shielding material with low absorption. Therefore, the curable composition containing the tungsten compound and / or the metal boride 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 smaller absorption to short-wave light than the visible region used for exposure, such as high-pressure mercury lamp, KrF, ArF, etc. used for image formation. For this reason, by combining the above-mentioned polymerizable compound, the photopolymerization initiator, and the alkali-soluble resin described later, an excellent pattern can be obtained, and the development residue can be further suppressed in the pattern formation.

Examples of tungsten compounds include tungsten oxide compounds, tungsten boride compounds, tungsten sulfide compounds and the like, and tungsten oxide compounds represented by the following general formula (composition formula) (I) are 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 metals, alkaline earth metals, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, Tl, Sn, Pb, Ti, Nb, V, Mo, Ta, Re, Be, Hf, Os, Bi, Rb, Cs, etc. may be mentioned, with preference given to alkali metals. 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 still more preferably Cs.

When x / y is 0.001 or more, infrared rays can be shielded sufficiently, and when 1.1 or less, generation of an impurity phase in the tungsten compound is more reliably avoided. 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 general formula (I) include Cs _0.33 WO ₃ , Rb _0.33 WO ₃ , K _0.33 WO ₃ , Ba _0.33 WO _{3 and the} like. Cs _0.33 WO ₃ or Rb _0.33 WO ₃ is preferable, and Cs _0.33 WO ₃ is more preferable.

  The tungsten compound is preferably in the form of 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 still more preferably 200 nm or less. When the average primary particle diameter is in such a range, it is difficult for the tungsten fine particles to block visible light due to light scattering, so that it is possible to make the light transmission in the visible light region more reliable. From the viewpoint of avoiding light scattering, the smaller the average primary particle size, the better, but from the viewpoint of ease of handling at the time of production, etc., the average primary particle size of the tungsten fine particles is usually 1 nm or more.

  Two or more types of tungsten compounds can be used.

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

As metal borides, lanthanum boride (LaB ₆ ), praseodymium boride (PrB ₆ ), neodymium boride (N dB ₆ ), cerium boride (CeB ₆ ), yttrium boride (YB ₆ ), titanium boride TiB ₂ ), zirconium boride (ZrB ₂ ), hafnium boride (HfB ₂ ), vanadium boride (VB ₂ ), tantalum boride (TaB ₂ ), chromium boride (CrB, CrB ₂ ), molybdenum boride ( One or more of MoB ₂ , Mo ₂ B ₅ , MoB), tungsten boride (W ₂ B ₅ ) and the like can be mentioned, and lanthanum boride (LaB ₆ ) is preferable.

  The metal boride is preferably in the form of 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 still more preferably 100 nm or less. When the average primary particle diameter is in such a range, the metal boride fine particles are less likely to block visible light due to light scattering, so that it is possible to make the light transmission in the visible light region more reliable. From the viewpoint of avoiding light scattering, the smaller the average primary particle diameter, the better, but from the viewpoint of ease of handling at the time of production, etc., the average primary particle diameter of metal boride fine particles is usually 1 nm or more.

  Two or more metal borides may 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 an inorganic pigment, titanium nitride-containing particles containing Fe atoms can also be used. For the production of titanium nitride-containing particles, a gas phase reaction method is usually used, and specific examples include an electric furnace method and a thermal plasma method. Among these production methods, the thermal plasma method is preferable from the viewpoints of low contamination with impurities, easy uniformity of particle diameter, high productivity, and the like.
As a method of generating thermal plasma, direct current arc discharge, multiphase arc discharge, radio frequency (RF) plasma, hybrid plasma, etc. may be mentioned, and radio frequency plasma with less contamination of impurities from the electrode is preferable. As a specific manufacturing method of titanium nitride-containing fine particles by the thermal plasma method, for example, titanium powder is evaporated by high frequency thermal plasma, nitrogen is introduced as a carrier gas into the apparatus, and titanium powder is nitrided in the cooling process. , Methods of synthesizing titanium nitride-containing particles, and the like. The thermal plasma method is not limited to the above.

  Although it does not specifically limit as a manufacturing method of titanium nitride containing particle | grains, The manufacturing method as described in Paragraph <0037>-<0089> of WO 2010/147098 can be referred to. For example, instead of the Ag powder of WO 2010/147098, a mixture of a component containing Fe described later and / or a component containing Si and a powder of titanium and a powder of titanium (titanium particles) is used as a raw material The titanium nitride-containing particles contained in the curable composition of the present invention can be produced.

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

The titanium powder material (titanium particles) used for producing titanium nitride-containing particles may contain atoms other than titanium atoms. Other atoms that may be included 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% by mass with respect to the total mass of the titanium powder material.
When the titanium powder material contains Si atoms, the content of Si atoms is preferably more than 0.002 mass% and less than 0.3 mass% with respect to the total mass of the titanium powder material, and 0.01 It is more preferable that it is -0.15 mass%, and it is still more preferable that it is 0.02-0.1 mass%. The patternability of a cured film improves more because content of Si atom is more than 0.002 mass%. When the content of Si atoms is less than 0.3% by mass, the polarity of the outermost layer of the obtained titanium nitride-containing particles is further stabilized. As a result, when the titanium nitride-containing particles are dispersed, the adsorptivity of the dispersant to the titanium nitride-containing particles is improved, the non-dispersion of the titanium nitride-containing particles is reduced, and generation of particles can be suppressed. Be
The water content in the titanium powder material (titanium particles) used to produce 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. Is more preferable, and it is even more preferable that it is not substantially contained.

  The titanium nitride-containing particle is obtained by using a thermal plasma method, and the diffraction angle 2θ (described later in detail) 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 °.

There is no particular limitation on the method of incorporating Fe atoms into titanium nitride-containing particles, for example, introducing Fe atoms in the step of obtaining titanium particles (titanium powder) used as a raw material of titanium nitride-containing particles described above Methods etc. More specifically, when titanium is produced by the Kroll method or the like, a reaction container made of a material containing an Fe atom such as stainless steel, or a press and a grinder for crushing titanium is used. Fe atoms can be attached to the surface of titanium particles by using a material containing Fe atoms.
When the thermal plasma method is used for producing titanium nitride-containing particles, components such as Fe particles and Fe oxides are added in addition to titanium particles as a raw material, and these are nitrided by the thermal plasma method. The titanium nitride-containing particles can contain Fe atoms.
The 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 acid sulfides. Etc. may be included in any form. The Fe atoms contained in the titanium nitride-containing particles may be present as an impurity at a position between crystal lattices, or may be present as an impurity in an amorphous state at grain boundaries.

As a result of intensive studies, the present inventor has found that the content of Fe atoms in titanium nitride-containing particles is related to the patternability and the corrosion resistance of the electrode. It is considered that Fe atoms contained in the titanium nitride-containing particles are excellent in adhesion to the electrode and the substrate, and titanium nitride in the titanium nitride-containing particles adheres to the electrode and the substrate through Fe atoms. After patterning of the cured film such as development processing, it is considered that Fe atoms remain on the electrode and the substrate, and titanium nitride is easily removed. Therefore, it is speculated that the patterning property of the cured film is improved by setting the content of Fe atoms in the titanium nitride-containing particles to a predetermined amount or more. On the other hand, when the content of Fe atoms contained in the titanium nitride-containing particles is too large, the amount of Fe atoms remaining on the electrode and the substrate increases, which is considered to cause corrosion of the electrode. Therefore, it is assumed that the corrosion resistance of the electrode is improved by setting the content of Fe atoms in the titanium nitride-containing particles to a predetermined amount or less.
The content of Fe atoms in the titanium nitride-containing particles is preferably more than 0.001% by mass and less than 0.4% by mass with respect to the total mass of the titanium nitride-containing particles. Especially, it is more preferable that it is 0.01-0.2 mass%, and it is still more preferable that it is 0.02-0.1 mass%. The patternability of a cured film improves more because content of Fe atom is more than 0.001 mass%. The corrosion resistance of the electrode by a cured film improves more because content of Fe atom is less than 0.4 mass% (It can suppress that a cured film corrodes an electrode). That is, when the content of Fe atoms in the titanium nitride-containing particles is in the above range, excellent patternability of the cured film and corrosion resistance of the electrode can be obtained.
The content of Fe atoms in the titanium nitride-containing particles can be measured by ICP (Inductively Coupled Plasma; high frequency inductively coupled plasma) emission spectroscopy.

The titanium nitride-containing particles preferably further contain Si atoms (silicon atoms). Thereby, the patterning property of a cured film improves more. The reason why the patterning property is improved by containing the Si atom is considered to be the same as the Fe atom 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 is preferably 0.01 to 0.15. It is more preferable that it is mass%, and it is still more preferable that it is 0.02-0.1 mass%. The patternability of a cured film improves more because content of Si atom is more than 0.002 mass%. When the content of Si atoms is less than 0.3% by mass, the polarity of the outermost layer of the titanium nitride-containing particles is further stabilized. As a result, when the titanium nitride-containing particles are dispersed, the adsorptivity of the dispersant to the titanium nitride-containing particles is improved, the non-dispersion of the titanium nitride-containing particles is reduced, and generation of particles can be suppressed. Be
The content of Si atoms in the titanium nitride-containing particles can be measured by the same method as the above-described Fe atoms.

It does not specifically limit as a method to make a titanium nitride containing particle contain Si atom, For example, in the stage which obtains the titanium particle (titanium powder) used as a raw material of titanium nitride containing particle mentioned above, introduce Si atom Methods etc. More specifically, when titanium is produced by the Kroll method or the like, a reaction container made of a material containing Si atoms is used, or Si atoms as materials of a press and a grinder when crushing titanium are used. The Si atom can be attached to the surface of the titanium particle by using one containing.
When the thermal plasma method is used for producing titanium nitride-containing particles, components such as Si particles and Si oxide are added in addition to titanium particles as a raw material, and these are nitrided by the thermal plasma method. And titanium nitride-containing particles can contain Si atoms.
Si atoms contained in titanium nitride-containing particles are ions, metal compounds (including complex compounds), intermetallic compounds, alloys, oxides, complex oxides, nitrides, oxynitrides, sulfides, and acid sulfides. Etc. may be included in any form. The Si atoms contained in the titanium nitride-containing particles may be present as an impurity at a position between crystal lattices, or may be present as an impurity in an amorphous state at grain boundaries.

The content of titanium atoms (Ti atoms) in the titanium nitride-containing particles is preferably 10 to 85% by mass and 15 to 75% by mass with respect to the total mass of the titanium nitride-containing particles. More preferably, it is further 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 10 to 40% by mass. The content of nitrogen atoms can be analyzed by the inert gas melting-thermal conductivity method.
The titanium nitride-containing particles contain titanium nitride (TiN) as a main component, and usually become prominent when oxygen is mixed in during their synthesis and when the particle diameter is small, but due to oxidation of the particle surface, etc. , And may partially contain an oxygen atom.
The content of oxygen atoms in the titanium nitride-containing particles is preferably 1 to 40% by mass, more preferably 1 to 35% by mass, based on the total mass of the titanium nitride-containing particles. It is further more preferable that it is -30 mass%. The content of oxygen atoms can be analyzed by inert gas melting-infrared absorption method.

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

The titanium nitride-containing particles may be composite particles comprising titanium nitride particles and metal particles.
Composite fine particles refer to particles in which titanium nitride particles and metal fine particles are complexed or in a highly dispersed state. Here, "composite" means that particles are constituted by both components of titanium nitride and metal, and "highly dispersed state" means that titanium nitride particles and metal particles are It means that the particles of each small amount component are present individually and uniformly, uniformly, without aggregation.
The metal fine particles are not particularly limited. For example, copper, silver, gold, platinum, palladium, nickel, tin, cobalt, rhodium, iridium, ruthenium, osmium, manganese, molybdenum, tungsten, niobium, tantalum, calcium, titanium, bismuth And antimony and lead, and at least one selected from these alloys. Among them, copper, silver, gold, platinum, palladium, nickel, tin, cobalt, rhodium and iridium, and at least one selected from these alloys are preferable, and copper, silver, gold, platinum and tin, and these More preferably, it is at least one selected from alloys of Silver is preferable from the viewpoint of being excellent in moisture resistance.
The content of the metal fine particles in the titanium nitride-containing particles is preferably 5% by mass to 50% by mass, and more preferably 10% by mass to 30% by mass, based on the total mass of the titanium nitride-containing particles. Is more preferred.

  In the titanium nitride-containing particles, it is preferable that the diffraction angle 2θ of the peak derived from the (200) plane when CuKα radiation is used as the X-ray source is more than 42.6 ° and 43.5 ° or less. A cured film (for example, a black matrix etc.) obtained by using a curable composition containing titanium nitride-containing particles having such features can achieve high OD (optical density) values.

When the X-ray diffraction spectrum of a titanium compound is measured using CuKα radiation as an X-ray source, the peak with the highest intensity is as follows: TiN has a peak derived from the (200) plane around 2θ = 42.5 °, TiO The peak derived from the surface is observed near 2θ = 43.4 °. On the other hand, although not the strongest peak, anatase-type TiO ₂ has a peak derived from the (200) plane near 2θ = 48.1 °, and a rutile TiO ₂ has a peak derived from the (200) plane 2θ = 39 . Observed near 2 °. Therefore, the peak position shifts to the high angle side with respect to 42.5 ° as the crystal state contains a large number of 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, and further, at the time of production From the viewpoint of excellent process margin, 42.7 ° or more and less than 43.5 ° are more preferable, and further, from the viewpoint of excellent particle performance reproducibility, 42.7 ° or more and less than 43.4 ° are further preferable. When titanium oxide TiO ₂ is contained as an accessory component, the peak derived from anatase-type TiO ₂ (101) as the strongest peak is a peak derived from rutile-type TiO ₂ (110) in the vicinity of 2θ = 25.3 °. Is observed near 2θ = 27.4 °. However, since TiO ₂ is white and causes a reduction in the light shielding properties of the black matrix, it is preferable that it be reduced to such an extent that it is not observed as a peak.

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

  The crystallite size is preferably 20 nm or more, and more preferably 20 to 50 nm. By forming a black matrix using titanium nitride-containing particles having a crystallite size of 20 nm or more, the transmitted light of the cured film exhibits blue to blue violet such that its peak wavelength is 475 nm or less, and has high light shielding property. A black matrix having ultraviolet sensitivity can be obtained. When the crystallite size is 20 nm or more, the proportion of the active particle surface to the particle volume becomes small and the balance becomes a good balance, and the heat resistance and / or the durability of the titanium nitride-containing particles are more excellent It becomes.

.. Metal nitride-containing particles containing atom A Further, as the inorganic pigment, metal nitride-containing particles, wherein the metal nitride-containing particles contain metal nitride-containing particles containing a predetermined atom A You can also.
Examples of the metal in the metal nitride-containing particles include Nb, V, Cr, Y, Zr, Nb, Hf, Ta, W, Re and the like, with Nb or V being more preferable.
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% by mass.

It does not restrict | limit especially as a manufacturing method of metal nitride containing particle | grains containing the said atom A, A well-known method can be used.
For the production of the metal nitride-containing particles, a gas phase reaction method is usually used, and specific examples thereof include an electric furnace method and a thermal plasma method. Among these production methods, the thermal plasma method is preferable from the viewpoints of low contamination with impurities, easy uniformity of particle diameter, high productivity, and the like.
As a specific manufacturing method of the metal nitride containing particle | grains by a thermal plasma method, the thing using a metal microparticle manufacturing apparatus (The apparatus similar to the "black composite particle manufacturing apparatus" mentioned later) is mentioned, for example. The metal particle manufacturing apparatus includes, for example, a plasma torch for generating thermal plasma, a material supply device for supplying metal source powder into the plasma torch, a chamber having a cooling function, a cyclone for classifying the metal particles generated, and metal particles. It consists of the recovery part which recovers.
In the present specification, metal fine particles mean particles having a primary particle diameter of 20 nm to 40 μm of particles containing a metal element.

It does not specifically limit as a manufacturing method of metal nitride containing particle | grains using a metal microparticle manufacturing apparatus, A well-known method can be used. Among them, the method for producing metal nitride-containing particles using a metal fine particle producing apparatus may include the following steps, in that the yield of metal nitride-containing particles having a predetermined average primary particle diameter described below is enhanced. preferable.
Step A: A step of supplying a nitrogen gas-free inert gas as a plasma gas into the plasma torch to generate a thermal plasma flame.
Step B: A step of supplying a metal source powder containing a transition metal to a thermal plasma flame in a plasma torch, evaporating the metal source powder, and obtaining a source metal of a gas phase.
Step C: A step of cooling the gas phase raw material metal to obtain transition metal-containing metal fine particles.
Step D: A step of supplying an inert gas containing nitrogen gas as a plasma gas in a plasma torch to generate a thermal plasma flame.
Step E: A step of supplying metal microparticles containing a transition metal to a thermal plasma flame in a plasma torch, evaporating the metal microparticles, and obtaining a raw material metal of a gas phase.
Step F: a step of cooling the gas phase raw material metal to obtain metal nitride-containing particles.
The process for producing metal nitride-containing particles may optionally include the following step G after step C and / or step F.
Step G: Step of classifying the obtained particles.
Furthermore, the following step A2 may be included prior to step A, between step A and step B, between step C and step D, or between step D and step E.
Step A2: A step of mixing the atom A with the metal raw material powder containing a transition metal.
Furthermore, before the step A2, the following steps A3-1 to A3-3 may be included.
Step A3-1: A step of supplying a nitrogen gas-free inert gas as a plasma gas in the plasma torch to generate a thermal plasma flame.
Step A3-2: A raw material powder containing the atom A is supplied to a thermal plasma flame in a plasma torch, and the raw material powder is evaporated to obtain the atom A in the gas phase.
Step A3-3: A step of cooling the gas phase atoms A to obtain atomized atoms A.
A step G may be further included after the step A3-3.
As used herein, atomized atom A means particles having a primary particle diameter of 20 nm to 40 μm, which contains atom A.

Furthermore, it is preferable that the manufacturing method of the said metal nitride containing particle | grains further contains the following process H after the process F (When the process G is included, after the process G after the process F).
Step H: A step of exposing the metal nitride-containing particles obtained in step F (or step G) to a mixed atmosphere of water vapor and nitrogen gas and nitriding it.
If desired, the method for producing metal nitride-containing particles may further include step G after step H. Below, the suitable aspect of each process is explained in full detail.

Process A
Step A is a step of supplying an inert gas containing no nitrogen gas as a plasma gas into the plasma torch to generate a thermal plasma flame. The method of generating the thermal plasma flame is not particularly limited, and a direct current arc discharge method, a multiphase arc discharge method, a high frequency plasma method, a hybrid plasma method, etc. may be mentioned, and a high frequency plasma method with little contamination of impurities from electrodes Is preferred.
The method of generating a thermal plasma flame by the high frequency plasma method is not particularly limited. For example, plasma gas is supplied into a plasma torch containing a high frequency oscillation coil and a quartz tube, and a high frequency current is applied to the above high frequency oscillation coil. There is a method of obtaining a thermal plasma flame by carrying out.
As a plasma gas in the process A, the inert gas which does not contain nitrogen gas is mentioned. Examples of the inert gas containing no nitrogen gas include argon gas and hydrogen gas. The inert gas containing no nitrogen gas may be used alone or in combination of two or more.

Process A2
The step A2 is a step of mixing the atom A with the metal raw material powder containing a transition metal. It does not restrict | limit especially as a mixing method of a raw material metal powder and the atom A, A well-known method can be used. For example, the above-mentioned material supply device for supplying metal source powder into the plasma torch may contain a mixing and dispersing function. Specifically, the material supply device described in paragraphs 0047 to 0058 of WO 2010/147098 can be used, the contents of which are incorporated herein. The method for producing metal nitride-containing particles may further contain the following steps A3-1 to A3-3 before the step A2.

Process B
Step B is a step of supplying a metal raw material powder containing a transition metal to a thermal plasma flame in a plasma torch and evaporating the metal raw material powder to obtain a raw material metal of a gas phase. The method of supplying the metal source powder to the thermal plasma flame in the plasma torch is not particularly limited, but that the gas phase source metal to be obtained is sprayed using a carrier gas in a more uniform state. preferable. It is preferable to use an inert gas containing no nitrogen gas as the carrier gas. The aspect of the inert gas containing no nitrogen gas is as described above.
When the method for producing metal nitride-containing particles includes the above step A2, the metal raw material powder is maintained in a uniformly dispersed state until the metal raw material powder is supplied into the plasma torch. Is preferred.

Process C
Step C is a step of cooling the raw material metal of the gas phase to obtain metal fine particles containing a transition metal. The method of cooling is not particularly limited, but it is preferable to use a chamber containing a cooling function. The raw material metal of the gas phase obtained in step B is introduced into a chamber containing the above-mentioned cooling function, and quenched in the chamber to produce metal fine particles of the following desired particle diameter. The generated metal fine particles are recovered by, for example, a recovery unit. As the atmosphere in the chamber, an inert gas containing no nitrogen gas is preferable. The aspect of the inert gas containing no nitrogen gas is as described above.
In addition, the metal fine particle containing a transition metal is obtained by passing through said process AC. The fine metal particles containing a transition metal are easy to evaporate in step E. Even when the metal raw material powder contains impurities, the impurities can be removed through the steps A to C.

