TW201827507A - Curable composition, compound, cured film, method for producing cured film, method for producing color filter, solid state imaging device, and infrared sensor - Google Patents

Abstract

Provided is a curable composition which has excellent storage stability and suppresses the generation of residue in unexposed portions, and from which a cured film having an excellent pattern shape can be obtained. Also provided are: a compound, a cured film, a method for producing a cured film, a method for producing a color filter, a solid state imaging device, and an infrared sensor. The curable composition contains: a polymerizable compound; a photopolymerization initiator; a compound having a thiol group and a group having polymerization inhibiting ability; and a coloring agent.

Description

Curable composition, compound, cured film, method for producing cured film, method for producing color filter, solid-state imaging device, and infrared sensor

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

A curable composition containing light-shielding particles such as carbon black has been known. As described above, the curable composition containing the light-shielding particles is used for various purposes, and is used, for example, for producing a cured film of a liquid crystal display device and a solid-state image sensor. More specifically, in the color filter used for the liquid crystal display device and the solid-state imaging device, a cured film called a black matrix is used on the glass substrate for the purpose of shielding light between the colored pixels and improving contrast. Further, in the solid-state imaging device, a cured film is used in order to prevent noise and improve image quality. Currently, compact and thin solid-state imaging devices are mounted on portable terminals of electronic devices such as mobile phones and PDAs (Personal Digital Assistants). Such a camera module usually includes a solid-state imaging element such as a CCD (Charge Coupled Device) image sensor and a CMOS (Complementary Metal-Oxide Semiconductor) image sensor and is used for A lens of a subject image is formed on the solid-state imaging element.

As such a curable composition, Patent Document 1 discloses a black photosensitive resin composition containing at least a black pigment, a binder resin, a photopolymerizable monomer, a photopolymerization initiator, and a solvent, and contains a specific structure. The lanthanide ester compound is used as a photopolymerization initiator. In the above-mentioned Patent Document 1, a polyfunctional thiol compound which can be used as a chain transfer agent in a radical polymerization process of a photopolymerizable monomer after light exposure can be described in order to impart higher sensitivity to a curable composition. In addition, it is described that a polymerization inhibitor is added to the curable composition in order to form a black matrix pattern having a line width of 5 μm or less with high precision. [Prior Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2014-182253

The inventors of the present invention conducted various studies on the curable composition described in Patent Document 1 and the cured film obtained by exposing the curable composition to a pattern. As a result, it was confirmed that the storage stability of the above-mentioned curable composition does not necessarily reach the level required at present, and further improvement is required. Further, it has been clarified that when exposure and development are carried out using the curable composition, residue is likely to be generated in the unexposed portion, and further improvement is required. Further, regarding the cured film, the pattern shape does not necessarily reach the level required at present, and specifically, it is confirmed that the occurrence of the undercut at the deep portion where the irradiation light is hard to reach during the exposure and the widening of the line width are confirmed, and further improvement is required. .

An object of the present invention is to provide a curable composition which is excellent in storage stability, suppresses generation of residue in an unexposed portion, and has a cured film having an excellent pattern shape. Further, another object of the present invention is to provide a compound, a cured film, a method for producing a cured film, a method for producing a color filter, a solid-state image sensor, and an infrared sensor.

As a result of intensive studies, the present inventors have found that the curable compound contains a compound having a group having a polymerization inhibiting ability and a thiol group, and the above problems can be solved, and the present invention has been completed. That is, it was found that the above object can be achieved by the following structure.