Process D
Process D is a process of supplying a nitrogen gas-containing inert gas as a plasma gas in a plasma torch to generate a thermal plasma flame. Nitrogen-containing inert gases include nitrogen gas and nitrogen gas containing an inert gas. The inert gas may, for example, be argon gas or hydrogen gas. The nitrogen gas containing an inert gas is not particularly limited, but the content of nitrogen gas is usually about 10 to 90 mol%, preferably about 30 to 60 mol%. The other aspects are the same as in step A.

Process E
Step E is a step of supplying metal microparticles containing a transition metal to a thermal plasma flame in a plasma torch, evaporating the metal microparticles, and obtaining a raw material metal of a gas phase. The method for supplying metal particles to the thermal plasma flame in the plasma torch is as described above, but as the carrier gas, an inert gas containing nitrogen is preferable. The aspect of the nitrogen-containing inert gas is as described above.
In step E, since the raw material metal that has become metal fine particles in steps A to C is supplied to the thermal plasma flame, the raw material metal in the gas phase is easily obtained, and the state of the raw material metal in the gas phase tends to be more uniform.

Process F
Step F is a step of cooling the raw material metal of the gas phase to obtain metal nitride-containing particles containing nitride of transition metal. The preferred embodiment of the cooling method is as described above, but as the atmosphere in the chamber, an inert gas containing nitrogen gas is preferable. Preferred embodiments of the inert gas containing nitrogen gas are as described above.

Process G
Step G is a step of classifying the obtained metal fine particles and / or metal nitride-containing particles. The classification method is not particularly limited, and for example, a cyclone can be used. The cyclone has a container on a cone, and has a function of generating a swirling flow in the container and classifying particles using centrifugal force. Classification is preferably performed under an inert gas atmosphere. The mode of the inert gas is as described above.

Process H
Step H is a step in which the metal nitride-containing particles are exposed to a mixed atmosphere of water vapor and nitrogen gas and subjected to a nitriding treatment. Through this process, the content of metal nitride in the metal nitride-containing particles can be further increased. The method for exposing the metal nitride-containing particles to a mixed atmosphere of water vapor and nitrogen gas is not particularly limited. For example, metal nitride-containing particles are introduced into a thermostat bath filled with a gas mixed with water vapor and nitrogen gas. There is a method in which the metal nitride-containing particles are allowed to stand or stirred for a predetermined time, and it is more preferable to allow the metal nitride-containing particles to be stabilized in terms of further stabilizing the surface and crystal boundaries.
The mixing ratio of water vapor and nitrogen gas is preferably such that the relative humidity is 25 to 95% if it is in the atmosphere. The time for standing or stirring is preferably 0.5 to 72 hours, and the temperature at that time is preferably 10 to 40 ° C.

Process A3-1 to A3-3
In steps A3-1 to A3-3, a nitrogen gas-free inert gas is supplied as a plasma gas in the plasma torch to generate a thermal plasma flame (A3-1), the thermal plasma flame in the plasma torch A step of supplying raw material powder containing atom A, evaporating the raw material powder to obtain atom A in the gas phase (A3-2), and cooling atom A in the gas phase; It is a process to obtain (A3-3). The mode in each step is the above step A, step B (in place of the metal raw material powder containing transition metal, using raw material powder containing atom A), and step C (metal fine particles containing transition metal) To obtain atomized atom A).
Through the above steps, atom A is atomized and atom A is easily evaporated in step E. Moreover, the impurities (metal components other than the atom A etc.) which the raw material powder containing the atom A contains can be removed through the said process.

Preferred Embodiment of Method of Manufacturing Metal Nitride-Containing Particles Containing Atom A As a preferable embodiment of a method of manufacturing metal nitride-containing particles containing atomic A, a method having the following steps in order may be mentioned.
Step A: A step of supplying a nitrogen gas-free inert gas as a plasma gas into the plasma torch to generate a thermal plasma flame.
Step B: A step of supplying a metal source powder containing a transition metal to a thermal plasma flame in a plasma torch, evaporating the metal source powder, and obtaining a source metal of a gas phase.
Step C: A step of cooling the gas phase raw material metal to obtain transition metal-containing metal fine particles.
Step G: Step of classifying the obtained particles.
Step A3-1: A step of supplying a nitrogen gas-free inert gas as a plasma gas in the plasma torch to generate a thermal plasma flame.
Step A3-2: A raw material powder containing the atom A is supplied to a thermal plasma flame in a plasma torch, and the raw material powder is evaporated to obtain the atom A in the gas phase.
Step A3-3: A step of cooling the gas phase atoms A to obtain atomized atoms A.
Step G: Step of classifying the obtained particles.
Step A2: A step of mixing the atom A (in this case, atomized A in this case) with the metal raw material powder (in this case, metal fine particles) containing a transition metal.
Step D: A step of supplying an inert gas containing nitrogen gas as a plasma gas in a plasma torch to generate a thermal plasma flame.
Step E: A step of supplying metal microparticles containing a transition metal to a thermal plasma flame in a plasma torch, evaporating the metal microparticles, and obtaining a raw material metal of a gas phase.
Step F: a step of cooling the gas phase raw material metal to obtain metal nitride-containing particles.
Step G: Step of classifying the obtained particles.
Step H: A step of exposing the metal nitride-containing particles obtained in step G to a mixed atmosphere of water vapor and nitrogen gas and nitriding it.
In the above-described series of steps, the order of steps A to C and steps A3-1 to A3-3 may be switched. That is, steps A to C may be performed after steps A3-1 to A3-3.

  According to a preferred embodiment of the method for producing metal nitride-containing particles containing atom A described above, metal raw material powder and impurities contained in raw material particles can be removed, and metal nitride having a desired average primary particle diameter Contained particles can be produced. The reason is that transition metals and / or atoms A are ionized by plasma treatment, and when the ions are cooled, transition metals, atoms A and impurities are micronized reflecting their respective melting points. It is guessed. At this time, the atom having a low melting point is rapidly formed into particles, and the atom having a high melting point is slowly formed into particles. Therefore, as described above, it is presumed that the microparticles once subjected to plasma treatment (Steps B and C, and Steps A3-2 and A3-3) tend to be single components (single crystals). If the particles of the single component obtained as described above are classified, the particles of the impurity can be removed by the difference in the density and / or the particle size of the particles of the transition metal and / or the particles of the atom A and the particles of the impurity. it can. The classification can be performed by appropriately setting classification conditions using, for example, a cyclone.

Purification of metal raw material powder and raw material powder Metal raw material powder containing transition metal (hereinafter referred to simply as “metal raw material powder”) that can be used in step B above and raw material powder containing atom A (hereinafter referred to simply as raw material Although it does not restrict | limit especially as a powder ".), It is preferable that it is a thing of high purity. The content of the transition metal in the metal raw material powder is not particularly limited, but is preferably 99.99% or more and more preferably 99.999% or more. The content of atom A in the raw material powder is the same.

  The metal raw material powder and / or the raw material powder may contain desired transition metals and / or atoms other than the atom A as impurities. Examples of the impurities contained in the metal source powder include boron, aluminum, silicon, manganese, iron, nickel and silver. Moreover, as an impurity contained in raw material powder, a metal element etc. are mentioned.

The method for producing metal nitride-containing particles may further include the following step A0 before step B (when step A2 is included, before step A2).
Step A0: a step of removing impurities from the metal source powder and / or the source powder.

Process A0
A method (separation and purification method) for removing impurities from the metal raw material powder and / or the raw material powder in the step A0 is not particularly limited, but, for example, niobium is described in paragraphs 0013 to 0030 of JP 2012-211048 A A method can be used, and the method according to this can be used also for other metal raw material powder and / or raw material powder.

Coating of Metal Nitride-Containing Particles The metal nitride-containing particles may be metal nitride-containing particles coated with an inorganic compound. That is, it may be coated metal nitride-containing particles having metal nitride-containing particles and a coating layer formed of an inorganic compound for coating the metal nitride-containing particles. Curable compositions containing metal nitride-containing particles coated with inorganic compounds have better dispersion stability.
The inorganic compound is not particularly limited, and oxides such as SiO ₂ , ZrO ₂ , TiO ₂ , GeO ₂ , Al ₂ O ₃ , Y ₂ O ₃ , and P ₂ O ₅ , and aluminum hydroxide and hydroxide. Examples include hydroxides such as zirconium. Among them, aluminum hydroxide is preferable in that it is easy to form a thinner film and to form a film having a higher coverage.
When it is intended to control the refractive index of the metal nitride-containing particles, silicon oxide is preferred as the low refractive index film, and zirconium hydroxide is preferred as the high refractive index film.
The method for coating the metal nitride-containing particles with the inorganic compound is not particularly limited, but the method for producing the metal nitride-containing particles preferably includes the following inorganic compound coating step.

Inorganic Compound Coating Step The inorganic compound coating step is a step of coating the metal nitride-containing particles described above with an oxide and / or a hydroxide. Although it does not restrict | limit especially as the method to coat | cover, For example, the following wet-coating methods etc. are mentioned.

  As a first wet coating method, first, the metal nitride-containing particles described above are mixed with water to prepare a slurry. Next, the above slurry is reacted with a water-soluble compound (for example, sodium silicate) containing at least one selected from the group consisting of Si, Zr, Ti, Ge, Al, Y and P, The alkali ions are removed by decantation and / or ion exchange resin or the like. Thereafter, the slurry is dried to obtain oxide-coated metal nitride-containing particles.

  As a second wet coating method, first, the above-described metal nitride-containing particles are mixed with an organic solvent such as alcohol to prepare a slurry. Next, an organometallic compound such as an alkoxide containing at least one selected from the group consisting of Si, Zr, Ti, Ge, Al, Y, and P is formed in the above slurry, and the above slurry is heated at a high temperature. Baking. When the above-mentioned slurry is calcined at high temperature, the sol-gel reaction proceeds to obtain oxide-coated metal nitride-containing particles.

  As a third wet coating method, a slurry containing an ionic liquid is produced using urea and aluminum chloride in the presence of metal nitride-containing particles. The metal nitride-containing particles are removed from the slurry, dried, and then the metal nitride-containing particles are fired to obtain metal hydroxide-containing particles coated with an aluminum hydroxide-containing hydroxide.

-Organic pigment As an organic pigment, color index (CI) pigment yellow 1,2,3,4,5,6,10,11,12,13,14,15,16,17,18,18, for example. 20, 24, 31, 32, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37, 1, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 16 7, 168, 169, 170, 171, 172, 173, 174, 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, 13, 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, 22, 23, 31, 38, 41, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 49: 2, 25: 2, 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, 170, 171, 172, 175, 176, 177, 178, 179, 184, 185, 187, 188, 190, 200, 202, 206, 208, 209, 210, 216, 220, 224, 226, 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, etc .; I. Pigment blue 1, 2, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, 66, 79, 80, etc .;
Can be 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, JP-B-2592207 and US Pat. No. 4,808,501. U.S. Pat. No. 5,667,920, U.S. Pat. No. 505,950, JP-A-5-333207, JP-A-6-35183, JP-A-6-51115, JP-A-6-194828, etc. Can be used. Classification according to chemical structure: pyrazole azo compound, pyromethene compound, anilino azo compound, triphenylmethane compound, anthraquinone compound, benzylidene compound, oxonol compound, pyrazolotriazole azo compound, pyridone azo compound, cyanine compound, phenothiazine compound, pyrrolopyrazole azomethine compound etc. Can be used. A dye multimer may be used as the dye. As a pigment | dye multimer, the compound described in Unexamined-Japanese-Patent No. 2011-213925, Unexamined-Japanese-Patent No. 2013-041097 is mentioned. A polymerizable dye having a 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.
An infrared absorber means the compound which has absorption in the wavelength range of infrared region (preferably wavelength 650-1,300 nm). Preferably, the infrared absorbing agent is preferably a compound having a maximum absorption wavelength in the wavelength range of 675 to 900 nm.
Examples of colorants having such spectral characteristics include pyrrolopyrrole compounds, copper compounds, cyanine compounds, phthalocyanine compounds, iminium compounds, thiol complex compounds, transition metal oxide compounds, squalilium compounds, naphthalocyanine compounds, quaterrylene Compounds, dithiol metal complex compounds, croconium compounds and the like can be mentioned.
As the phthalocyanine compound, naphthalocyanine compound, iminium compound, cyanine compound, squalium compound and croconium compound, the compounds disclosed in paragraphs 0010 to 0081 of JP-A-2010-111750 may be used, and the contents thereof are described in the present specification. Be incorporated. The cyanine compound can be referred to, for example, "Functional pigment, Shin Ookawara / Ken Matsuoka / Keijiro Kitao / Tsunehiro Hiraiso, Kodansha Scientific", the contents of which are incorporated herein.

  Compounds disclosed in paragraphs 0004 to 0016 of JP-A 07-164729 and / or compounds disclosed in paragraphs 0027 to 0062 of JP-A 2002-146254 as colorants having the above-mentioned spectral characteristics, JP-A 2011-164583 It is also possible to use near-infrared absorbing particles comprising crystallites of oxides containing Cu and / or P disclosed in paragraphs 0034 to 0067 of the gazette and having a number average aggregate particle diameter of 5 to 200 nm.

The compound having a maximum absorption wavelength in the wavelength range of 675 to 900 nm is preferably at least one selected from the group consisting of cyanine compounds, pyrrolopyrrole compounds, squarylium compounds, phthalocyanine compounds, and naphthalocyanine compounds.
The infrared absorber is preferably a compound that dissolves in water at 25 ° C. in 1% by mass or more, and more preferably a compound that dissolves in water at 25 ° C. by 10% by mass or more. The solvent resistance is improved by using such a compound.
The pyrrolopyrrole compounds can be referred to in paragraphs [0049] to [0062] of JP-A-2010-222557, the contents of which are incorporated herein. Cyanine compounds and squarylium compounds are described in paragraphs 0022 to 0063 of WO 2014/088063, paragraphs 0053 to 0118 of WO 2014/030628, and paragraphs 0028 to 0074 in JP 2014-59550, International Paragraphs 0013 to 0091 of Publication 2012/169447, Paragraphs 0019 to 0033 of JP 2015-176046, Paragraphs 0053 to 0099 of JP 2014-63144, Paragraphs of JP 2014-52431 Nos. 0085 to 0150, paragraphs 0076 to 0124 of JP 2014-44301, paragraphs 0045 to 0078 of JP 2012-8532, paragraphs 0027 to 0067 of JP 2015-172102, JP Paragraph Nos. 0029 to 0067 of 0151 to 20040, Paragraph Nos. 0029 to 0085 of Japanese Patent Laid-Open No. 2015-40895, Paragraphs 0022 to 0036 of Japanese Patent Laid-Open No. 2014-126642, Paragraph No. 0011 to 0017, paragraph 0010 to 0025 of JP 2015-157893, paragraph 0013 to 0026 of JP 2014-095007, paragraph 0013 to 0047 of JP 2014-80487, and JP 2013 Paragraph No. 0007-0028 grade | etc., Of -227403 gazette can be referred to and this content is integrated in this specification.

The infrared absorber is preferably at least one selected from the group consisting of compounds represented by the following general formulas 1 to 3.
General formula 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.
General formula 1-A

In the general formula 1-A, Z ^1A represents a nonmetallic atomic group forming a nitrogen-containing heterocyclic ring, R ^2A represents an alkyl group, an alkenyl group or an aralkyl group, and d represents 0 or 1 , A wavy line represents a connecting hand.
General formula 2

In General 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 , and R ⁴ and R ⁵ may be respectively bonded 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 are each independently hydrogen Represents an atom or a substituent,
R ⁶ may be covalently bonded or coordinately bonded to R ^1a or R ^3, and R ⁷ may be covalently bonded or coordinately bonded to R ^1b or R ⁵ .
General formula 3

In the general formula 3, Z ¹ and Z ² are each independently a nonmetallic atomic group forming a 5- or 6-membered nitrogen-containing heterocyclic ring 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 consisting of an odd number of methine,
a and b are each independently 0 or 1;
When a is 0, a carbon atom and a nitrogen atom are bonded by a double bond, and when b is 0, a carbon atom and a nitrogen atom are bonded by a single bond,
When the site represented by Cy in the formula is a cation moiety, X ¹ represents an anion, c represents the number necessary to balance the charge, and the site represented by Cy in the formula is an anion moiety Where X ¹ represents a cation, c represents the number necessary to balance the charge, and c is a molecule in which the charge at the site represented by Cy in the formula is neutralized within the molecule 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. As the pigment derivative, from the viewpoint of the dispersibility and the dispersion stability of the colorant A, a pigment derivative having an acidic group or a basic group is preferable. It is particularly preferred that the pigment derivative has a basic group. The combination of the resin (dispersant) described above and the pigment derivative is preferably a combination in which the dispersant is an acidic dispersant and the pigment derivative has a basic group.

Examples of organic pigments for constituting pigment derivatives include diketopyrrolopyrrole pigments, azo pigments, phthalocyanine pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, perinone pigments, perylene pigments, thioindigo pigments And isoindoline based pigments, isoindolinone based pigments, quinophthalone based pigments, srene based pigments, metal complex based pigments and the like.
As an acidic group which a pigment derivative has, a sulfonic acid group, a carboxylic acid group, and its salt are preferable, a carboxylic acid group and a sulfonic acid group are more preferable, and a sulfonic acid group is still more preferable. As a basic group which a pigment derivative has, an amino group is preferable and a tertiary amino group is more preferable.

  When the curable composition contains a pigment derivative, the content of the pigment derivative is preferably 1 to 30% by mass, and more preferably 3 to 20% by mass with respect to the mass of the pigment. The pigment derivative may use only 1 type and may use 2 or more types together.

<Polymerization inhibitor>
The curable composition may contain a polymerization inhibitor. By including the polymerization inhibitor, the curable composition has more excellent stability over time. In the present specification, the temporal stability means that a cured film having an excellent pattern shape can be obtained even when the curable composition is prepared and stored for a predetermined period of time.
The polymerization inhibitor has an effect of suppressing the progress of the reaction between the polyfunctional thiol compound and the polymerizable compound in the curable composition during storage, and it is presumed that the above-mentioned effect can be obtained.
0.001-1 mass% is preferable with respect to the total solid of a curable composition, as for content of a polymerization inhibitor, 0.005-1 mass% is more preferable, and 0.05-1 mass% is further more preferable. preferable.
When the content of the polymerization inhibitor is in the above range, the curable composition has more excellent temporal stability.

  The polymerization inhibitor is not particularly limited, and a known compound used as a polymerization inhibitor can be used. As a compound used as a polymerization inhibitor, a phenol type compound, a quinone type compound, a hindered amine type compound, a phenothiazine type compound, a nitrobenzene type compound etc. are mentioned, for example. The above compounds may be used alone or in combination of two or more.

  Examples of phenolic compounds include phenol, 4-methoxyphenol, hydroquinone, 2-tert-butylhydroquinone, catechol, 4-tert-butyl-catechol, 2,6-di-tert-butylphenol, 2,6-di- tert-Butyl-4-methylphenol, 2,6-di-tert-butyl-4-ethylphenol, 4-hydroxymethyl-2,6-di-tert-butylphenol, pentaerythritol tetrakis (3,5-di-tert -Butyl-4-hydroxyhydrocinnamate), 4-methoxy-1-naphthol, 1,4-dihydroxynaphthalene and the like.

  As a phenol type compound, the phenol type compound shown by Formula (IH-1) is preferable.

In formula (IH-1), R _{1 to} R ₅ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, a hydroxy group, an amino group, an aryl group, an alkoxy group, a carboxyl group, an alkoxycarbonyl group, or an acyl Represents a group. R _{1 to} R ₅ may be linked each other to form a ring.

As R _{1 to} R ₅ in the formula (IH-1), a hydrogen atom, an alkyl group having 1 to 5 carbon atoms (eg, a methyl group and an ethyl group), an alkoxy group having 1 to 5 carbon atoms (eg, methoxy) And ethoxy group, an alkenyl group having 2 to 4 carbon atoms (e.g., a vinyl group), or a phenyl group is preferable.
Among them, R ₁ and R ₅ are each independently more preferably a hydrogen atom or a tert-butyl group, R ₂ and R ₄ are more preferably a hydrogen atom, and R ₃ is a hydrogen atom, an alkyl having 1 to 5 carbon atoms A group or an alkoxy group having 1 to 5 carbon atoms is more preferable.

  Examples of the quinone compounds include 1,4-benzoquinone, 1,2-benzoquinone, and 1,4-naphthoquinone.

  As a hindered amine compound, the polymerization inhibitor represented by a following formula (IH-2) is mentioned, for example.

R ₆ in the formula (IH-2) represents a hydrogen atom, a hydroxy group, an amino group, an alkoxy group, an alkoxycarbonyl group or an acyl group. Among them, a hydrogen atom or a hydroxy group is preferable, and a hydroxy group is more preferable.
R _{7 to} R _{10 in} formula (IH-2) each independently represent a hydrogen atom or an alkyl group. The alkyl group R ₇ to R ₁₀ represent preferably an alkyl group having 1 to 5 carbon atoms, more preferably a methyl group or an ethyl group.

As a polymerization inhibitor, each said compound may be used individually by 1 type, may use 2 types together, and may use 3 or more types together.
The polymerization inhibitor preferably contains a phenolic compound. Among them, the polymerization inhibitor more preferably contains two or more phenolic compounds. Curable compositions containing different phenolic compounds have a better inventive effect.
The polymerization inhibitor preferably contains a phenolic compound and a hindered amine compound. A curable composition containing a phenolic compound and a hindered amine compound has more excellent effects of the present invention.

<Solvent>
The curable composition preferably contains a solvent. The solvent includes water and an organic solvent. The curable composition preferably contains an organic solvent.
When the curable composition contains a solvent, the solid content of the curable composition is preferably 10 to 30% by mass. When the solid content of the curable composition is at least the lower limit value, the viscosity is low and the coating property is improved. Furthermore, since the concentration of the highly reactive compound is lowered, the stability over time is improved. When the solid content of the curable composition is less than or equal to the upper limit value, the viscosity is maintained to a certain extent, and the coatability is improved. Furthermore, the coloring agent with a heavy specific gravity becomes difficult to settle, and the stability over time is improved.

(Organic solvent)
When the curable composition contains an organic solvent, the content of the organic solvent is preferably 70 to 90% by mass with respect to the total mass of the curable composition.
The organic solvents may be used alone or in combination of two or more. When two or more organic solvents are used in combination, the total amount thereof is preferably in the above range.

  The organic solvent is not particularly limited. For example, acetone, methyl ethyl ketone, cyclohexane, ethylene dichloride, tetrahydrofuran, toluene, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether Acetylacetone, cyclohexanone, cyclopentanone, diacetone alcohol, ethylene glycol monomethyl ether acetate, ethylene glycol ethyl ether acetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether acetate, 3-methoxypropanol, methoxymethoxyethanol, diethylene glycol Monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxypropyl acetate, N, N-dimethylformamide, dimethyl sulfoxide, γ-butyrolactone, 3 Methyl ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, methyl 3-methoxypropionate, 2-heptanone, ethyl carbitol acetate, butyl carbitol acetate, ethyl acetate, butyl acetate, methyl lactate and ethyl lactate Etc.

  When containing two or more organic solvents, the above methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2 -It is preferable to be composed of two or more selected from the group consisting of heptanone, cyclohexanone, cyclopentanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether, and propylene glycol monomethyl ether acetate.

(water)
The curable composition may contain water. Water may be intentionally added, or may be unavoidably contained in the curable composition by adding each component contained in the curable composition.
The content of water is preferably 0.01 to 1% by mass with respect to the total mass of the curable composition. When the content of water is in the above range, generation of pinholes is suppressed when producing a cured film, and furthermore, the moisture resistance of the cured film is improved.

<Dispersing agent>
The curable composition preferably contains a dispersant. The dispersant contributes to the improvement of the dispersibility of the colorant. In the present specification, the dispersant and the binder resin described later are different components.

When the curable composition contains a dispersant, the content of the dispersant is preferably 0.05 to 50% by mass, and 0.05 to 30% by mass with respect to the total solid content of the curable composition. More preferable.
The pattern shape of the cured film obtained by hardening | curing a curable composition as content of a dispersing agent is 0.05-30 mass% with respect to the total solid of a curable composition is more excellent.
The dispersant may be used alone or in combination of two or more. When two or more dispersants are used in combination, the total amount is preferably within the above range.

As the dispersant, for example, a known pigment dispersant can be appropriately selected and used. Among these, high molecular compounds are preferable.
As the dispersant, polymer dispersants [for example, polyamide amine and its salt, polycarboxylic acid and its salt, high molecular weight unsaturated acid ester, modified polyurethane, modified polyester, modified poly (meth) acrylate, (meth) acrylic type Copolymer, naphthalenesulfonic acid formalin condensate], polyoxyethylene alkyl phosphate ester, polyoxyethylene alkyl amine, and pigment derivative etc. can be mentioned.
The polymer compounds can be further classified into linear polymers, terminal modified polymers, graft polymers, and block polymers according to their structures.

(Polymer compound)
The polymer compound adsorbs to the surface of the colorant (for example, the inorganic pigment) to be dispersed, and acts to prevent reaggregation of the material to be dispersed. Therefore, terminal-modified polymers, graft polymers, and block polymers containing anchor sites on the pigment surface are preferred.

The polymer compound preferably contains a structural unit containing a graft chain. In the present specification, the “structural unit” is synonymous with the “repeating unit”.
A polymer compound containing a structural unit containing such a graft chain has an affinity to a solvent due to the graft chain, and therefore, the dispersibility of a coloring agent such as a black pigment and the dispersion stability after time Stability). A polymer compound containing a structural unit containing a graft chain has an affinity to a polymerizable compound or another usable resin by the presence of the graft chain. As a result, alkaline development is less likely to produce a residue.
The longer the graft chain, the higher the steric repulsion effect and the better the dispersibility of the black pigment and the like. On the other hand, when the graft chain is too long, the adsorptivity to color pigments such as black pigments is reduced, and the dispersibility of black pigments and the like tends to be reduced. For this reason, the graft chain preferably has 40 to 10,000 atoms excluding hydrogen atoms, more preferably 50 to 2,000 atoms excluding hydrogen atoms, and excluding hydrogen atoms. More preferably, the number of atoms is 60 to 500.
Here, the graft chain means from the root of the main chain of the copolymer (the atom bonded to the main chain in the group branched from the main chain) to the end of the group branched from the main chain.

The graft chain preferably contains a polymer structure, and as such a polymer structure, for example, poly (meth) acrylate structure (for example, poly (meth) acrylic structure), polyester structure, polyurethane structure, polyurea structure, polyamide Examples include structures and polyether structures.
The graft chain is selected from the group consisting of a polyester structure, a polyether structure and a poly (meth) acrylate structure in order to improve the interaction between the graft chain and the solvent and thereby enhance the dispersibility of the black pigment etc. It is preferably a graft chain containing at least one, more preferably a graft chain containing at least one of a polyester structure or a polyether structure.

  The macromonomer containing such a graft chain is not particularly limited, but a macromonomer containing a reactive double bondable group can be suitably used.

  As a commercially available macromonomer which corresponds to a structural unit containing a graft chain contained in a polymer compound and which is suitably used for the synthesis of the polymer compound, AA-6 (trade name, manufactured by Toagosei Co., Ltd.), AA-10 (Trade name, manufactured by Toa Gosei Co., Ltd.), AB-6 (trade name, produced by Toa Gosei Co., Ltd.), AS-6 (trade name, produced by Toa Gosei Co., Ltd.), AN-6 (trade name, produced by Toa Gosei Co., Ltd.) -6 (trade name, manufactured by Toa Gosei Co., Ltd.), AA-714 (trade name, produced by Toa Gosei Co., Ltd.), AY-707 (trade name, produced by Toa Gosei Co., Ltd.), AY-714 (trade name, produced by Toa Gosei Co., Ltd. AK-5 (trade name, manufactured by Toa Gosei Co., Ltd.), AK-30 (trade name, Toa Gosei Co., Ltd.), AK-32 (trade name, Toa Gosei Co., Ltd.), Blenmer PP-100 (trade name, NOF Corporation) Brenmer PP-500 (trade name, manufactured by NOF Corporation), Brenmer PP-800 (trade) Name, manufactured by NOF Corporation, BLEMMER PP-1000 (trade name, manufactured by NOF Corporation), BLEMMER 55-PET-800 (trade name, manufactured by NOF Corporation), BLEMMER PME-4000 (trade name, manufactured by NOF Corporation) Blemmer PSE-400 (trade name, manufactured by NOF Corporation), Blemmer PSE-1300 (trade name, manufactured by NOF Corporation), Blemmer 43PAPE-600B (trade name, manufactured by NOF Corporation), and the like. Among them, AA-6 (trade name, manufactured by Toa Gosei Co., Ltd.), AA-10 (trade name, Toa Gosei Co., Ltd. made), AB-6 (trade name, produced by Toa Gosei Co., Ltd.), AS-6 (trade name, Toa Gosei Co., Ltd., AN-6 (trade name, Toa Gosei Co., Ltd.), and Blemmer PME-4000 (trade name, NOF Corporation) are preferred.

The dispersant preferably contains at least one structure selected from the group consisting of methyl polyacrylate, polymethyl methacrylate and cyclic or linear polyesters. More preferably, the dispersant contains at least one structure selected from the group consisting of methyl polyacrylate, polymethyl methacrylate and linear polyesters. More preferably, the dispersant contains at least one structure selected from the group consisting of a polymethyl acrylate structure, a polymethyl methacrylate structure, a polycaprolactone structure, and a polyvalerolactone structure. The dispersant may contain the above structure alone in one dispersant, or may contain a plurality of these structures in one dispersant.
Here, a polycaprolactone structure means what contains the structure which ring-opened (epsilon) -caprolactone as a repeating unit. The polyvalerolactone structure refers to one containing a structure in which δ-valerolactone is ring-opened as a repeating unit.
Specific examples of the dispersant having a polycaprolactone structure include those in which j and k in the following formula (1) and the following formula (2) are 5. Moreover, as a specific example of the dispersing agent containing a polyvalerolactone structure, what is j and 4 in following formula (1) and following formula (2) is mentioned.
Specific examples of the dispersant containing a methyl polyacrylate structure include those in which X ⁵ in the following formula (4) is a hydrogen atom and R ⁴ is a methyl group. Specific examples of dispersants containing polymethyl methacrylate structure, X ⁵ in formula (4) is a methyl group, and R ⁴ is a methyl group.

· Structural unit containing graft chain The polymer compound preferably contains, as a structural unit containing a graft chain, a structural unit represented by any one of the following formulas (1) to (4), and the following formula It is more preferable to contain a structural unit represented by any one of (1A), the following formula (2A), the following formula (3A), the following formula (3B), and the following (4).

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. Each of X ¹ , X ² , X ³ , X ⁴ and X ⁵ is preferably independently a hydrogen atom or an alkyl group having 1 to 12 carbon atoms (number of carbon atoms) from the viewpoint of the restriction on synthesis, Independently, a hydrogen atom or a methyl group is more preferable, and a methyl group is still more preferable.

In formulas (1) to (4), Y ¹ , Y ² , Y ³ and Y ⁴ each independently represent a divalent linking group, and the linking group is not particularly restricted in terms of structure. Specific examples of the divalent linking group represented by Y ¹ , Y ² , Y ³ and Y ⁴ include the following linking groups (Y-1) to (Y-21), and the like. . In the structures shown below, A and B each represent a binding site. Among the structures shown below, (Y-2) or (Y-13) is more preferable from the easiness 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, but specifically, an alkyl group, a hydroxy group, an alkoxy group, an aryloxy group, a heteroaryloxy group, an alkylthioether group, an arylthioether group, a heteroarylthioether group, and an amino group Etc. Among these, as the organic groups represented by Z ¹ , Z ² , Z ³ and Z ⁴ , those having a steric repulsion effect are particularly preferable from the viewpoint of improving the dispersibility, and each of them independently has 5 carbon atoms Among them, 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 among them. . The alkyl group contained in the alkoxy group may be linear, branched or cyclic.

In formulas (1) to (4), n, m, p and q are each independently an integer of 1 to 500.
In Formula (1) and Formula (2), j and k respectively independently represent the integer of 2-8. J and k in the formulas (1) and (2) are preferably integers of 4 to 6, and most preferably 5 from the viewpoint of the temporal stability and developability of the curable composition.

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, plural R ^{3 s} may be the same as or different from each other.
In Formula (4), R ⁴ represents a hydrogen atom or a monovalent organic group, and the monovalent organic group is not particularly limited in structure. R ⁴ is preferably a hydrogen atom, an alkyl group, an aryl group or a heteroaryl group, more preferably a hydrogen atom or an alkyl group. When R ⁴ is an alkyl group, it is preferably 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, and has 1 to 20 carbon atoms The linear alkyl group of these is more preferable, and a C1-C6 linear alkyl group is still more preferable. In the formula (4), when q is 2 to 500, a plurality of X ⁵ and R ^{4 in} the graft copolymer may be the same or different.

The polymer compound can contain structural units containing graft chains that differ in two or more types of structures. That is, structural units represented by the formulas (1) to (4) having mutually different structures may be contained in the molecule of the polymer compound, and in the formulas (1) to (4), n, m, p , And q each represents an integer of 2 or more, in the formula (1) and the formula (2), j and k may contain mutually different structures in the side chain, and the formula (3) and the formula ( In 4), a plurality of R ^{3 's} , R ^{4' s} and X ^{5 's} in the molecule may be the same or different.

The structural unit represented by the formula (1) is more preferably a structural unit represented by the following formula (1A) from the viewpoint of the temporal stability and developability of the curable composition.
The structural unit represented by the formula (2) is more preferably a structural unit represented by the following formula (2A) from the viewpoint of the temporal stability and developability of the curable composition.

Wherein ^(1A), X ^1, Y 1, ^{Z 1} and n are as defined ^{X 1,} Y 1, ^{Z 1} and n in Formula (1), and preferred ranges are also the same. Wherein ^(2A), X ^2, Y 2, ^{Z 2} and m are as defined ^{X 2,} Y 2, ^{Z 2} and m in the formula (2), and preferred ranges are also the same.

  The structural unit represented by the formula (3) is more preferably a structural unit represented by the following formula (3A) or the formula (3B) from the viewpoint of the temporal stability and developability of the curable composition. .

Wherein (3A) or ^(3B), X ^3, Y 3, ^{Z 3} and p are as defined ^{X 3,} Y 3, ^{Z 3} and p in formula (3), and preferred ranges are also the same.

  The polymer compound more preferably contains a structural unit represented by Formula (1A) as a structural unit containing a graft chain.

  In the polymer compound, the structural units containing a graft chain (for example, the structural units represented by the above formulas (1) to (4)) are 2 to 90% by mass conversion based on the total mass of the polymer compound Is preferably contained in the range of 5 to 30%, and more preferably in the range of 5 to 30%. When the structural unit containing a graft chain is contained in this range, the dispersibility of the black pigment is high, and the developability at the time of forming a cured film is good.

Hydrophobic Structural Unit The polymer compound preferably contains a hydrophobic structural unit different from the structural unit containing a graft chain (ie, not corresponding to a structural unit containing a graft chain). However, in the present specification, the hydrophobic structural unit is a structural unit having no acid group (for example, a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, a phenolic hydroxy group, etc.).

  The hydrophobic structural unit is preferably a (corresponding) structural unit derived from a compound (monomer) having a C log P value of 1.2 or more, more preferably derived from a compound having a C log P value of 1.2 to 8. It is a structural unit. Thereby, the effect of the present invention can be expressed more reliably.

ClogP values are from Daylight Chemical Information System, Inc. Is a value calculated by the program "CLOGP" available from This program provides the value of "computed logP" calculated by the fragment approach of Hansch, Leo (see the following document). The fragment approach is based on the chemical structure of the compound, dividing the chemical structure into substructures (fragments) and estimating the logP value of the compound by summing the logP contributions assigned to the fragment. The details are described in the following documents. As used herein, ClogP values are intended to be those calculated by the program CLOGP v4.82.
A. J. Leo, Comprehensive Medicinal Chemistry, Vol. 4, C.I. Hansch, P .; G. Sammnens, J.J. B. Taylor and C. 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 logPoct from structure. Chem. Rev. , 93, 1281-1306, 1993.

log P means the common logarithm of partition coefficient P (Partition Coefficient), and it quantitatively determines how an organic compound is distributed in the equilibrium of oil (generally 1-octanol) and water. Is a physical property value represented as a numerical value, and is represented by the following equation.
logP = log (Coil / Cwater)
In the formula, Coil represents the molar concentration of the compound in the oil phase, and Cwater represents the molar concentration of the compound in the aqueous phase.
When the logP value becomes larger than 0, the oil solubility increases, and when it is negative and the absolute value increases, the water solubility increases, which has a negative correlation with the water solubility of the organic compound, and the affinity of the organic compound is negative. It is widely used as a parameter to estimate water quality.

  The polymer compound preferably contains, as a hydrophobic structural unit, at least one structural unit selected from structural units derived from monomers represented by the following formulas (i) to (iii).

In formulas (i) to (iii), R ¹ , R ² and R ³ each independently represent a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom or the like), or a carbon number of 1 to 4 6 represents an alkyl group (for example, a methyl group, an ethyl group, a propyl group, etc.).
R ¹ , R ² and R ³ are preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and more preferably a hydrogen atom or a methyl group. More preferably, R ² and R ³ are hydrogen atoms.
X represents an oxygen atom (-O-) or an imino group (-NH-), preferably an oxygen atom.

L is a single bond or a divalent linking group. As the divalent linking group, a divalent aliphatic group (for example, an alkylene group, a substituted alkylene group, an alkenylene group, a substituted alkenylene group, an alkynylene group, a substituted alkynylene group), a divalent aromatic group (for example, an arylene group) , substituted arylene group), a divalent heterocyclic group an oxygen atom (-O-), sulfur atom (-S-), an imino group (-NH-), a substituted imino group ^{(-NR 31} -, wherein ^{R 31} Are aliphatic groups, aromatic groups or heterocyclic groups), carbonyl groups (-CO-), and combinations thereof.

  The divalent aliphatic group may have a cyclic structure or a branched structure. 1-20 are preferable, as for carbon number of an aliphatic group, 1-15 are more preferable, and 1-10 are still more preferable. The aliphatic group may be an unsaturated aliphatic group or a saturated aliphatic group, but is preferably a saturated aliphatic group. The aliphatic group may have a substituent. Examples of the substituent 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 still more preferable. The aromatic group may have a substituent. Examples of the substituent include a halogen atom, an aliphatic group, an aromatic group and a heterocyclic group.

The divalent heterocyclic group preferably contains a 5- or 6-membered ring as a heterocyclic ring. The heterocycle may be fused to another heterocycle, an aliphatic ring or an aromatic ring. The heterocyclic group may have a substituent. Examples of the substituent include a halogen atom, a hydroxy group, an oxo group (= O), a thioxo group (= S), an imino group (= NH), and a substituted imino group (= N-R ³² , wherein R ³² is a fat) Group, aromatic group or heterocyclic group), aliphatic group, aromatic group or 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 an oxyalkylene structure repeated two or more times. As a polyoxyalkylene structure, a polyoxyethylene structure or a polyoxypropylene structure is preferable. The polyoxyethylene structure is represented by-(OCH ₂ CH ₂ ) n-, and n is preferably an integer of 2 or more, and more preferably an integer of 2 to 10.

Z represents an aliphatic group (for example, an alkyl group, a substituted alkyl group, an unsaturated alkyl group, a substituted unsaturated alkyl group), an aromatic group (for example, an aryl group, a substituted aryl group, an arylene group, a substituted arylene group), Heterocyclic groups or combinations thereof are mentioned. 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 A group or a heterocyclic group) or a carbonyl group (-CO-) may be included.

The aliphatic group may have a cyclic structure or a branched structure. 1-20 are preferable, as for carbon number of an aliphatic group, 1-15 are more preferable, and 1-10 are still more preferable. The aliphatic group further includes a ring-aggregated hydrocarbon group and a crosslinked cyclic hydrocarbon group, and examples of the ring-aggregated hydrocarbon group include a bicyclohexyl group, a perhydronaphthalenyl group, a biphenyl group, and -A cyclohexylphenyl group etc. are included. As the bridged cyclic hydrocarbon ring, for example, pinane, bornane, norpinane, norbornane, bicyclooctane ring (bicyclo [2.2.2] octane ring, bicyclo [3.2.1] octane ring, etc.) 2 Tricyclic hydrocarbon rings such as cyclic hydrocarbon rings, homobredane, adamantane, tricyclo [5.2.1.0 ^2,6 ] decane, and tricyclo [4.3.1.1 ^2,5 ] undecane rings And tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10] dodecane, and, perhydro-1,4-methano-5,8 methanolate 4 cyclic hydrocarbon ring such as naphthalene ring and the like. Examples of the bridged cyclic hydrocarbon ring include fused cyclic hydrocarbon rings such as perhydronaphthalene (decalin), perhydroanthracene, perhydrophenanthrene, perhydroacenaphthene, perhydrofluorene, perhydroindene, and perhydro Also included are fused rings in which a plurality of 5- to 8-membered cycloalkane rings such as phenalene rings are fused.
The aliphatic group is preferably a saturated aliphatic group rather than an unsaturated aliphatic group. The aliphatic group may have a substituent. Examples of substituents include halogen atoms, aromatic groups and heterocyclic groups. However, the aliphatic group does not have 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 still more preferable. The aromatic group may have a substituent. Examples of substituents include halogen atoms, aliphatic groups, aromatic groups and heterocyclic groups. However, the aromatic group does not have an acid group as a substituent.

The heterocyclic group preferably contains a 5- or 6-membered ring as a heterocyclic ring. The heterocycle may be fused to another heterocycle, an aliphatic ring or an aromatic ring. The heterocyclic group may have a substituent. Examples of the substituent include a halogen atom, a hydroxy group, an oxo group (= O), a thioxo group (= S), an imino group (= NH), and a substituted imino group (= N-R ³² , wherein R ³² is a fat) Group, an aromatic group or a heterocyclic group), an aliphatic group, an aromatic group and a heterocyclic group. However, the heterocyclic group does not have an acid group as a substituent.

In formula (iii), R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom, a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom, etc.), an alkyl group having 1 to 6 carbon atoms ( For example, a methyl group, an ethyl group, a propyl group etc.), Z, or LZ is represented. Here, L and Z are as defined above. As R < ⁴ >, R < ⁵ > and R < ⁶ >, a hydrogen atom or a C1-C3 alkyl group is preferable, and a hydrogen atom is more preferable.

As a monomer represented by Formula (i), R ¹ , R ² and R ³ are a hydrogen atom or a methyl group, and L is a single bond or a divalent linkage containing an alkylene group or an oxyalkylene structure Compounds in which X is an oxygen atom or an imino group, and Z is an aliphatic group, a heterocyclic group or an aromatic group are preferable.
As a monomer represented by the 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 preferable.
As a monomer represented by the formula (iii), a compound in which R ⁴ , R ⁵ and R ⁶ are a hydrogen atom or a methyl group and Z is an aliphatic group, a heterocyclic group or an aromatic group is preferable. .

Examples of representative compounds represented by formulas (i) to (iii) include radically polymerizable compounds selected from acrylic esters, methacrylic esters, styrenes and the like.
As examples of representative compounds represented by formulas (i) to (iii), reference can be made to the compounds described in paragraphs 0089 to 0093 of JP 2013-249417 A, the contents of which are incorporated herein. Be

  In the polymer compound, the hydrophobic structural unit is preferably contained in a range of 10 to 90%, and more preferably in a range of 20 to 80%, in terms of mass relative to the total mass of the polymer compound. Favorable pattern formation is obtained because content is the said range.

A functional group capable of forming an interaction with a colorant such as a black pigment A polymer compound can introduce a functional group capable of forming an interaction with a colorant such as a black pigment. Here, the polymer compound preferably further contains a structural unit containing a functional group capable of forming an interaction with a colorant such as a black pigment.
Examples of the functional group capable of forming an interaction with the colorant such as the black pigment include an acid group, a basic group, a coordinating group, and a functional group having reactivity.
When the polymer compound contains an acid group, a basic group, a coordinating group, or a functional group having reactivity, a structural unit containing an acid group, a structural unit containing a basic group, It is preferable to contain a structural unit containing a reactive group or a structural unit having reactivity.
In particular, when the polymer compound further contains an alkali-soluble group such as a carboxylic acid group as an acid group, the polymer compound can be provided 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 contributing to the dispersion of the colorant such as a black pigment contains alkali solubility. A curable composition containing such a polymer compound is excellent in the light shielding property of the exposed area, and the alkali developability of the unexposed area is improved.
When the polymer compound contains a structural unit containing an acid group, the polymer compound tends to be compatible with the solvent, and the coatability tends to be improved.
This is because the acid group in the structural unit containing the acid group easily interacts with the coloring agent such as the black pigment, and the polymer compound stably disperses the coloring agent such as the black pigment, and the coloring agent such as the black pigment It is presumed that the viscosity of the polymer compound for dispersing is lowered and the polymer compound itself is also easily dispersed stably.

  The structural unit containing an alkali-soluble group as an acid group may be the same structural unit as the above-mentioned structural unit containing a graft chain or may be a different structural unit. Are different structural units (ie, do not correspond to the hydrophobic structural units described above).

Examples of the acid group which is a functional group capable of forming an interaction with a coloring agent such as a black pigment include, for example, a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, or a phenolic hydroxy group. At least one of a sulfonic acid group and a phosphoric acid group is preferable, and a carboxylic acid group is more preferable in that the adsorptivity to a colorant such as a black pigment is good and the dispersibility of the colorant is high.
That is, the polymer compound preferably further contains a structural unit containing at least one of a carboxylic acid group, a sulfonic acid group, and a phosphoric acid group.

The polymer compound may have one or more structural units containing an acid group.
The polymer compound may or may not contain a structural unit containing an acid group, but when it is contained, the content of the structural unit containing an acid group is the total mass of the polymer compound in terms of mass. On the other hand, it is preferably 5 to 80%, and more preferably 10 to 60% from the viewpoint of suppressing damage to the image strength due to alkali development.

As a basic group which is a functional group capable of forming an interaction with a coloring agent such as a black pigment, for example, a heterocyclic ring containing a primary amino group, a secondary amino group, a tertiary amino group, and an N atom And an amide group etc. Preferred is a tertiary amino group in that the adsorptivity to a coloring agent such as a black pigment is good and the dispersibility of the coloring agent is high. The polymer compound can contain one or more of these basic groups.
The polymer compound may or may not contain a structural unit containing a basic group, but when it is contained, the content of the structural unit containing a basic group is the total of the polymer compound in terms of mass. 0.01% or more and 50% or less is preferable with respect to the mass, and 0.01% or more and 30% or less is more preferable from the viewpoint of inhibition of developability inhibition.

As a coordinating group which is a functional group capable of forming an interaction with a coloring agent such as a black pigment, and a functional group having reactivity, for example, an acetylacetoxy group, a trialkoxysilyl group, an isocyanate group, an acid anhydride, And acid chlorides and the like. Preferred is an acetylacetoxy group in that the adsorptivity to a colorant such as a black pigment is good and the dispersibility of the colorant is high. The polymer compound may have one or more of these groups.
The polymer compound may or may not contain a structural unit containing a coordinating group, or a structural unit containing a functional group having reactivity, but when it is contained, the content of these structural units In terms of mass, 10% to 80% of the total mass of the polymer compound is preferable, and 20% to 60% is more preferable from the viewpoint of inhibition of development inhibition.

  When the polymer compound contains, in addition to the graft chain, a functional group capable of forming an interaction with a coloring agent such as a black pigment, a functional group capable of forming an interaction with the coloring agent such as the various black pigments described above There is no particular limitation as to how these functional groups are introduced, as long as they are contained, but the polymer compound is derived from the monomers represented by the following general formulas (iv) to (vi) It is preferable to contain one or more structural units selected from structural units of

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

X ₁ in the formula (iv) represents an oxygen atom (-O-) or an imino group (-NH-), preferably an oxygen atom.
Y in 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. Examples of the divalent linking group include a divalent aliphatic group (for example, an alkylene group, a substituted alkylene group, an alkenylene group, a substituted alkenylene group, an alkynylene group, and a substituted alkynylene group), a divalent aromatic group (for example, , an arylene group, and a substituted arylene group), a divalent heterocyclic group an oxygen atom (-O-), sulfur atom (-S-), an imino group (-NH-), substituted imino bond ^{(-NR 31} '- Here, R ³¹ ′ is an aliphatic group, an aromatic group or a heterocyclic group), a carbonyl bond (—CO—), and a combination thereof.

  The divalent aliphatic group may have a cyclic structure or a branched structure. 1-20 are preferable, as for carbon number of an aliphatic group, 1-15 are more preferable, and 1-10 are still more preferable. The aliphatic group is preferably a saturated aliphatic group rather than an unsaturated aliphatic group. The aliphatic group may have a substituent. Examples of substituents include halogen atoms, hydroxy groups, aromatic groups and heterocyclic groups.

  6-20 are preferable, as for carbon number of a bivalent aromatic group, 6-15 are more preferable, and 6-10 are still more preferable. The aromatic group may have a substituent. Examples of the substituent include a halogen atom, a hydroxy group, an aliphatic group, an aromatic group and a heterocyclic group.

The divalent heterocyclic group preferably contains a 5- or 6-membered ring as a heterocyclic ring. One or more of other heterocycles, aliphatic rings or aromatic rings may be fused to the heterocycle. The heterocyclic group may have a substituent. Examples of the substituent include a halogen atom, a hydroxy group, an oxo group (= O), a thioxo group (= S), an imino group (= NH), and a substituted imino group (= N-R ³² , wherein R ³² is a fat) Group, an aromatic group or a heterocyclic group), an aliphatic group, an aromatic group and a heterocyclic group.

L ₁ 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 ₁ may contain a polyoxyalkylene structure containing an oxyalkylene structure repeated twice or more. As a polyoxyalkylene structure, a polyoxyethylene structure or a polyoxypropylene structure is preferable. The polyoxyethylene structure is represented by-(OCH ₂ CH ₂ ) n-, and n is preferably an integer of 2 or more, and more preferably an integer of 2 to 10.

In formulas (iv) to (vi), Z ₁ represents a functional group capable of forming an interaction with a coloring agent such as a black pigment in addition to a graft chain, and is a carboxylic acid group and a tertiary amino group Is preferred, and a carboxylic acid group is more preferred.

In formula (vi), R ¹⁴ , R ¹⁵ and R ¹⁶ each independently represent a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom or the like), an alkyl group having 1 to 6 carbon atoms ( for example, a methyl group, an ethyl group, a propyl group, etc.), - _{Z 1,} or an _L 1 -Z _1. Wherein _{L 1} and _{Z 1} are the same meaning as _{L 1} and _{Z 1} in the above, it is the preferable examples. As R <^14> , R <^15> and R < ¹⁶ >, a hydrogen atom or a C1-C3 alkyl group is preferable each independently, and a hydrogen atom is more preferable.

As a monomer represented by Formula (iv), R ¹¹ , R ¹² and R ¹³ each independently represent a hydrogen atom or a methyl group, and L ₁ is a divalent having an alkylene group or an oxyalkylene structure. Compounds in which X ₁ is an oxygen atom or an imino group and Z ₁ is a carboxylic acid group are preferable.
As a monomer represented by 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 Compounds are preferred.
Furthermore, 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, and L ₁ represents a single bond or an alkylene group, and Z Compounds in which ₁ is a carboxylic acid group are preferred.

The representative examples of the monomers (compounds) represented by Formula (iv) to Formula (vi) are shown below.
Examples of monomers include methacrylic acid, crotonic acid and isocrotonic acid, compounds containing an addition polymerizable double bond and a hydroxyl group in the molecule (for example, 2-hydroxyethyl methacrylate) and succinic anhydride. Reactant, Reactant of compound having addition polymerizable double bond and hydroxy group in molecule with phthalic anhydride, Compound having addition polymerizable double bond and hydroxy group in molecule and tetrahydroxyphthalic acid Reactant with an anhydride, Reactant of a compound containing an addition polymerizable double bond and a hydroxy group in the molecule with trimellitic anhydride, and a compound containing an addition polymerizable double bond and a hydroxy group in the molecule Reactants with pyromellitic anhydride, acrylic acid, acrylic acid dimer, acrylic acid oligomer, maleic acid, itaconic acid, fumaric acid, 4-vinyl benzoic acid , Vinylphenol, and, and 4-hydroxyphenyl methacrylamide.

  The content of the structural unit containing a functional group capable of forming an interaction with a colorant such as a black pigment is from the viewpoint of the interaction with the colorant such as a black pigment, the temporal stability, and the permeability to a developer. 0.05 mass%-90 mass% are preferable with respect to the total mass of a high molecular compound, 1.0 mass%-80 mass% are more preferable, 10 mass%-70 mass% are still more preferable.

-Other structural units Furthermore, in order to improve various performances such as image strength, the polymer compound is a structural unit containing a graft chain, a hydrophobic structural unit, and a black color, as long as the effects of the present invention are not impaired. A structural unit different from a structural unit containing a functional group capable of forming an interaction with a coloring agent such as a pigment, has another structural unit having various functions (for example, a functional group having an affinity to a dispersion medium used for dispersion) And the like) may further be included.
Examples of such other structural units include structural units derived from radically polymerizable compounds selected from acrylonitriles and methacrylonitriles and the like.
The polymer compound can use one or more of these other structural units, and its content is preferably 0% or more and 80% or less based on the total mass of the polymer compound in terms of mass. 10% or more and 60% or less is more preferable. Sufficient pattern formability is maintained in the above range of content.

Physical Properties of Polymer Compound The acid value of the polymer compound is preferably in the range of 0 mg KOH / g to 250 mg KOH / g, more preferably 10 mg KOH / g to 200 mg KOH / g, and more preferably 20 mg KOH / g to 120 mg KOH / g. A range is more preferred.
When the acid value of the polymer compound is 160 mg KOH / g or less, pattern peeling during development when forming a cured film can be more effectively suppressed. When the acid value of the polymer compound is 10 mg KOH / g or more, the alkali developability becomes better. In addition, when the acid value of the polymer compound is 20 mg KOH / g or more, sedimentation of the colorant such as a black pigment can be further suppressed, the number of coarse particles can be further reduced, and the temporal stability of the curable composition can be obtained. It can improve more.

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

The weight average molecular weight of the polymer compound is, when forming a cured film, as a polystyrene conversion value by GPC (Gel Permeation Chromatography: gel permeation chromatography) method from the viewpoint of suppression of pattern peeling during development and developability when forming a cured film; It is preferably 000 or more and 300,000 or less, more preferably 5,000 or more and 200,000 or less, still more preferably 6,000 or more and 100,000 or less, and 10,000 or more and 50,000 or less Is particularly preferred.
The GPC method is based on HLC-8020GPC (manufactured by Tosoh Corporation) using TSKgel Super HZM-H, TSKgel Super HZ 4000, TSKgel Super HZ 2000 (Tosoh, 4.6 mm ID × 15 cm) as a column, and THF (tetrahydrofuran) as an eluent. .

  The polymer compound can be synthesized based on a known method, and as a solvent used when synthesizing the polymer compound, for example, ethylene dichloride, cyclohexanone, methyl ethyl ketone, acetone, methanol, ethanol, propanol, butanol, ethylene glycol monomethyl Ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, 1-methoxy-2-propanol, 1-methoxy-2-propyl acetate, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, toluene, Ethyl acetate, methyl lactate, ethyl lactate and the like can be mentioned. These solvents may be used alone or in combination of two or more.

Specific examples of the polymer compound include “DA-7301” manufactured by Tochigi Kasei Co., Ltd., “Disperbyk-101 (polyamide amine phosphate), 107 (carboxylic acid ester), 110 (acid group-containing copolymer” manufactured by BYK Chemie ), 111 (phosphate based dispersant), 130 (polyamide), 161, 162, 163, 164, 165, 166, 170, 190 (polymer copolymer), “BYK-P104, P105 (high molecular weight non-polymer)” Saturated polycarboxylic acid) ", EFKA 4047, 4050 to 4010 to 4165 (polyurethane-based), EFKA 4330 to 4340 (block copolymer), 4400 to 4402 (modified polyacrylate), 5010 (polyester amide), 5765 (manufactured by EFKA) High molecular weight polycarboxylates), 6220 (fatty acid polys ), 6745 (Phthalocyanine derivative), 6750 (Azo pigment derivative) ”,“ Adispar PB 821, PB 822, PB 880, PB 881 ”manufactured by Ajinomoto Fine Techno Co.,“ Flower TG-710 (urethane oligomer) ”manufactured by Kyoeisha Chemical Co., Ltd.,“ Polyflow ” No. 50E, No. 300 (acrylic copolymer), manufactured by Kushimoto Chemical Co., Ltd. “Disparone KS-860, 873 SN, 874, # 2150 (aliphatic polyvalent carboxylic acid), # 7004 (polyether ester), DA -703-50, DA-705, DA-725 ", Kao Corporation" Demol RN, N (Naphtalene 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 nonyl phenyl ether) "," Acetamine 86 (stearylamine acetate) ", manufactured by Nippon Lubrizol" Sorsparse 5000 (phthalocyanine derivative), 22000 (azo pigment derivative), 13240 (polyester amine), 3000, 12000, 17000, 20000, 27000 (polymer having a functional part at the end), 24000, 28000, 32000, 38500 (graft copolymer), manufactured by Nikko Chemicals Co., Ltd. "NIKKOL T106 (polyoxyethylene sorbitan mono-ester)" Oleate), MYS-IEX (polyoxyethylene monostearate), manufactured by Kawaken Fine Chemicals Co., Ltd. Hinoact T-8000 E, etc. manufactured by Shin-Etsu Chemical Co., Ltd., organosiloxane polymer KP 341, 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", "Morita Sangyo" EFKA-46, EFKA-47, EFKA-47EA, EFKA polymer 100, EFKA polymer 400 " , EFKA Polymer 401, EFKA Polymer 450 ", San Nopco" Dispers Aid 6, Dispers Aid 8, Dispers Aid 15, Dispers Polymer dispersants such as Suade 9100, "ADEKA PLURONIC L31, F38, L42, L44, L61, L64, L68, L72, P72, P77, P84, F87, P94, L101, P101, P108, L121, P121, ADEKA" And "Ionette (trade name) S-20" manufactured by Sanyo Chemical Industries, Ltd. and the like. Also, Acrybase FFS-6752, Acrybase FFS-187, Acrycure-RD-F8, and Cyclomer P can be used.
As a commercial item of the amphoteric resin, for example, DISPERBYK-130, DISPERBYK-140, DISPERBYK-142, DISPERBYK-145, DISPERBYK-180, DISPERBYK-187, DISPERBYK-187, DISPERBYK-191, DISPERBYK-2001, DISPERBYK-2001, DISPERBYK-2010, manufactured by Bick Chemie, Inc. DISPERBYK-2012, DISPERBYK-2025, BYK-9076, Ajisper PB 821 manufactured by Ajinomoto Fine Techno Co., Ltd., Azi sasper PB 822, and Azi sasper PB 881 and the like.
One of these polymer compounds may be used alone, or two or more thereof may be used in combination.

  As specific examples of the polymer compound, the polymer compounds described in paragraphs “0127” to “0129” of JP 2013-249417 A can be referred to, and the contents thereof are incorporated in the present specification.

As the dispersant, in addition to the above-mentioned polymer compounds, graft copolymers of paragraphs 0037 to 0115 of JP 2010-106268 A (columns 0075 to 0133 of corresponding US 2011/0124824) can be used, and the contents of these can be used. Are incorporated by reference and incorporated herein.
In addition to the above, a configuration including a side chain structure formed by combining the acidic group of paragraphs 0028 to 0084 (corresponding column 0075 to 0133 in US2011 / 02729759 of JP2011-153283A) via a linking group. Polymeric compounds containing components can be used, the contents of which can be incorporated and incorporated herein.

<Binder resin>
The curable composition preferably contains a binder resin.
As for content of binder resin, 0.1-30 mass% is preferable with respect to the total solid of a curable composition.
When the content of the binder resin is 0.3 to 25% by mass or more based on the total solid content of the curable composition, the pattern shape of a cured film obtained by curing the curable composition is more excellent.
The binder resin may be used alone or in combination of two or more. When using 2 or more types of binder resin together, it is preferable that the total amount is in the said range.

It is preferable to use a linear organic polymer as the binder resin. As such a linear organic polymer, known ones can be optionally used. Preferably, linear organic polymers that are soluble or swellable in water or weakly alkaline water are selected to enable water development or weakly 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 binder resin is a linear organic polymer, and promotes at least one alkali solubility in a molecule (preferably, a molecule having a (meth) acrylic copolymer or a styrenic copolymer as a main chain) It can select suitably from the alkali-soluble resin containing the group to be. From the viewpoint of heat resistance, polyhydroxystyrene resins, polysiloxane resins, (meth) acrylic resins, (meth) acrylamide resins, (meth) acrylic / (meth) acrylamide copolymer resins, epoxy resins and Polyimide resins are preferred, and from the viewpoint of control of developability, (meth) acrylic resins, (meth) acrylamide resins, (meth) acrylic / (meth) acrylamide copolymer resins or polyimide resins are more preferred.
Examples of the group that promotes alkali solubility (hereinafter, also referred to as an acid group) include, for example, a carboxylic acid group, a phosphoric acid group, a sulfonic acid group, and a phenolic hydroxy group. Especially, what is soluble in an organic solvent and developable by weak alkali aqueous solution is preferable, and the alkali-soluble resin containing the structural unit derived from (meth) acrylic acid is mentioned as a more preferable thing. These acid groups may be of only one type, or of two or more types.

As binder resin, the radical polymer which contains a carboxylic acid group in a side chain is mentioned, for example. As radical polymers containing a carboxylic acid group in the side chain, for example, JP-A-59-44615, JP-B-54-34327, JP-B-58-12577, JP-B-54-25957, JP-A-54. Examples thereof are those described in JP-A-92723, JP-A-59-53836, and JP-A-59-71048. As a radical polymer containing a carboxylic acid group in the side chain, a resin obtained by homopolymerizing or copolymerizing a monomer containing a carboxylic acid group, and an acid anhydride obtained by homopolymerizing or copolymerizing a monomer containing an acid anhydride Examples thereof include resins obtained by hydrolyzing, half esterifying or half amidating units, and epoxy acrylates in which an epoxy resin is modified with unsaturated monocarboxylic acid and acid anhydride.
As a monomer containing a carboxylic acid group, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, 4-carboxystyrene and the like can be mentioned. Acidic cellulose derivatives containing a carboxylic acid group in the side chain are also mentioned as an example.
As a monomer containing an acid anhydride, maleic anhydride etc. are mentioned. In addition, polymers obtained by adding a cyclic acid anhydride to a polymer containing a hydroxy group are useful.
An acetal-modified polyvinyl alcohol-based binder resin containing an acid group is described in European Patent No. 993966, European Patent No. 1204000, and JP-A No. 2001-318463. An acetal-modified polyvinyl alcohol-based binder resin containing an acid group is suitable because it is excellent in the balance between film strength and developability.
Furthermore, polyvinyl pyrrolidone, polyethylene oxide or the like is useful as the water-soluble linear organic polymer. Also, in order to increase the strength of the cured film, alcohol-soluble nylon, polyether which is a reaction product of 2,2-bis- (4-hydroxyphenyl) -propane and epichlorohydrin, and the like are useful.
The polyimide resins described in WO 2008/123097 are also useful.

Among these, [benzyl (meth) acrylate / (meth) acrylic acid / optionally other addition polymerizable vinyl monomer] copolymer, and [allyl (meth) acrylate / (meth) acrylic acid / optionally Other addition polymerizable vinyl monomers] The copolymer is excellent in the balance of film strength, sensitivity and developability and is preferable.
Examples of commercially available products include Acrybase FF-187, FF-426 (Fujikura Kasei Co., Ltd.), Acrycure-RD-F8 (Nippon Catalyst), and Cyclomer P (ACA) 230AA manufactured by Daicel Ornex.

  For example, a known radical polymerization method can be applied to the production of the binder resin. Those skilled in the art can easily set the polymerization conditions such as temperature, pressure, kind and amount of radical initiator, and kind of solvent in producing the binder resin by the radical polymerization method.

It is also preferable to use, as a binder resin, a polymer containing a structural unit containing a graft chain and a structural unit containing an acid group (alkali soluble group).
The definition of the structural unit containing a graft chain is the same as the structural unit containing a graft chain contained in the above-mentioned dispersant, and the preferred range is also the same.
Examples of the acid group include a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, or a phenolic hydroxy group, and at least one of a carboxylic acid group, a sulfonic acid group, and a phosphoric acid group is preferable. And carboxylic acid groups are more preferred.

(Structural unit containing an acid group)
As a structural unit containing an acid group, it is preferable to contain one or more types of structural units selected from the structural unit derived from the monomer represented by following formula (vii)-formula (ix).

In formulas (vii) to (ix), each of R ²¹ , R ²² and R ²³ independently represents a hydrogen atom, a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom, etc.) or a carbon number of 1 -Represents an alkyl group of 6 to 6 (e.g., a methyl group, an ethyl group, a propyl group, etc.).
In formulas (vii) to (ix), R ²¹ , R ²² and R ²³ each independently preferably represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and each independently represents a hydrogen atom or More preferably, it is a methyl group. In formula (vii), each of R ²¹ and R ²³ is particularly preferably a hydrogen atom.

_{X 2} in the formula (vii) represents an oxygen atom (-O-) or imino group (-NH-), preferably an oxygen atom.
Moreover, Y in Formula (viii) represents a methine group or a nitrogen atom.

L _{2 in} Formula (vii) to Formula (ix) represents a single bond or a divalent linking group. Examples of the divalent linking group include a divalent aliphatic group (for example, an alkylene group, a substituted alkylene group, an alkenylene group, a substituted alkenylene group, an alkynylene group, and a substituted alkynylene group), a divalent aromatic group (for example, , Arylene group, and substituted arylene group), divalent heterocyclic group, oxygen atom (-O-), sulfur atom (-S-), imino group (-NH-), substituted imino bond (-NR ⁴¹ '- Here, R ⁴¹ ′ represents an aliphatic group, an aromatic group or a heterocyclic group), a carbonyl bond (—CO—), and a combination thereof.

  The divalent aliphatic group may have a cyclic structure or a branched structure. 1-20 are preferable, as for carbon number of an aliphatic group, 1-15 are more preferable, and 1-10 are still more preferable. The aliphatic group is preferably a saturated aliphatic group rather than an unsaturated aliphatic group. The aliphatic group may have a substituent. Examples of substituents include halogen atoms, hydroxy groups, aromatic groups and heterocyclic groups.

  6-20 are preferable, as for carbon number of a bivalent aromatic group, 6-15 are more preferable, and 6-10 are still more preferable. The aromatic group may have a substituent. Examples of the substituent include a halogen atom, a hydroxy group, an aliphatic group, an aromatic group and a heterocyclic group.

The divalent heterocyclic group preferably contains a 5- or 6-membered ring as a heterocyclic ring. One or more of other heterocycles, aliphatic rings or aromatic rings may be fused to the heterocycle. The heterocyclic group may have a substituent. Examples of the substituent include a halogen atom, a hydroxy group, an oxo group (= O), a thioxo group (= S), an imino group (= NH), and a substituted imino group (= N-R ⁴² , wherein R ⁴² is a fat) Group, an aromatic group or a heterocyclic group), an aliphatic group, an aromatic group and a heterocyclic group.

L ₂ 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 ₂ may contain a polyoxyalkylene structure containing an oxyalkylene structure repeated twice or more. As a polyoxyalkylene structure, a polyoxyethylene structure or a polyoxypropylene structure is preferable. The polyoxyethylene structure is represented by-(OCH ₂ CH ₂ ) n-, and n is preferably an integer of 2 or more, and more preferably an integer of 2 to 10.

In formulas (vii) to (ix), Z ₂ is an acid group, preferably a carboxylic acid group.

In formula (ix), R ²⁴ , R ²⁵ and R ²⁶ each independently represent a hydrogen atom, a halogen atom (for example, fluorine, chlorine, bromine or the like), or an alkyl group having 1 to 6 carbon atoms (for example, methyl group, an ethyl group, a propyl group, etc.), - represents a _{Z 2,} or _L 2 -Z _2. Here _{L 2} and _{Z 2} has the same meaning as _{L 2} and _{Z 2} in the above, and preferred examples are also the same. As R <^24> , R <^25> and R < ²⁶ >, a hydrogen atom or a C1-C3 alkyl group is preferable each independently, and a hydrogen atom is more preferable.

As a monomer represented by the formula (vii), R ²¹ , R ²² and R ²³ each independently represent a hydrogen atom or a methyl group, and L ₂ is a divalent having an alkylene group or an oxyalkylene structure. The linking group is preferably a compound wherein X ₂ is an oxygen atom or an imino group, and Z ₂ is a carboxylic acid group.
As a monomer represented by Formula (vii), R ²¹ is a hydrogen atom or a methyl group, L ₂ is an alkylene group, Z ₂ is a carboxylic acid group, and Y is a methine group Compounds are preferred.
Furthermore, as a monomer represented by Formula (ix), a compound in which R ²⁴ , R ²⁵ and R ²⁶ are each independently a hydrogen atom or a methyl group and Z ₂ is a carboxylic acid group is preferable.

  The binder resin can be synthesized by the same method as the above-mentioned dispersant containing a graft chain-containing structural unit, and the preferable acid value and weight average molecular weight are also the same.

The binder resin may have one or more structural units containing an acid group.
The content of the structural unit containing an acid group is preferably 5 to 95% by mass conversion with respect to the total mass of the binder resin, and from the viewpoint of suppressing damage to the image strength by alkali development, 10 to 90% is more preferable.

<Surfactant>
The curable composition preferably contains a surfactant. The surfactant contributes to the improvement of the coatability of the curable composition.

When the curable composition contains a surfactant, the content of the surfactant is preferably 0.001% to 2.0% by mass with respect to the total solid content of the curable composition.
The surfactant may be used alone or in combination of two or more. When two or more surfactants are used in combination, the total amount is preferably within the above range.

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

  For example, when the curable composition contains a fluorine-based surfactant, liquid properties (in particular, fluidity) of the curable composition are further improved. That is, in the case of forming a film using a curable composition containing a fluorine-based surfactant, the wettability to the surface to be coated is improved by reducing the interfacial tension between the surface to be coated and the coating liquid. The coating property on the surface to be coated is improved. For this reason, even in the case where a thin film of about several μm is formed with a small amount of liquid, it is effective in that film formation with uniform thickness with small thickness unevenness can be more suitably performed.

  3-40 mass% is suitable for the fluorine content rate in a fluorine-type surfactant, 5-30 mass% is more preferable, and 7-25 mass% is still more preferable. The fluorine-based surfactant having a fluorine content in this range is effective in terms of the uniformity of the thickness of the coating film and / or the liquid saving property, and the solubility in the curable composition is also good. .

Examples of fluorine-based surfactants include Megafac F171, F172, F173, F176, F177, F141, F142, F143, F44, R30, F437, F475, F479, and the like. Same F482, same F554, same F780 (above, DIC Corporation), Florard FC430, same FC431, same FC171 (above, Sumitomo 3M Corporation), Surfron S-382, same SC-101, same SC 103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, KH-40 (all manufactured by Asahi Glass Co., Ltd.), PF636, PF656, PF6320, PF6520, PF7002 (manufactured by OMNOVA) and the like can be mentioned.
A block polymer can also be used as a fluorine-type surfactant, and the compound of Unexamined-Japanese-Patent No. 2011-89090 is mentioned as a specific example, for example. The compound (F-1) represented by a following formula is also mentioned as a fluorine-type surfactant. In the compound (F-1), 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 relationship of a + c = 14, b = 17, respectively. The weight average molecular weight of the following compound is, for example, 15,311.

  Specific examples of nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane and their ethoxylates and propoxylates (eg, glycerol propoxylate, glycerine ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene Stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester (Pluronic L10, L31, L61, L62 manufactured by BASF, 10R5, 17R2, 25R2, Tetronics 304, 701, 704, 901, 904, 150R1), Sparse 20000 (Lubrizol Japan Co., Ltd.), and the like. In addition, Pionin D-6112-W manufactured by Takemoto Oil & Fat Co., Ltd., NCW-101, NCW-1001 and NCW-1002 manufactured by Wako Pure Chemical Industries, Ltd. can also be used.

  Specific examples of cationic surfactants include phthalocyanine derivatives (trade name, EFKA-745, manufactured by Morishita Sangyo Co., Ltd.), organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid Co) polymer poly flow No. 75, no. 90, no. 95 (manufactured by Kyoeisha Chemical Co., Ltd.), W001 (Yusho Co., Ltd.), and the like.

  Specific examples of the anionic surfactant include W004, W005, W017 (Yusho Co., Ltd.) and the like.

  As silicone type surfactant, for example, Toray Dow Corning Co., Ltd. product "Tore silicone DC3PA", "Tore silicone SH7PA", "Tore silicone DC11PA", "Tore silicone SH21PA", "Tore silicone SH28PA", "Tore silicone SH21PA" Silicone SH29PA, Toray Silicone SH30PA, Toray Silicone SH8400, Momentive Performance Materials, Inc. "TSF-4440", "TSF-4300", "TSF-4445", "TSF-4460", "TSF “4452”, “KP341”, “KF6001”, “KF6002” manufactured by Shin-Etsu Silicone Co., Ltd., “BYK307”, “BYK323”, “BYK330” manufactured by BIC Chemie, and the like.

<Silane coupling agent>
The silane coupling agent is a compound having a hydrolyzable group and other functional groups in the molecule. In addition, hydrolysable groups, such as an alkoxy group, are couple | bonded with the silicon atom.
The hydrolyzable group is a substituent which is directly bonded to a silicon atom and can form a siloxane bond by hydrolysis reaction and / or condensation reaction. As a hydrolysable group, a halogen atom, an alkoxy group, an acyloxy group, and an alkenyloxy group are mentioned, for example. When the hydrolyzable group contains a carbon atom, the carbon number thereof is preferably 6 or less, more preferably 4 or less. In particular, an alkoxy group having 4 or less carbon atoms or an alkenyloxy group having 4 or less carbon atoms is preferable.
When forming a cured film on a substrate, the silane coupling agent contains a fluorine atom and a silicon atom (but excluding the silicon atom to which a hydrolyzable group is bonded) in order to improve the adhesion between the substrate and the cured film. Preferably, a fluorine atom, a silicon atom (excluding a silicon atom to which a hydrolyzable group is bonded), an alkylene group substituted with a silicon atom, a linear alkyl group having 8 or more carbon atoms, and 3 carbon atoms It is desirable not to include the above branched chain alkyl group.

The silane coupling agent preferably contains a group represented by the following formula (Z). * Represents a bonding position.
Formula (Z) *-Si- (R _Z1 ) ₃
In formula (Z), R _Z1 represents a hydrolyzable group, and the definition is as described above.

The silane coupling agent preferably contains one or more curable functional groups selected from the group consisting of (meth) acryloyloxy groups, epoxy groups, and oxetanyl groups. The curable functional group may be directly bonded to the silicon atom, or may be bonded to the silicon atom via a linking group.
In addition, as a suitable aspect of the curable functional group contained in the said silane coupling agent, a radically polymerizable group is also mentioned.

  The molecular weight of the silane coupling agent is not particularly limited, and is often 100 to 1,000, preferably 270 or more, and more preferably 270 to 1,000, from the viewpoint of handleability.

One of the preferable embodiments of the silane coupling agent includes a silane coupling agent X represented by the formula (W).
Formula (W) R _Z2- Lz-Si- (R _Z1 ) ₃
R _z1 represents a hydrolyzable group, and the definition is as described above.
R _z2 represents a curable functional group, the definition is as described above, and the preferred range is also as described above.
Lz represents a single bond or a divalent linking group. If Lz represents a divalent linking group, the divalent As the linking group, an alkylene group optionally substituted with a halogen atom, an arylene group optionally halogen atoms substituted, -NR 12 ^{-, -} CONR _{^{12 -, - CO -, -}} CO 2 -, SO 2 NR 12 -, - O -, - S -, - SO 2 -, or combinations thereof. Among them, at least one selected from the group consisting of an alkylene group which may be substituted by a C 2-10 halogen atom and an arylene group which may be substituted by a C 6-12 halogen atom, or these groups and ^{-NR 12 -, - CONR 12 -} , - CO -, - CO 2 -, SO 2 NR 12 -, - O -, - S-, and SO ₂ -, at least selected from the group consisting of group is preferred, which consist of a combination of one group, an alkylene group optionally substituted with a halogen atom having 2 to 10 carbon _{atoms, -CO 2 -, - O -} , - CO -, - CONR 12 -, or And the group consisting of the combination of these groups is more preferable. Here, the above R ¹² represents a hydrogen atom or a methyl group.

  As the silane coupling agent X, N-β-aminoethyl-γ-aminopropyl-methyldimethoxysilane (Shin-Etsu Chemical Co., Ltd. trade name: KBM-602), N-β-aminoethyl-γ-aminopropyl-tri Methoxysilane (Shin-Etsu Chemical Co., Ltd., trade name KBM-603), N-β-aminoethyl-γ-aminopropyl-triethoxysilane (Shin-Etsu Chemical Co., Ltd. trade name KBE-602), γ-aminopropyl- Trimethoxysilane (Shin-Etsu Chemical Co., Ltd., trade name KBM-903), γ-aminopropyl-triethoxysilane (Shin-Etsu Chemical Co., Ltd. trade name, KBE-903), 3-methacryloxypropyl trimethoxysilane (Shin-Etsu Chemical Manufactured by Kogyo Co., Ltd., trade name KBM-503), and glycidoxyoctyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd.) Trade name KBM-4803) and the like.

Another preferred embodiment of the silane coupling agent is a silane coupling agent Y having at least a silicon atom, a nitrogen atom and a curable functional group in the molecule and containing a hydrolyzable group bonded to the silicon atom. Can be mentioned.
The silane coupling agent Y may have at least one silicon atom in the molecule, and the silicon atom can be bonded to the following atoms and substituents. They may be the same atoms, substituents or different. The atom which can be bonded, the substituent, is a hydrogen atom, a halogen atom, a hydroxy group, an alkyl group having 1 to 20 carbon atoms, an alkenyl group, an alkynyl group, an aryl group, an alkyl group and / or an amino group which can be substituted with an aryl group A silyl group, a C1-C20 alkoxy group, an aryloxy group etc. are mentioned. These substituents may further be substituted with silyl, alkenyl, alkynyl, aryl, alkoxy, aryloxy, thioalkoxy, alkyl and / or aryl, amino, halogen, sulfonamide, and the like. It may be substituted with an alkoxycarbonyl group, an amido group, a urea group, an ammonium group, an alkyl ammonium group, a carboxylic acid group, or a salt thereof, a sulfo group, a salt thereof or the like.
In addition, at least one hydrolyzable group is bonded to the silicon atom. The definition of the hydrolyzable group is as described above.
The silane coupling agent Y may contain a group represented by Formula (Z).

The silane coupling agent Y preferably has at least one nitrogen atom in the molecule, and the nitrogen atom is preferably present in the form of a secondary amino group or a tertiary amino group, that is, the nitrogen atom is a substituent It is preferred to contain at least one organic group. In addition, as a structure of an amino group, you may exist in a molecule | numerator in the form of the partial structure of a nitrogen-containing heterocyclic ring, and you may exist as substituted amino groups, such as aniline.
Here, as the organic group, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a combination thereof, and the like can be mentioned. These may further have a substituent and examples of the substituent that can be introduced include silyl group, alkenyl group, alkynyl group, aryl group, alkoxy group, aryloxy group, thioalkoxy group, amino group, halogen atom, sulfonamide Groups, alkoxycarbonyl groups, carbonyloxy groups, amido groups, urea groups, alkyleneoxy groups ammonium groups, alkyl ammonium groups, carboxylic acid groups, or salts thereof, sulfo groups and the like.
The nitrogen atom is preferably bonded to the curable functional group via any organic linking group. Preferred examples of the organic linking group include the nitrogen atom described above and substituents which can be introduced into the organic group bonded thereto.

The definition of the curable functional group contained in the silane coupling agent Y is as described above, and the preferable range is also as described above.
The silane coupling agent Y may have at least one or more curable functional groups in one molecule, but may have two or more curable functional groups. From the viewpoint of sensitivity and stability, the curable functional group is preferably contained in the molecule in an amount of 2 to 20, more preferably 4 to 15 and still more preferably 6 to 10.

  Although the molecular weight in particular of the silane coupling agent X and the silane coupling agent Y is not restrict | limited, The above-mentioned range (270 or more is preferable) is mentioned.

  The content of the silane coupling agent in the curable composition is preferably 0.1 to 10% by mass, more preferably 0.5 to 8% by mass, with respect to the total solid content in the curable composition. The content is more preferably from 0 to 6% by mass.

  The curable composition may contain one type of silane coupling agent alone, or may contain two or more types. When a curable composition contains 2 or more types of silane coupling agents, the sum total should just be in the said range.

<UV absorber>
The curable composition may contain a UV absorber. Thereby, the shape of the pattern of a cured film can be made more excellent (fine).
As the UV absorber, UV absorbers of salicylate type, benzophenone type, benzotriazole type, substituted acrylonitrile type and triazine type can be used. As specific examples of these, the compounds of paragraphs 0137 to 0142 of JP 2012-068418 A (corresponding to paragraphs 0251 to 0254 of corresponding US 2012/0068292) can be used, and the contents thereof can be incorporated and incorporated herein .
In addition, diethylamino-phenylsulfonyl ultraviolet absorber (manufactured by Daito Kagaku Co., Ltd., trade name: UV-503) and the like are preferably used.
As an ultraviolet absorber, the compound illustrated by Unexamined-Japanese-Patent No.2012-32556, Paragraph 0134-0148 is mentioned.
0.001-15 mass% is preferable with respect to the total solid of a curable composition, as for content of a ultraviolet absorber, 0.01-10 mass% is more preferable, 0.1-5 mass% is further more preferable preferable.

<Thermal polymerization initiator>
The curable composition may contain a thermal polymerization initiator.
The one-minute half-life temperature of the thermal polymerization initiator is preferably 120 to 300 ° C., more preferably 150 to 250 ° C., and still more preferably 150 to 230 ° C., from the viewpoint of the stability and curability of the photosensitive resin composition. 170 to 200 ° C. is particularly preferred. When the one-minute half-life temperature of the thermal polymerization initiator is equal to or higher than the above lower limit, the coating does not harden too much at the time of drying, and the developability is good. When the one-minute half-life temperature of the thermal polymerization initiator is equal to or less than the above lower limit value, the curability is good.
The molecular weight of the thermal polymerization initiator is preferably 100 or more, more preferably 150 or more, still more preferably 200 or more, and particularly preferably 250 or more from the viewpoint of volatility. For example, 1,000 or less is preferable, and 500 or less is more preferable. When the molecular weight of the thermal polymerization initiator is at least the above lower limit value, volatilization of the thermal polymerization initiator at the time of drying of the coating film can be effectively suppressed, and the curability is good.

  The thermal polymerization initiator may be a compound that generates radicals by heat (hereinafter, simply referred to as a thermal radical generator) or a compound that generates an acid by heat (hereinafter, simply referred to as a thermal acid generator). Can. In particular, heat radical generators are preferred. Since the thermal radical generator can promote radical polymerization of the ethylenically unsaturated group, the polymerization reaction of the crosslinking agent is more effective when a compound containing a group having an ethylenically unsaturated bond is used as the crosslinking agent. And can be cured in a shorter time. The reaction in which the polymerization reaction is initiated and promoted by the thermal acid generator is ring-opening polymerization of epoxy. Since ring-opening polymerization of epoxy is slower in polymerization rate than radical polymerization, curing may not be sufficiently promoted.

(Heat radical generator)
A well-known heat radical generating agent can be used as a heat radical generating agent. The thermal radical generator is a compound that generates radicals by the energy of heat and initiates or accelerates the polymerization reaction of the crosslinking agent.
As a thermal radical generator, aromatic ketones, onium salt compounds, organic peroxides, thio compounds, hexaarylbiimidazole compounds, ketoxime ester compounds, borate compounds, azinium compounds, metallocene compounds, active ester compounds, carbon halogen Compounds having a bond, azo compounds and the like can be mentioned. Among them, azo compounds are more preferable.

[Method of producing a curable composition]
The method of producing the curable composition comprises the following mixing and dispersing steps. It is preferable to include a standing step and / or a filtration step. Below, the suitable aspect is explained in full detail about each process.

[Mixing and dispersion process]
The mixing and dispersing step is a step of mixing the above components by a known mixing method (for example, a stirrer, a homogenizer, a high pressure emulsifying device, a wet crusher, and a wet disperser) to obtain a curable composition. In the mixing and dispersing step, each component constituting the curable composition may be blended at one time, or may be sequentially blended after each component is dissolved or dispersed in an organic solvent. There are no particular restrictions on the order of introduction and the working conditions at the time of blending. The mixing and dispersing step may comprise the step of making a dispersion.

(Step of producing a dispersion)
The step of preparing a dispersion is a step of mixing a colorant, a dispersant, and a solvent, and dispersing the colorant according to the method described above to prepare a dispersion. Other components can be mixed with the prepared dispersion to produce a curable composition.
The mechanical force used to disperse the pigment in the process of preparing the dispersion includes compression, squeezing, impact, shearing and cavitation. Specific examples of these processes include bead mills, sand mills, roll mills, high speed impellers, sand grinders, flow jet mixers, high pressure wet atomization and ultrasonic dispersion. In addition, "Distribution Technology, issued by Information Technology Co., Ltd., July 15, 2005" and "Dispersion technology centering on suspension (solid / liquid dispersion system) and actual practical application materials of industrial application, Management Development Center Publication Partly, Oct. 10, 1978 "can be preferably used.
In the step of preparing the dispersion, the pigment may be finely divided by a salt milling step. As materials, equipment, processing conditions, and the like used in the salt milling step, those described in, for example, JP-A-2015-194521 and JP-A-2012- 046629 can be used.
The method for producing a curable composition preferably includes the step of obtaining the colorant by a thermal plasma method. The step of obtaining the colorant is carried out before mixing the above-mentioned components. The aspect of the specific manufacturing process of the coloring agent by a thermal plasma method is as above-mentioned.

<Standing process>
The colorant may undergo the following standing step before being subjected to the mixing and dispersing step or the step of preparing a dispersion.
In the stationary step, the coloring agent obtained by the thermal plasma method is not exposed to the atmosphere after the production thereof, and within a closed container in which the oxygen concentration is controlled, for a predetermined time (preferably 12 to 72 hours, more preferably It is a process of leaving still for 12 to 48 hours, more preferably 12 to 24 hours. At this time, it is more preferable that the water content in the closed container is controlled.

At this time, oxygen _{(O 2)} concentration and the water content in the sealed container is preferably not more than respectively 100 ppm, more preferably 10ppm or less, and more preferably 1ppm or less.
The oxygen (O ₂ ) concentration and the water content in the closed container can be determined by adjusting the oxygen concentration and the amount of water in the inert gas supplied into the closed container. As the inert gas, nitrogen gas and argon gas are preferably used, and among these, it is more preferable to use nitrogen gas.
After the above-mentioned settling step, the surface of the colorant and the grain boundaries become stable. Thereby, generation | occurrence | production of the pinhole of the cured film obtained by hardening | curing a curable composition can be suppressed.
In addition, it is possible to replace the above-mentioned stationary process by the process H demonstrated in the manufacturing method of a coloring agent, and it is preferable to replace by the process H in that the curable composition has the more excellent effect of this invention. .

<Filtration process>
A filtration process is a process of filtering the curable composition manufactured by the above-mentioned mixing and dispersion process with a filter. In the filtration step, foreign matter can be removed from the curable composition and / or defects can be reduced.
Any filter may be used without particular limitation as long as it is conventionally used for filtration applications and the like. For example, a filter made of a fluorine resin such as PTFE (polytetrafluoroethylene), a polyamide resin such as nylon, a polyolefin resin such as polyethylene or polypropylene (PP) (containing high density and ultrahigh molecular weight), etc. . Among these materials, polypropylene (containing high density polypropylene) and nylon are preferable.
The pore size of the filter is suitably about 0.1 to 7.0 μm, preferably about 0.2 to 2.5 μm, more preferably about 0.2 to 1.5 μm, about 0.3 to 0.7 μm. More preferable. Within this range, it is possible to reliably remove fine foreign matters such as impurities and aggregates contained in the pigment while suppressing filter filtration clogging.
When using filters, different filters may be combined. At this time, the filtering with the first filter may be performed only once or may be performed twice or more. When different filters are combined to perform filtering twice or more, it is preferable that the second and subsequent pore sizes be the same or larger than the pore size of the first filtering. The first filters of different pore sizes may be combined within the above range. The pore size here can refer to the nominal value of the filter manufacturer. As a commercially available filter, for example, it is possible to select from various filters provided by Nippon Pall Ltd., Advantech Toyo Ltd., Nippon Entegris Ltd. (old Japan Microlith Ltd.) or Kitz Micro Filter Inc. .
The second filter can be made of the same material as the first filter described above. The diameter of the second filter is suitably about 0.2 to 10.0 μm, preferably about 0.2 to 7.0 μm, and more preferably about 0.3 to 6.0 μm.

[Cured film (light shielding film)]
A cured film is obtained by curing the above-mentioned curable composition. The cured film contains a colorant. The cured film is preferably used as a light shielding film, and more specifically, is preferably used to shield the peripheral portion of the light receiving unit of the image sensor.
Hereinafter, the case where a cured film is used as a light shielding film of the peripheral part of the light receiving part of an image sensor is demonstrated as an example.

The thickness of the light shielding film is not particularly limited, but the thickness after drying is preferably 0.2 μm to 50 μm, more preferably 0.3 μm to 10 μm from the viewpoint that the light shielding film has more excellent effects of the present invention. Is more preferable, and 0.3 μm or more and 5 μm or less is more preferable. Since the curable composition has a high optical density per unit volume (because of the high light-shielding property), it is possible to reduce the film thickness more than a curable composition using a conventional black pigment.
The size of the light shielding film (length of one side of the light shielding film provided around the sensor light receiving portion) is preferably 0.001 mm or more and 10 mm or less in that the light shielding film has more excellent effects of the present invention. 05 mm or more and 7 mm or less are more preferable, and 0.1 mm or more and 3.5 mm or less are more preferable.

[Method of producing a cured film]
Next, a method of manufacturing a cured film (light shielding film) will be described.
Hereinafter, the manufacturing method will be described in detail for each step.

The method for producing a cured film includes the following curable composition layer forming step and exposure step. The method for producing a cured film preferably further includes a development step.
Curable Composition Layer Forming Step: A step of forming a curable composition layer on a support.
Exposure step: a step of exposing the curable composition layer.
Development step: A step of developing a curable composition layer after exposure to form a patterned cured film (light shielding film).

Specifically, the curable composition is applied onto a substrate directly or through another layer to form a curable composition layer (curable composition layer forming step), and a predetermined mask pattern is formed. The cured film can be manufactured by exposing through light and curing only the coated film portion irradiated with light (exposure step) and developing with a developer (development step).
Hereinafter, each said process is demonstrated.

<Step of Forming Curable Composition Layer>
The curable composition layer forming step is a step of forming a curable composition layer on a support (hereinafter also referred to as a "substrate"). Among them, it is preferable to include a coating step of coating the curable composition on a support to form a curable composition layer, and directly coating the curable composition on the support to obtain a support on the support. It is more preferable to include the application process which forms a curable composition layer.
As the substrate, for example, non-alkali glass used in liquid crystal display devices, soda glass, Pyrex (registered trademark) glass, quartz glass, those obtained by attaching a transparent conductive film thereto, photoelectrics used in solid-state imaging devices, etc. A conversion element substrate (for example, a silicon substrate etc.), a CCD (Charge Coupled Device) substrate, a CMOS (Complementary Metal-Oxide Semiconductor) substrate, etc. may be mentioned.
The support may be provided with a subbing layer for the purpose of improving the adhesion with the upper layer, preventing the diffusion of substances or flattening the surface of the substrate (hereinafter, also referred to as a "subbing support").

  As a coating method of the curable composition on the substrate, various coating methods such as slit coating, inkjet method, spin coating, cast coating, roll coating, and screen printing can be applied.

  When producing a color filter containing a black matrix for a solid-state imaging device, the coating thickness of the curable composition is preferably 0.35 μm or more and 1.5 μm or less from the viewpoint of resolution, and 0. 40 micrometers or more and 1.0 micrometers or less are more preferable.

  The curable composition applied on the substrate is usually dried at 70 ° C. or more and 110 ° C. or less for 2 minutes or more and 4 minutes or less. Thereby, a curable composition layer can be formed.

<Exposure process>
The exposure step is a step of exposing the curable composition layer (coated film) formed in the curable composition layer forming step through a mask and curing only the coated film portion irradiated with light.
The exposure is preferably performed by irradiation with an actinic ray or radiation, in particular, ultraviolet rays such as g-ray, h-ray and i-ray are preferable, and a high pressure mercury lamp is more preferable. The amount of exposure is not particularly limited, but can be appropriately selected depending on the type of pigment used and / or the mask pattern shape. For example, for a coating film formed by the curable composition containing a black pigment described in Example, the lower limit of the amount of exposure is preferably 50 mJ / cm ² or more, 80 mJ / cm ² or more is more preferable. Upper limit of the amount of exposure is preferably 1,500 mJ / cm ² or less, less than 500 mJ / cm ² is more preferable. The manufacturing method of a cured film (light shielding film) has more excellent stability and productivity as an exposure amount is 80 mJ / cm < ² > or more and less than 500 mJ / cm < ² >.
Further, with respect to the coating film formed by the curable composition containing a chromatic pigment as described in Example, the lower limit of the amount of exposure is preferably 50 mJ / cm ² or more, 80 mJ / cm ² or more is more preferable. Upper limit of the amount of exposure is preferably 1,500 mJ / cm ² or less, more preferably less than 500 mJ / cm ^2, still more preferably less than 400 mJ / cm ^2, less than 300 mJ / cm ² is particularly preferred. If the exposure dose is less than 80 to 300 mJ / cm ² , the method for producing a cured film has more excellent stability and productivity.
In light shielding film formation for solid-state imaging devices, exposure with an i-line stepper is preferable from the viewpoint of improving resolution.

<Development process>
The developing step is a step of developing the exposed curable composition layer. A patterned cured film can be obtained by the development step.
It is preferable that the manufacturing method of the said cured film contains the image development process and the following washing | cleaning process. In the development step, an alkali development treatment (development step) is performed to elute a portion which is not irradiated with light in the exposure step into an aqueous alkali solution. As a result, only the photocured portion (the coated film portion irradiated with light) remains.
As a developing solution, when producing the light-shielding color filter containing the black matrix for solid-state image sensors, the organic alkali developing solution which does not produce a damage in the circuit of a base etc. is preferable. The development temperature is preferably 20 to 30 ° C., and the development time is preferably 20 to 90 seconds.

  Examples of the alkaline aqueous solution include inorganic developers and organic developers. As the inorganic developer, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, sodium borate or sodium metaborate, the concentration of which is 0.001 to 10% by mass, preferably 0.01 to 1 The alkaline aqueous solution melt | dissolved so that it may become mass% is mentioned. As an organic developer, ammonia water, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine or 1,8-diazabicyclo- [5.4.0]- The alkaline aqueous solution which melt | dissolved alkaline compounds, such as 7- undecene, so that a density | concentration may be 0.001-10 mass%, preferably 0.01-1 mass% is mentioned. An appropriate amount of a water-soluble organic solvent such as methanol and ethanol and / or a surfactant may be added to the alkaline aqueous solution. As the developing method, for example, a paddle developing method and a shower developing method can be used.

<Washing process>
The washing step is a step of washing (rinsing) the developed curable composition layer with pure water or the like. The washing method is not particularly limited, and known washing methods can be used.

  The method for producing the cured film may include a post-baking step of heating the cured film and / or a curing step of exposing the entire surface of the cured film after the developing step.

A color filter containing a cured film (black matrix) is suitable for a solid-state imaging device such as a CCD image sensor and / or a CMOS image sensor. In particular, the present invention is suitable for a high resolution CCD image sensor and / or a CMOS image sensor or the like having one million pixels or more. That is, the color filter containing the said cured film is suitable for a solid-state image sensor. The color filter may have a structure in which a cured film forming each color pixel is embedded in a space partitioned in a lattice shape, for example, by partition walls.
The cured film (black matrix) is disposed, for example, between a light receiving portion of each pixel constituting a CCD image sensor and / or a CMOS image sensor and the like, and a microlens for collecting light.

[Solid-state imaging device]
The solid-state imaging device contains the cured film (black matrix). The solid-state imaging device preferably contains a black matrix, and further, if necessary, a color filter containing a patterned film composed of pixels of other colors (three or four colors).
The solid-state imaging device is not particularly limited as long as it contains the black matrix and functions as a solid-state imaging device. For example, a light receiving area of a solid-state imaging device (CCD image sensor, CMOS image sensor, etc.) is formed on a substrate. The solid-state image sensor which contains the light receiving element which consists of several photodiode and polysilicon etc. and contains the said black matrix in the surface on the opposite side of the light receiving element formation surface of a board | substrate is mentioned.
The color filter may have a structure in which a cured film forming each color pixel is embedded in a space partitioned in, for example, a grid shape by partition walls. The partition walls in this case preferably have a low refractive index for each color pixel. As an example of the solid-state image sensor containing such a structure, the solid-state image sensor as described in Unexamined-Japanese-Patent No. 2012-227478 and Unexamined-Japanese-Patent No. 2014-179577 is mentioned.

[Image display device]
The cured film can be suitably used for an image display device (for example, a liquid crystal display device, an organic electroluminescent display device, etc.).

  For the definition of the image display device and the details of each image display device, for example, “Electronic display device (authored by Akio Sasaki, published by Industry Research Association, 1990)”, and “Display device (authored by Ibuki, Chapter Book) Co., Ltd.) issued in The liquid crystal display device is described, for example, in “Next-generation liquid crystal display technology (edited by Tatsuo Uchida, published by Industry Research Association, 1994)”. The cured film is suitable for, for example, a liquid crystal display device of the type described in the above-mentioned "next-generation liquid crystal display technology".

  As one embodiment of the liquid crystal display device containing the cured film, for example, a color filter, a liquid crystal layer, and a liquid crystal driving means (a simple matrix driving method, an active matrix driving method) between at least one pair of light transmitting substrates A liquid crystal display device containing at least a system). The liquid crystal display device contains a plurality of pixel groups, and each pixel constituting the pixel group contains a color filter separated from each other by the cured film (black matrix).

  As another embodiment of the liquid crystal display device, at least one of the pair of light transmitting substrates includes at least a color filter, a liquid crystal layer, and a liquid crystal driving unit, and the liquid crystal driving unit is an active element (for example, (Thin Film Transistor)), and a color filter containing the above-mentioned cured film (black matrix) between each active element.

  The color filter containing the cured film is suitable for a liquid crystal display device of a color TFT (Thin Film Transistor) system. The color TFT liquid crystal display device is described, for example, in “Color TFT liquid crystal display (Kyoritsu Publishing Co., Ltd., published in 1996)”. Furthermore, the color filter is a liquid crystal display device with a wide viewing angle, such as a horizontal electric field drive system such as IPS (In Plane Switching); a pixel division system such as MVA (Multi-domain Vertical Alignment); STN (Super-Twist) Nematic), TN (Twisted Nematic), VA (Vertical Alignment), OCS (on-chip spacer), FFS (fringe field switching), R-OCB (Reflective Optically Compensated Bend), and the like.

  The color filter is suitable for a bright and high-definition liquid crystal display device of a color-filter on array (COA) system. In the COA type liquid crystal display device, the required characteristics for the color filter may be required for the interlayer insulating film, that is, low dielectric constant and stripping solution resistance in addition to the normal required characteristics. The COA type liquid crystal display device containing the color filter has a better resolution or a better durability. In addition, in order to satisfy the required characteristics of low dielectric constant, a resin film may be further included on the color filter layer.

  These image display methods are described, for example, on page 43 of "EL, PDP, LCD display-latest trends in technology and market-(Toray Research Center, Research Division, 2001)". In the above, EL stands for Electroluminescence, PDP stands for Plasma Display Panel, and LCD stands for liquid crystal display.

The liquid crystal display device is composed of various members such as an electrode substrate, a polarizing film, a retardation film, a backlight, a spacer, and a viewing angle ensuring film, in addition to the color filter. The color filter can be applied to a liquid crystal display device configured of these known members. For these members, for example, “'94 Liquid crystal display peripheral materials and chemicals market (Kentaro Shima, Inc. CMSC Co., Ltd., 1994 issue),” and “2003 liquid crystal related market current status and future prospects (second volume) (Omoteyoshi Yoshi) (Fuji Chimera Research Institute, Inc., 2003)).
For backlight, see SID meeting Digest 1380 (2005) (A. Konno et. Al), and / or monthly display December 2005, pages 18 to 24 (Yasuhiro Shima), pages 25 to 30 (Takaaki Yagi) It is described in etc.

  The cured film is a portable device such as a personal computer, a tablet, a mobile phone, a smartphone and a digital camera; an office automation (OA) device such as a printer complex machine and a scanner; a surveillance camera, a barcode reader, and an automatic teller machine ATM: industrial equipment such as automated teller machine), high-speed camera and personal identification using face image authentication; automotive camera equipment; medical camera equipment such as endoscopes, capsule endoscopes and catheters; Optical filters used for biosensors, cameras for military reconnaissance, cameras for stereographic maps, weather and ocean observation cameras, land resource exploration cameras, and space instruments such as exploration cameras for astronomy and deep space targets in space, etc. Module shading member and shading layer, It is suitable for anti-reflection member and the antireflection layer on.

The said cured film can be used also for uses, such as micro LED (Light Emitting Diode) and micro OLED (Organic Light Emitting Diode). The said cured film is suitable for the member which provides a light shielding function or an antireflection function other than the optical filter and optical film which are used for micro LED and micro OLED.
Examples of micro LEDs and micro OLEDs include those described in JP-A-2015-500562 and JP-A-2014-533890.

The said cured film is suitable as an optical and optical film used for a quantum dot display. Moreover, the said cured film is suitable as a member which provides a light shielding function and a reflection preventing function.
Examples of quantum dot displays are disclosed in U.S. Patent Application Publication No. 2013/0335657, U.S. Patent Application Publication No. 2014/0036536, U.S. Patent Application Publication No. 2014/0036203, and U.S. Patent Application Publication No. 2014/0035960 Those mentioned are mentioned.

  Hereinafter, the present invention will be described in more detail based on examples. The materials, amounts used, proportions, treatment contents, treatment procedures, etc. shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Accordingly, the scope of the present invention is not limitedly interpreted by the examples shown below.

[Synthesis of Multifunctional Thiol Compound S-15]
The multifunctional thiol compound S-15 represented by the following formula was synthesized by the following method.

In the formula, "Et" represents an ethyl group _(-CH 2 CH _3), and so on.

In a nitrogen atmosphere, pentaerythritol tetra (3-mercaptopropionate) (manufactured by TCI) (2.00 g) and acrylic acid (0.295 g) were dissolved in tetrahydrofuran (THF) (10.0 g) (The obtained solution is hereinafter referred to as "reaction solution"). Next, the internal temperature of the reaction solution was cooled to 5 ° C. or less. Triethylamine (0.450 g) was added to the reaction solution after cooling. Thereafter, the temperature of the reaction solution was raised to 50.degree. After the temperature rise, the reaction solution was stirred for 3 hours. Ethyl acetate (50 g) and 1N hydrochloric acid (50 g) were added to the reaction solution after stirring. Thereafter, the reaction solution was separated into an aqueous phase and an organic phase. Subsequently, the organic phase is washed with water (50 g), sodium sulfate is added to the obtained organic phase, the solid is filtered off from the organic phase, and the obtained filtrate is concentrated under reduced pressure to obtain S- 15 (2.01 g) (yield 87.6%) were obtained. The structure of S-15 obtained was identified by ¹ H-NMR (nuclear magnetic resonance). The identification results are shown below.

( ¹ H-NMR 300 MHz deuterated chloroform): 1.35 (t, 3 H), 2.53 (t, 2 H), 2.66-2.71 (m, 8 H), 2.73-2.80 (m , 10 H), 4.09 (s, 8 H).

[Synthesis of Multifunctional Thiol Compound S-16]
The multifunctional thiol compound S-16 represented by the following formula was synthesized by the following method.

In a nitrogen atmosphere, pentaerythritol tetra (3-mercaptopropionate) (manufactured by TCI) (2.00 g) and 2-hydroxyethyl acrylate (0.475 g) were dissolved in tetrahydrofuran (10.0 g). The reaction mixture was obtained. Next, the internal temperature of the reaction solution was cooled to 5 ° C. or less. Triethylamine (0.450 g) was added to the reaction solution after cooling. Thereafter, the temperature of the reaction solution was raised to 50.degree. After the temperature rise, the reaction solution was stirred for 3 hours. Thereafter, hexane (50 g) was added to the reaction solution, and the supernatant component of the reaction solution after hexane addition was removed. To the reaction solution after removal of the supernatant component, hexane (50 g) was added again, and the supernatant component of the reaction solution after re-addition of hexane was removed. Thereafter, the solvent remaining in the reaction solution was removed by evaporation under reduced pressure to obtain S-16 (2.01 g) (yield 88.8%). The obtained structure of S-16 was identified by ¹ H-NMR. The identification results are shown below.

( ¹ H-NMR 300 MHz deuterated chloroform): 1.35 (t, 3 H), 2.64-2.71 (m, 10 H), 2.73-2.82 (m, 10 H), 3.79-3 .87 (m, 2H), 4.09 (s, 8H), 4.22-4.29 (m, 2H).

[Synthesis of Polyfunctional Thiol Compound S-17]
The multifunctional thiol compound S-17 represented by the following formula was synthesized by the following method.

In the above formulae, “Me” intends a methyl group (—CH ₃ ), and so forth.

In a nitrogen atmosphere, pentaerythritol tetra (3-mercaptopropionate) (manufactured by TCI) (2.00 g) and 2- (dimethylamino) ethyl acrylate (0.586 g) in tetrahydrofuran (10.0 g) The reaction solution was obtained by Next, the internal temperature of the reaction solution was cooled to 5 ° C. or less. Triethylamine (0.450 g) was added to the reaction solution after cooling. Thereafter, the temperature of the reaction solution was raised to 50.degree. After the temperature rise, the reaction solution was stirred for 3 hours. Thereafter, hexane (50 g) was added to the reaction solution, and the supernatant component of the reaction solution after hexane addition was removed. To the reaction solution after removal of the supernatant component, hexane (50 g) was added again, and the supernatant component of the reaction solution after re-addition of hexane was removed. Thereafter, the solvent remaining in the reaction solution was removed by evaporation under reduced pressure to obtain S-17 (2.15 g) (yield 83.1%). The structure of S-17 obtained was identified by ¹ H-NMR. The identification results are shown below.

( ¹ H-NMR 300 MHz deuterated chloroform): 0.62 to 0.711 (m, 2 H), 1.70 to 1.85 (m, 2 H), 1.36 (t, 3 H), 2.57 (t) , 2H), 2.62-2.70 (m, 10H), 2.73-2.85 (m, 10H), 3.79-3.87 (m, 2H), 4.08 (s, 8H) ), 4.19 (t, 2 H).

[Synthesis of Multifunctional Thiol Compound S-26]
The multifunctional thiol compound S-26 represented by the following formula was synthesized by the following method.

In a nitrogen atmosphere, pentaerythritol tetra (3-mercaptopropionate) (manufactured by TCI) (2.00 g) and 3- (trimethoxysilyl) propyl acrylate (1.92 g) in tetrahydrofuran (10.0 g) The reaction solution was obtained by dissolving in. Next, the internal temperature of the reaction solution was cooled to 5 ° C. or less. Triethylamine (0.450 g) was added to the reaction solution after cooling. Thereafter, the temperature of the reaction solution was raised to 50.degree. After the temperature rise, the reaction solution was stirred for 3 hours. Thereafter, hexane (50 g) was added to the reaction solution, and the supernatant component of the reaction solution after hexane addition was removed. To the reaction solution after removal of the supernatant component, hexane (50 g) was added again, and the supernatant component of the reaction solution after re-addition of hexane was removed. Thereafter, the solvent remaining in the reaction solution was removed using evaporation under reduced pressure to obtain S-26 (2.23 g) (yield 75.4%). The structure of S-26 obtained was identified by ¹ H-NMR. The identification results are shown below.

( ¹ H-NMR 300 MHz deuterated chloroform): 1.35 (t, 3 H), 2.59 (t, 2 H), 2.64-2.71 (m, 8 H), 2.73-2.82 (m , 10 H), 3.58 (s, 9 H), 4.02-4.11 (s, 10 H).

[Synthesis of Multifunctional Thiol Compounds S-8, 20, 22, 24, 25, 64 to 66, 69, 71, 73 to 75, 88 to 90, and 112 to 114]
Multifunctional thiol compound S-8, 20, 22, 24, 25, 64 to 66, 69, 71, 73 to 75, 88 to 90, and 112 to 114 by the same method as described above except that the raw materials are appropriately changed. Was synthesized.
The structures of the polyfunctional thiol compounds identified by ¹ H-NMR are as shown in Tables 1-1 to 1-6.

[Preparation of Curable Composition of Examples 1 to 23 and Comparative Examples 2 and 3]
The polyfunctional thiol compound shown in each column of Table 2 and the following components were mixed to prepare curable compositions of Examples 1 to 23 and Comparative Examples 2 and 3.

<Composition>
Organic solvent 1 (cyclohexanone) ... 17.12 parts by mass alkali-soluble resin 1 (benzyl methacrylate / methacrylic acid (47/53 [mass ratio]), 30 mass% propylene glycol monomethyl ether solution, Mw = 11,000) ... 1.23 parts by mass alkali-soluble resin 2 (Acrycure RD-F8 (manufactured by Nippon Shokubai)) 0.23 parts by mass Polymerizable compound (radically polymerizable compound, Shin-Nakamura Chemical Co., Ltd. manufactured by NK Ester A -DPH-12E) ... 1.96 parts by mass Polymerization inhibitor (paramethoxyphenol) ... 0.0007 parts by mass Photopolymerization initiator (IRGACURE OXE 02) ... 0.975 parts by mass Polyfunctional thiol compound ( Polyfunctional thiol compounds listed in Table 2 below ... 0.35 parts by mass Fluorinated surfactant (manufactured by DIC, trade name: Megaf) C. F-475, 1% by mass propylene glycol monomethyl ether acetate solution) 2.50 parts by mass Achromatic coloring agent 1: Dye solution 1 (dye solution prepared by the following method) 24. 57 mass Part chromatic coloring agent 2: Pigment dispersion P1 (CI Pigment Blue 15: 6 dispersion prepared by the following method, solid content concentration 11.8 mass%) ... 51.40 parts by mass

  In addition, in Table 2, T-1 and T-2 show the following polyfunctional thiol compounds (multifunctional thiol compound which does not have an interactive group).

Preparation of Dye Solution 1
Dye solution 1 was prepared by mixing the following components.
Organic solvent (cyclohexanone) ... 21.55 parts by mass Dye (A-1 of the following structure) ... 3.02 parts by mass

Preparation of Pigment Dispersion P1
The pigment dispersion P1 was prepared by the following procedure.
C. I. Pigment Blue 15: 6 (blue pigment, hereinafter, also referred to as "PB 15: 6") 19.4 parts by mass (average primary particle size 55 nm), pigment dispersant DISPERBYK-161 (solid content concentration 30% by mass, BYK manufactured) 2.95 parts by mass, alkali-soluble resin 1 (benzyl methacrylate / methacrylic acid (47/53 [mass ratio]), 30 mass% propylene glycol monomethyl ether solution, Mw = 11,000) in terms of solid content 2.95 A mixed solution consisting of parts by mass (9.93 parts by mass of solution) and 165.3 parts by mass of propylene glycol monomethyl ether was mixed and dispersed by a beads mill (zirconia beads 0.3 mm in diameter) for 3 hours. Thereafter, dispersion treatment was performed at a flow rate of 500 g / min under a pressure of 2000 kg / cm ³ using a high pressure disperser NANO-3000-10 (manufactured by Nippon Bei E.) with a pressure reducing mechanism. This dispersion process is repeated 10 times to obtain a pigment dispersion P1, C.I. I. Pigment Blue 15: 6 dispersion was obtained. It was 24 nm when the average primary particle diameter of the pigment was measured by the dynamic light scattering method (Microtrac Nanotrac UPA-EX150 (made by Nikkiso Co., ltd.)) About the obtained pigment dispersion liquid P1.

[Preparation of Curable Composition of Comparative Example 1]
A curable composition was prepared in the same manner as in Example 1 except that the polyfunctional thiol compound was not added.

[Performance evaluation]
Exposure sensitivity was evaluated by the following method about the curable composition of each Example and a comparative example. Moreover, it evaluated by the following method about the adhesiveness to the glass base material of the pattern formed by the following method on the glass base material using said curable composition. The evaluation results are summarized in Table 2 below.

[Exposure sensitivity]
The curable composition of each example and comparative example is spin-coated on a glass substrate, and then dried to form a coating film (curable composition layer) having a film thickness of 1.0 μm on the glass substrate It formed. Spin coating conditions were 300 rpm for 5 seconds, then 800 rpm for 20 seconds, and drying conditions were 100 ° C. for 80 seconds. Next, the obtained coating film (curable composition layer) was used with a test photomask having a line width of 2.0 μm, and a proximity type exposure machine having an ultra-high pressure mercury lamp (manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.) ) ^by, and exposed at various exposure amounts of ^{10mJ / cm 2 ~2,000mJ / cm 2} , to cure the curable composition layer in a pattern. Next, using a 60% by mass CD-2000 (manufactured by Fujifilm Electronics Materials Co., Ltd.) developer, the cured film after exposure is developed under conditions of 25 ° C. for 60 seconds, and a patterned cured film is formed. I got Thereafter, the obtained patterned cured film was rinsed with running water for 20 seconds and then air-dried.
The exposure sensitivity was evaluated by the minimum exposure amount at which the pattern line width after development of the area irradiated with light in the exposure step is 1 μm or more. The smaller the exposure sensitivity value, the better the exposure sensitivity of the curable composition. The exposure sensitivity is preferably less than 300 mJ / cm ^{2 for} practical use under the above test conditions. The results are summarized in Table 2.

[Adhesiveness]
In the cured film in pattern form prepared in the test of the exposure sensitivity, it was observed by SEM (Scanning Electron Microscope) whether or not a pattern defect occurred, and evaluated based on the following criteria. The results are summarized in Table 2.

-Evaluation criteria-
A: No pattern defect was observed at all.
B: The number of pattern defects was 1 to 3 per 1.0 μm square of pattern.
C: The number of pattern defects was 4 or more and 10 or less per 1.0 μm pattern.
D: The number of pattern defects was 11 or more per 1.0 μm square pattern.
In addition, evaluation "B" or more is a practical range.

From the results shown in Table 2, the curable compositions (curable compositions containing a coloring colorant) of Examples 1 to 23 containing a predetermined polyfunctional thiol compound have excellent exposure sensitivity, and It had excellent adhesion to the support.
On the other hand, in the case of the curable composition of Comparative Example 1 which does not contain a polyfunctional thiol compound, the above-mentioned effect was not obtained. The above-described effects were not obtained with the polyfunctional thiol compounds of Comparative Example 2 and Comparative Example 3 containing a polyfunctional thiol compound having no interactive group.
The curable composition of Examples 2, 10, 18, and 21 in which m of the polyfunctional thiol compound represented by the formula (2) is 3 or more is more excellent than the curable composition of Example 1. Had an exposure sensitivity.
The curable composition of Example 10 has a better adhesion to a support as compared to the curable composition of Example 18 in which m + n is equal and m / n is larger. Was.
The interaction group different from the thiol group is a carboxylic acid group or a salt thereof, a hydroxyl group, an amino group, a pyridinyl group, a phosphoric acid group or a salt thereof, a sulfonic acid group or a salt thereof, or -Si (R ^X ) _p (R The curable compositions of Examples 2 to 6, 8 and 9, which are ^Y ) _3-p , have a cured film obtained on the support compared to Example 7 in which the interactive group is a phenyl group. It had better adhesion.

[Examples 55 and 56]
In the preparation of the curable composition of Example 1, the content of the polyfunctional thiol compound was changed from 0.35 parts by mass to 0.17 parts by mass (Example 55), and 0.70 parts by mass (Example 56). The same evaluation as described above gave the same results as in Example 1.

[Examples 57 and 58]
In preparation of the curable composition of Example 1, the content of the polymerizable compound was changed from 1.96 parts by mass to 1.5 parts by mass (Example 57) and 3.0 parts by mass (Example 58). The same evaluation as described above gave the same results as in Example 1.

Preparation of Curable Compositions of Examples 24 to 54, 59, and Comparative Examples 4 to 6
The multifunctional thiol compound shown in each column of Table 4 and each component were mixed in the composition described in Table 3 to prepare curable compositions of Examples 24 to 54, 59, and Comparative Examples 5 and 6. . A curable composition of Comparative Example 4 was prepared in the same manner as in Example 24 except that the polyfunctional thiol compound was not added.
The final solid content of each curable composition was adjusted with an organic solvent to be 28% by mass. Further, the organic solvent was used in combination such that the mass ratio of each curable composition was PGMEA (propylene glycol monomethyl ether acetate) / butyl acetate / cyclohexanone = 27/18/27.

<Colorant>
Each coloring agent was produced by the following method.

(Titanium nitride containing particles (TiN-1))
First, Ti nanoparticles (TC-200, manufactured by Toho Tech Co., Ltd.) were plasma-treated in Ar gas to form Ti nanoparticles. The Ti nanoparticles after plasma treatment were allowed to stand for 24 hours under the condition of 30 ° C. and an O ₂ concentration of 50 ppm or less under Ar gas atmosphere. Then, _{O 2} concentration 30 ° C. in a state of introducing _{O 2} gas into the Ar atmosphere so that 100 ppm, (pretreatment Ti particles) 24 hours standing was.
Thereafter, the obtained Ti nanoparticles were classified using a Hosokawa Micron TTSP separator under a condition of a yield of 10% to obtain a powder of Ti particles. The primary particle diameter of the obtained powder was 120 nm when the average particle diameter of 100 particles was determined by an arithmetic mean by TEM observation.
Titanium nitride-containing particles TiN-1 were manufactured using an apparatus according to the apparatus for manufacturing black composite particles described in FIG. 1 of WO 2010/147098.
Specifically, in the black composite particle production apparatus, high frequency voltages of about 4 MHz and about 80 kVA are applied to the high frequency oscillation coil of the plasma torch, and argon gas 50 L / min and nitrogen 50 L / min as plasma gas from the plasma gas supply source. A mixed gas of min was supplied to generate an argon-nitrogen thermal plasma flame in a plasma torch. The carrier gas of 10 L / min was supplied from the atomizing gas supply source of the material supply device.
With respect to the Ti particles obtained as described above, Fe powder (JIP270M, manufactured by JFE Steel Corporation) and Si powder (Silicon powder SI006031), the mass ratio of each is Ti / Fe / Si = residue / 0 It mixed so that it became .05 / 0.05. This mixture was supplied into a thermal plasma flame in a plasma torch together with a carrier gas, argon gas, evaporated in the thermal plasma flame and highly dispersed in the gas phase.
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 amount was 1,000 L / min. The pressure in the cyclone was 50 kPa, and the feed rate of each material from the chamber to the cyclone was 10 m / s (average value).
Thus, titanium nitride-containing particles TiN-1 were obtained.

The contents of titanium (Ti) atoms, iron (Fe) atoms and silicon (Si) atoms were measured for the obtained titanium nitride-containing particles TiN-1 by ICP emission spectrometry. For ICP emission spectroscopy, an ICP emission spectrometer "SPS 3000" (trade name) manufactured by Seiko Instruments Inc. was used.
The content of nitrogen atoms was measured using an oxygen / nitrogen analyzer "EMGA-620 W / C" (trade name) manufactured by Horiba, Ltd., and calculated by the inert gas melting-thermal conductivity method. As a result of the above, the mass ratio of each atom contained in titanium nitride-containing particles TiN was Ti / N / Fe / Si = 57/34 / 0.0030 / 0.0020.

The powder sample was packed in a standard sample holder made of aluminum, and the X-ray diffraction of titanium nitride-containing particles TiN-1 was measured by a wide-angle X-ray diffraction method (trade name "RU-200R" manufactured by Rigaku Denki Co., Ltd.). As measurement conditions, the X-ray source is CuKα radiation, the output is 50 kV / 200 mA, the slit system is 1 ° -1 ° -0.15 mm-0.45 mm, the measurement step (2θ) is 0.02 °, and the scan speed is It was 2 ° / min.
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 the (200) plane, the crystallite size constituting the particles was determined using Scheller's equation. As a result, the diffraction angle of the peak was 42.62 °, and the crystallite size was 10 nm. Incidentally, X-rays diffraction peak due to TiO ₂ was observed.

(Titanium nitride containing particles TiN-2)
As Ti particles, instead of “TC-200” manufactured by Tohotech Co., Ltd. “578347” manufactured by Sigma Aldrich Co., and using Fe powder and Si powder, the mass ratio of each is Ti / Fe / Si = residue / Titanium nitride-containing particles TiN-2 were obtained in the same manner as TiN-1 except for mixing to be 0.5 / 1.
The diffraction angle of the peak measured by X-ray diffraction was 42.81 °, and the crystallite size was 12 nm.

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

(Preparation of titanium black A-1)
100 g of titanium oxide MT-150A (trade name, manufactured by Tayca Corporation) having an average particle diameter of 15 nm, BET (Brunauer, Emmett, Teller) silica particles AEROSIL 300 (registered trademark) 300/30 (Evonik) having a specific surface area of 300 m ² / g 25g, and 100 g of Disperbyk 190 (trade name, manufactured by BIC Chemie Co., Ltd.) were weighed, and these were added to 71 g of ion electric exchange water to obtain a mixture. Then, using a KURABO MAZERSTAR KK-400W, the mixture was treated at a revolution speed of 1,360 rpm and a rotation speed of 1,047 rpm for 30 minutes to obtain a uniform aqueous mixture solution. The mixture aqueous solution was filled in a quartz container and heated to 920 ° C. in an oxygen atmosphere using a small rotary kiln (manufactured by Motoyama Co., Ltd.). Thereafter, the inside of the small rotary kiln was replaced with nitrogen, and the nitriding reduction treatment was carried out by flowing ammonia gas at 100 mL / min for 5 hours at the same temperature. After completion, the powder collected was crushed in a mortar to obtain titanium black [a dispersion containing titanium black particles and Si atoms] containing Si atoms and having a specific surface area of 73 m ² / g in powder form (in the following, “titanium It is written as “Black A-1”).

(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 Mitsutsu Chemical Co., Ltd. was prepared as a raw material (hereinafter, also referred to as "metal raw material powder").
Next, the metal raw material powder was plasma treated in Ar gas to form Nb nanoparticles. The conditions of the above-mentioned plasma processing were according to the following plasma processing (1).

・ Plasma treatment (1)
Plasma treatment (1) was performed by the following method. Plasma processing (1) was performed under the following conditions using an apparatus according to the above-described black composite particle manufacturing apparatus.
・ High frequency voltage applied to high frequency oscillation coil: Frequency about 4 MHz, voltage about 80 kVA
Plasma gas: Argon gas (supply amount 100 L / min)
・ Carrier gas: Argon gas (supply amount 10 L / min)
· Chamber atmosphere: argon gas (supply rate 1,000 l / min, chamber flow rate 5 m / sec)
・ Atmosphere inside the cyclone: Argon gas, internal pressure 50 kPa
・ Material supply speed from chamber to cyclone: 10 m / s (average value)

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

  Next, the Nb nanoparticles and Fe nanoparticles obtained above were mixed to obtain a raw material metal powder. The raw material metal powder was plasma-treated in nitrogen gas to obtain niobium nitride-containing particles. The conditions of the said plasma processing followed the following plasma processing (2).

Plasma treatment (2)
Plasma treatment (2) was performed by the following method. In addition, the apparatus used the same thing as plasma processing (1).
・ High frequency voltage applied to high frequency oscillation coil: Frequency about 4 MHz, voltage about 80 kVA
Plasma gas: argon gas and nitrogen gas (supply amount: 50 L / min each)
・ Carrier gas: Nitrogen gas (supply amount 10L / min)
・ Atmosphere in the chamber: Nitrogen gas (Supply amount 1,000 L / min, Chamber flow rate 5 m / sec)
・ Atmosphere inside the cyclone: Nitrogen gas, internal pressure 50 kPa
・ Material supply speed from chamber to cyclone: 10 m / s (average value)

Using nitrogen gas, introduce nitrogen gas at 20 ° C under the condition that the relative humidity is 95% using Ar gas by Nippon Shintech Co., Ltd. manufactured by Nippon Shintech Co., Ltd. using nitrogen gas at 24 ° C. Let stand for a while. Thereafter, the obtained particles were classified using a Hosokawa Micron-made TTSP separator under conditions of a yield of 10% to obtain niobium nitride-containing particles (NbN). In addition, nitrogen gas was supplied to the separator.
The content of iron (Fe) atoms in the obtained niobium nitride-containing particles was measured by ICP emission spectrometry, to be 50 mass ppm.

(Preparation of vanadium nitride-containing particles (VN) containing Fe atoms)
In the preparation of niobium nitride-containing particles containing Fe atoms, Fe atoms are similarly prepared except that metal vanadium powder VHO manufactured by Solar Mining Co., Ltd. is used in place of niobium (powder) <100-325 mesh> manufactured by Mitsukazu Chemical Co., Ltd. Vanadium nitride-containing particles (VN) were produced. The content of iron (Fe) atoms in the obtained vanadium nitride-containing particles was measured by ICP emission spectrometry, and was 50 mass ppm.

<Dispersing agent>
As a dispersant, dispersant A having the following structure was used. The numerical value described in each structural unit is intended to indicate the mass% of each structural unit with respect to the total structural unit.

Dispersant A

<Binder resin>
The following resin A was used as a binder resin. The numerical value described in each structural unit is intended to mean mol% of each structural unit with respect to all structural units. In addition, in the formula of resin A, each symbol represents the following.
BzMA: benzyl methacrylate MMA: methyl methacrylate

・ Resin A

<Polymerizable compound>
Polymerizable compound M1: dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd., trade name "KAYARAD", see the following formula)

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

<Photoinitiator>
OXE-01: Irgacure OXE01 (trade name, manufactured by BASF Japan Ltd., corresponding to an oxime compound)

-OXE-02: Irgacure OXE 02 (trade name, manufactured by BASF Japan Ltd., corresponding to an oxime compound)

PI-3: A photopolymerization initiator having the following structure (corresponding to an oxime compound)

-NCI-831 (trade name, manufactured by ADEKA, corresponding to an oxime compound)

IRG-379: IRGACURE 379 EG (trade name, manufactured by BASF Japan Ltd., not applicable to oxime compound)

<Surfactant>
· F-1: a compound represented by the following formula (weight average molecular weight (Mw) = 15, 311)
However, in the following formulas, the structural units represented by formulas (A) and (B) are 62 mol% and 38 mol%, respectively. In the structural unit represented by the formula (B), a, b and c satisfy the relationship of a + c = 14, b = 17, respectively.

<Organic solvent>
PGMEA: Propylene glycol monomethyl ether acetate Cyclopentanone butyl acetate

Preparation of Colorant Dispersion
First, the colorant, the dispersant and the organic solvent were mixed for 15 minutes with a stirrer (EUROSTAR manufactured by IKA) to obtain a mixed solution of the above components. Next, using the NPM-Pilot manufactured by Shinmaru Enterprises Co., Ltd., the resulting mixture was subjected to dispersion treatment under the following conditions to obtain a colorant dispersion.

<Distribution condition>
· Bead diameter: φ 0.05 mm, (Nikkato zirconia beads, YTZ)
・ Bead packing rate: 65% by volume
・ Mill circumferential speed: 10 m / sec
・ Separator circumferential speed: 13 m / s
・ The amount of mixed liquid to be dispersed: 15 kg
Circulating flow rate (pump supply rate): 90 kg / hour
Processing solution temperature: 19 to 21 ° C.
・ Cooling water: Water ・ Processing time: About 22 hours

[Performance evaluation]
[Exposure sensitivity]
Using each curable composition on a Si substrate whose surface has been treated with SiO _{2, the} number of rotations is adjusted to obtain a cured film having a film thickness of 1.5 μm, and a coating film (curable composition is obtained by spin coating Layer). The formed coating film was dried by heat treatment (prebake) for 2 minutes at 100 ° C. on a hot plate. An i-line stepper (FPA 3000i5 + manufactured by CANON KABUSHIKI KAISHA) is used on the coated film (curable composition layer) coated substrate after the above prebaking, and the above coating film is exposed through a photomask on which a 200 μm long × 20 μm wide line pattern is formed. did. The coated film after exposure was subjected to paddle development for 30 seconds using a coater developer ACT8 manufactured by Tokyo Electron, using tetramethylammonium hydroxide as a developer. After development, a shower rinse process was performed with pure water for 20 seconds. The minimum exposure amount maintained without peeling of the pattern after development was evaluated as the exposure sensitivity. The exposure sensitivity is preferably less than 500 mJ / cm ^{2 for} practical use under the above test conditions. The results are summarized in Table 4.

[Adhesiveness]
In the cured film in pattern form prepared in the test of the exposure sensitivity, it was observed by SEM (Scanning Electron Microscope) whether or not a pattern defect occurred, and evaluated based on the following criteria. The results are summarized in Table 4.

-Evaluation criteria-
A: No pattern defect was observed at all.
B: The number of pattern defects was 1 to 3 per 1.0 μm square of pattern.
C: The number of pattern defects was 4 or more and 10 or less per 1.0 μm pattern.
D: The number of pattern defects was 11 or more per 1.0 μm square pattern.
In addition, evaluation "B" or more is a practical range.

[Pattern shape]
The patterned cured film produced in the evaluation of the exposure sensitivity was post-baked (temperature: 220 ° C., time: 300 seconds). The pattern shape of the cured film after post-baking was measured by a length measurement SEM (Scanning Electron Microscope). Specifically, the film thickness at the edge of the line pattern and the film thickness at the center were measured, and the ratio (film thickness at the edge of the pattern / film thickness at the center) was calculated and evaluated according to the following criteria. In addition, evaluation "2 or more" is a practical range.
7: The ratio is greater than 0.98 and less than 1.00, and no difference in the film thickness between the central portion and the end portion of the pattern is observed in observation by SEM.
6: The ratio is more than 0.96 and not more than 0.98, and a slight difference is observed between the film thickness at the central portion and the edge portion of the pattern.
5: The ratio is greater than 0.94 and less than or equal to 0.96, and there is a difference between the film thickness at the center and the edge of the pattern.
4: A ratio is greater than 0.92 and less than or equal to 0.94, the film thickness at the end is thin and slightly distorted, but there is no problem in practical use.
3: The ratio is greater than 0.90 and less than or equal to 0.92, the film thickness at the end is thin and distorted, but there is no problem in practical use.
2: The ratio is greater than 0.80 and less than 0.90, and the film thickness at the end is thin, but a level at which practical use is possible.
1: The ratio is 0.80 or less, and the film thickness at the end is thin and unacceptable.

[Developability]
In the pattern-like cured film prepared in the above evaluation of exposure sensitivity, when exposed, the presence or absence of a residue in an area (unexposed area) shielded by a photomask and not irradiated with light is a SEM (magnification: 20, The development was evaluated by observation at a magnification of 000). Evaluation criteria are as follows, and the results are summarized in Table 4.

-Evaluation criteria-
A: In the unexposed area, no residue was observed B: In the unexposed area of 1.0 μm, 1 or more and 3 or less residues were observed.
C: 4 or more and 10 or less residues were observed in the unexposed area 1.0 μm square D: 11 or more residues were observed in the unexposed area 1.0 μm square
Practically, "C" or more is preferable, and "A" and "B" are evaluated as having excellent performance.

From the results shown in Table 4, the curable compositions (curable compositions containing a black pigment) of Examples 24 to 54 and 59 containing a predetermined polyfunctional thiol compound have excellent exposure sensitivity. And had excellent adhesion to the support.
On the other hand, the curable composition of the comparative example 4 which does not contain a polyfunctional thiol compound did not have the said effect. The polyfunctional thiol compound of Comparative Example 5 and Comparative Example 6 containing the polyfunctional thiol compound having no interactive group did not have the above effect.
The curable compositions of Examples 25 to 54 and 59 in which m of the polyfunctional thiol compound represented by the formula (2) is 3 or more are more comparable to the curable composition of Example 24. It had excellent exposure sensitivity.
The curable composition wherein the interaction group different from the thiol group is a hydroxy group (Example 26), an amino group (Example 27), or a pyridinyl group (Example 31) has an interaction different from the thiol group It had more excellent developability as compared with the curable composition in which the group is a phenyl group (Example 30) or a Si group (Example 32).
A curable composition wherein the interaction group different from the thiol group is a carboxylic acid group (Example 25), a phosphoric acid group (Example 28), or a sulfonic acid group (Example 29) is a thiol group Compared with the curable composition in which the different interactive group is a hydroxy group (Example 26), an amino group (Example 27), or a pyridinyl group (Example 31), it has further excellent developability. The This is presumed to be due to the difference in the solubility of the unexposed area due to the difference in the interaction group different from the thiol group.
The curable composition of Example 33 has a more excellent pattern shape as compared to the curable composition of Example 41 in which m + n is equal and m / n is larger, and it is to a support. It had better adhesion.
The curable compositions of Examples 33, 47, 48, 49, and 50 in which the photopolymerization initiator is an oxime compound have better exposure sensitivity as compared with the curable composition of Example 59. It was

  In Table 4, the upper arrow means the same as the column immediately above, and "-" means that the curable composition does not contain the component.

  A curable composition was prepared and evaluated in the same manner as in Example 33 except that the polymerizable compound M2 was used in place of the polymerizable compound M1, and the same result as in Example 33 was obtained. .

  Instead of the polymerizable compound M1, a mixture of the polymerizable compounds M1 and M2 (the content mass ratio of M1 and M2 in the mixture is the content mass of M1: the content mass of M2 = 1: 1, relative to the entire curable composition The curable composition was prepared and evaluated in the same manner as in Example 33 except that the content of the above mixture was the same as the content of the polymerizable compound M1 in Example 33. The same results as in Example 33 were obtained.

[Preparation of carbon black dispersion (CB dispersion) and evaluation of curable composition]
In the preparation of the above-mentioned colorant dispersion, the colorant used is carbon black (trade name "color black S170", manufactured by Degussa, average primary particle diameter 17 nm, BET specific surface area 200 m ² / g, carbon produced by gas black method A carbon black dispersion (CB dispersion) was obtained by the same method except using black).

  In the preparation of the curable composition of Example 33, titanium nitride-containing particles TiN are used instead of the colorant dispersion added so as to contain 58% by mass of titanium nitride-containing particles TiN-1 in the curable composition. A mixture of a colorant dispersion containing C-1 and the above CB dispersion (titanium nitride-containing particles in the curable composition TiN-1: carbon black in the curable composition = 45: 13 (mass ratio), The total content of titanium nitride-containing particles TiN-1 and carbon black in the above curable composition is 58% by mass.) A curable composition is similarly prepared except that it is used The evaluation was done. As a result of the evaluation, it was found that the same evaluation (including exposure sensitivity and adhesion) as in Example 33 was obtained.

[Preparation of chromatic pigment dispersion (PY dispersion) and evaluation of curable composition]
In the same manner as in the preparation of the colorant dispersion, except that the colorant is Pigment Yellow 150 (manufactured by Hangzhou Star-up Pigment Co., Ltd., trade name: 6150 pigment yellow 5GN), a chromatic pigment dispersion (PY dispersion) was obtained.

  In the preparation of the curable composition of Example 33, titanium nitride-containing particles TiN are used instead of the colorant dispersion added so as to contain 58% by mass of titanium nitride-containing particles TiN-1 in the curable composition. Mixture of a colorant dispersion containing C.-1 and the above PY dispersion (titanium nitride-containing particles in the curable composition TiN-1: pigment yellow 150 in the curable composition = 45: 13 (mass ratio), The total content of titanium nitride-containing particles TiN-1 and pigment yellow 150 in the curable composition is 58% by mass.) A curable composition is similarly prepared except that it is used The evaluation was done. As a result of the evaluation, the same evaluation (including exposure sensitivity and adhesion) as in Example 33 was obtained. In addition, as a cured film, it became a darker film further.

[Preparation of chromatic pigment dispersion (PR dispersion)]
In the preparation of the above-mentioned colorant dispersion, the colorant is C.I. I. A chromatic pigment dispersion (PR dispersion) was obtained by the same method except using Pigment Red 254 (manufactured by Ciba Specialty Chemicals).

[Preparation of chromatic pigment dispersion (PB dispersion)]
In the preparation of the above-mentioned colorant dispersion, the colorant is C.I. I. A chromatic pigment dispersion (PB dispersion) was obtained by the same method except using Pigment Blue 15: 6 (manufactured by DIC Corporation).

[Preparation of chromatic pigment dispersion (PV dispersion)]
In the preparation of the above-mentioned colorant dispersion, the colorant is C.I. I. A chromatic pigment dispersion (PV dispersion) was obtained by the same method except using Pigment Violet 23 (manufactured by Clariant).

  In the preparation of the curable composition of Example 33, the above titanium nitride-containing pigment is substituted for the colorant dispersion instead of the colorant dispersion added to contain 58 mass% of titanium nitride-containing particles TiN-1 in the curable composition. Mixture of particles TiN-1, PY, PR, PB, and PV dispersion (ratio of titanium nitride-containing particles TiN-1, PY, PR, PB, and PV in the curable composition; titanium nitride-containing particles TiN -1: PY: PR: PB: PV = 70: 17: 37: 36: 10 (mass ratio), total of titanium nitride-containing particles TiN-1 in the curable composition, PY, PR, PB, and PV A curable composition was similarly prepared except that the content was 58% by mass), and the evaluation was performed using this. As a result of the evaluation, it was found that the same evaluation (including exposure sensitivity and adhesion) as in Example 33 was obtained, and furthermore, a film excellent in the light shielding property in the infrared region was obtained.

  In the preparation of the curable composition of Example 33, the above titanium nitride-containing pigment is substituted for the colorant dispersion instead of the colorant dispersion added to contain 58 mass% of titanium nitride-containing particles TiN-1 in the curable composition. Mixture of particles TiN-1 and compound SQ-23 shown below (ratio of titanium nitride-containing particles TiN-1 in the curable composition, and compound SQ-23; titanium nitride-containing particles TiN-1: compound SQ -23 = 50: 8 (mass ratio), the total content of titanium nitride-containing particles TiN-1 and the compound SQ-23 in the curable composition is 58% by mass. The curable composition was prepared and evaluated using this. As a result of the evaluation, it was found that the same evaluation (including exposure sensitivity and adhesion) as in Example 33 was obtained, and furthermore, a film excellent in the light shielding property in the infrared region was obtained.

  In the preparation of the curable composition of Example 33, the above titanium nitride-containing pigment is substituted for the colorant dispersion instead of the colorant dispersion added to contain 58 mass% of titanium nitride-containing particles TiN-1 in the curable composition. Mixture of particles TiN-1 and the following compound A-52 (ratio of titanium nitride-containing particles TiN-1 in the curable composition, and compound A-52; titanium nitride-containing particles TiN-1: compound A-52 = 50: 8 (mass ratio), the total content of titanium nitride-containing particles TiN-1 in the curable composition and the compound A-52 is 58% by mass. A curable composition was prepared and evaluated using this. As a result of the evaluation, it was found that the same evaluation (including exposure sensitivity and adhesion) as in Example 33 was obtained, and furthermore, a film excellent in the light shielding property in the infrared region was obtained.

・ Compound SQ-23

Compound A-52 (in the following formula, Ph represents a phenyl group)

Evaluation was performed in the same manner as in Example 1 except that the surfactant F-1 was not used. As a result of the evaluation, it was found that the same result as in Example 1 was obtained.

Claims (24)

A curable composition comprising a polyfunctional thiol compound, a polymerizable compound, and a photopolymerization initiator,
A curable composition, wherein the polyfunctional thiol compound contains two or more thiol groups and an interactive group different from the thiol group. The curable composition according to claim 1, wherein the polyfunctional thiol compound is a compound represented by formula (1).

In the formula, L ¹ and L ² each independently represent a divalent linking group, m represents an integer of 2 to 14, n represents an integer of 1 to 15, and L ³ represents a m + n-valent linking group And R ¹ represents an interactive group different from the thiol group.
L ¹ and L ² may be the same or different from each other, and m L ^{1 's} , n L ^{2' s} , and n R ^{1 's} may be the same or different, respectively. Good. The curable composition according to claim 1, wherein the polyfunctional thiol compound is a compound represented by formula (2).

In the formula, R ² and R ³ each independently represent a divalent linking group having 1 or more carbon atoms, m represents an integer of 2 to 14, n represents an integer of 1 to 15, and M ¹ Each independently represents a single bond, -O-, -S-, -N (R ⁴ )-, -C (= O)-, -C (= O) -O-, -O-C (= O ) -O-, -C (= O) -NH-, -O-C (= O) -NH-, -S (= O)-, -S (= O) -O-, -S (= O) _{) 2 -, - S (=} O) 2 -O-, or an -CH = N-, ^{R 4} represents a monovalent organic group, ^{L 3} represents a m + n valent linking group, ^{R 1} is the It represents an interactive group different from a thiol group.
R ² and R ³ may be identical to or different from each other, and n R ^{1 's} , m R ^{2' s} , n R ^{2 's} , n R ^{3' s} , m M ^{1 's} , And n M ¹ may be the same or different.   The curable composition of Claim 2 or 3 whose said m is an integer of 3-14. The interaction group different from the thiol group is a hydroxyl group, an amino group, a pyridinyl group, a pyridinium group, an ammonium group, a phosphonium group, a carboxylic acid group or a salt thereof, a phosphoric acid group or a salt thereof, a sulfonic acid group or a salt thereof The aryl group according to any one of claims 1 to 4, which is at least one selected from the group consisting of: an aryl group, -Si (R ^X ) _p (R ^Y ) _{3 -p} , and-(OR ^A ) _q -R ^Z The curable composition according to any one of the preceding claims.
Here, p represents an integer of 1 to 3, R ^X represents a hydrolysable group, R ^Y represents a monovalent organic group other than a hydrolysable group, and p R ^X and 3-p Each R ^Y may be the same or different. Further, R ^Z represents a hydrogen atom, an alkyl group or an alkoxy group, q represents an integer of 1 to 4, and R ^A represents an alkylene group having 1 to 15 carbon atoms.   The interaction group different from the thiol group is a hydroxyl group, an amino group, a pyridinyl group, a pyridinium group, an ammonium group, a phosphonium group, a carboxylic acid group or a salt thereof, a phosphoric acid group or a salt thereof, and a sulfonic acid group or a salt thereof The curable composition according to any one of claims 1 to 5, which is at least one selected from the group consisting of salts.   The interaction group different from the thiol group is selected from the group consisting of a hydroxyl group, an amino group, a pyridinyl group, a carboxylic acid group or a salt thereof, a phosphoric acid group or a salt thereof, and a sulfonic acid group or a salt thereof The curable composition according to any one of claims 1 to 6, which is at least one.   The curable composition according to any one of claims 1 to 7, further comprising a colorant.   The curable composition according to claim 8, wherein the colorant contains a black pigment.   The curable composition according to any one of claims 1 to 9, wherein the photopolymerization initiator is an oxime compound.   A cured film obtained by curing the curable composition according to any one of claims 1 to 10.   A color filter comprising the cured film according to claim 11.   A light shielding film comprising the cured film according to claim 11.   A solid-state imaging device comprising the cured film according to claim 11.   An image display apparatus comprising the cured film according to claim 11. A curable composition layer forming step of forming a curable composition layer on a support using the curable composition according to any one of claims 1 to 10,
Exposing the curable composition layer, and an exposure step.   The curing according to claim 16, wherein the step of forming the curable composition layer comprises the step of applying the curable composition onto the support to form the curable composition layer on the support. Method of producing a membrane And developing the exposed curable composition layer.
The manufacturing method of the cured film of Claim 16 or 17 including the washing | cleaning process which wash | cleans the said developed curable composition layer.   A multifunctional thiol compound containing two or more thiol groups and an interactive group different from the thiol group. The multifunctional thiol compound of Claim 19 which is a compound represented by Formula (1).

In the formula, L ¹ and L ² each independently represent a divalent linking group, m represents an integer of 2 to 14, n represents an integer of 1 to 15, and L ³ represents a m + n-valent linking group. R ¹ represents an interactive group different from the thiol group.
L ¹ and L ² may be identical to or different from each other, and m pieces of L ¹ , n pieces of L ² and n pieces of R ¹ may be identical to or different from each other . The polyfunctional thiol compound according to claim 19 or 20, which is a compound represented by the formula (2).

In the formula, R ² and R ³ each independently represent a divalent linking group having 1 or more carbon atoms, m represents an integer of 2 to 14, n represents an integer of 1 to 15, and M ¹ Each independently represents a single bond, -O-, -S-, -N (R ⁴ )-, -C (= O)-, -C (= O) -O-, -O-C (= O ) -O-, -C (= O) -NH-, -O-C (= O) -NH-, -S (= O)-, -S (= O) -O-, -S (= O) _{) 2 -, - S (=} O) 2 -O-, or an -CH = N-, ^{R 4} represents a monovalent organic group, ^{L 3} represents a m + n valent linking group, ^{R 1} is the It represents an interactive group different from a thiol group.
R ² and R ³ may be identical to or different from each other, and n R ^{1 's} , m R ^{2' s} , n R ^{2 's} , n R ^{3' s} , m M ^{1 's} , And n M ¹ may be the same or different.   The multifunctional thiol compound of Claim 20 or 21 whose said m is an integer of 3-14. The interaction group different from the thiol group is a hydroxyl group, an amino group, a pyridinyl group, a pyridinium group, an ammonium group, a phosphonium group, a carboxylic acid group or a salt thereof, a phosphoric acid group or a salt thereof, a sulfonic acid group or a salt thereof The aryl group according to any one of claims 19 to 22, which is at least one selected from the group consisting of: an aryl group, -Si (R ^X ) _p (R ^Y ) _{3 -p} , and-(OR ^A ) _q -R ^Z A multifunctional thiol compound according to any one of the preceding claims.
Here, p represents an integer of 1 to 3, R ^X represents a hydrolysable group, R ^Y represents a monovalent organic group other than a hydrolysable group, and p R ^X and 3-p Each R ^Y may be the same or different. Further, R ^Z represents a hydrogen atom, an alkyl group or an alkoxy group, q represents an integer of 1 to 4, and R ^A represents an alkylene group having 1 to 15 carbon atoms. The interaction group different from the thiol group is a hydroxyl group, an amino group, a pyridinyl group, a pyridinium group, an ammonium group, a phosphonium group, a carboxylic acid group or a salt thereof, a phosphoric acid group or a salt thereof, and a sulfonic acid group or a salt thereof The multifunctional thiol compound according to any one of claims 19 to 23, which is at least one selected from the group consisting of salts.