[1] A curable composition comprising: a compound containing a group having a polymerization inhibiting ability and a thiol group; a polymerizable compound; a photopolymerization initiator; and a color former. [2] The curable composition according to the above [1], wherein the compound having a group having the polymerization inhibiting ability and a thiol group has a value R1 represented by the following formula (1) of from 1 to 50%. Formula (1): R1 = [number of groups having polymerization inhibition ability / (number of thiol groups + number of groups having polymerization inhibition ability)] × 100 [3] Sturability as described in [2] In the composition, in the compound containing a group having a polymerization inhibiting ability and a thiol group, the value R1 represented by the above formula (1) is from 3 to 30%. [4] The curable composition according to [2], wherein the compound having the group having the polymerization inhibiting ability and the thiol group has a value R1 represented by the above formula (1) of 8 to 15%. [5] The curable composition according to any one of [1] to [4] wherein the content of the photopolymerization initiator is relative to a compound containing a group having a polymerization inhibiting ability and a thiol group. The content is 1 to 100 times in mass ratio. [6] The curable composition according to any one of [1] to [5] wherein the content of the compound having a group having the above polymerization inhibiting ability and a thiol group is 0.01 to 3 with respect to the total solid content. quality%. [7] The curable composition according to any one of [1] to [6] wherein the group having the above polymerization inhibiting ability is selected from the group consisting of a phenol-based compound and represented by the formula (IH-2) Any one of the compounds of the group of compounds derivatizes a monovalent group. [8] The curable composition according to any one of [1] to [7] wherein the compound having a group having the above polymerization inhibiting ability and a thiol group is a compound represented by the following formula (1). . In the compound represented by the above formula (1), the numerical value R3 represented by the following formula (3) and the numerical value R4 represented by the following formula (4) are both more than 0%. Formula (3): R3 = [number of Q ₂ / (number of thiol groups + number of Q ₂ )] × 100 Formula (4): R4 = [number of thiol groups / (number of thiol groups + Q number _2)] × 100 [9] of [1] to [8] the curable composition according to any one, which further contain a thiol compound, the thiol compound containing no group having polymerization inhibition ability of . [10] A compound containing a group having a polymerization inhibiting ability and a thiol group. [11] The compound according to [10], wherein the group having the above polymerization inhibiting ability is derived from any one selected from the group consisting of a phenolic compound and a compound represented by the formula (IH-2). A monovalent group. [12] The compound according to [10] or [11], which is represented by the following formula (1). In the compound represented by the above formula (1), the numerical value R3 represented by the following formula (3) and the numerical value R4 represented by the following formula (4) are both numbers exceeding 0%. Formula (3): R3 = [number of Q ₂ / (number of thiol groups + number of Q ₂ )] × 100 Formula (4): R4 = [number of thiol groups / (number of thiol groups + Q The number of ₂ ) is 100% [13] A cured film obtained by hardening the curable composition according to any one of [1] to [9]. [14] A method for producing a cured film, comprising: a step of forming a curable composition layer, wherein the curable composition layer is formed using the curable composition according to any one of [1] to [9]; The hard curable composition layer is exposed to a pattern; and a developing step is performed to remove the unexposed portion to form a cured film. [15] A method of producing a color filter comprising the method for producing a cured film according to [14]. [16] A solid-state photographic element comprising the cured film according to [13] as a color filter. [17] An infrared sensor comprising the cured film of [13] as a color filter. [Effect of the invention]

According to the present invention, it is possible to provide a curable composition which is excellent in storage stability, suppresses generation of residue in an unexposed portion, and has a cured film having an excellent pattern shape. Moreover, according to the present invention, it is possible to provide a compound, a cured film, a method for producing a cured film, a method for producing a color filter, a solid-state image sensor, and an infrared sensor.

Hereinafter, the present invention will be described in detail. The description of the constituent elements described below may be performed based on representative embodiments of the present invention, but the present invention is not limited to such an embodiment. In the present specification, the numerical range indicated by "~" indicates a range including the numerical values described before and after "~" as the lower limit and the upper limit. Further, in the expression of the group (atomic group) in the present specification, the expressions in which the substitution and the unsubstituted are not described together with the substituent-free group are also included. For example, "alkyl" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group). In the present specification, "actinic ray" or "radiation" means, for example, far ultraviolet rays, extreme ultraviolet ray (EUV), X-rays, and electron beams typified by a bright line spectrum of a mercury lamp and an excimer laser. Further, in the present specification, "light" means actinic rays or radiation. The "exposure" in the present specification includes not only exposure by far ultraviolet rays, X-rays, and EUV light represented by mercury lamps and excimer lasers, but also electron beams and ion beams, unless otherwise specified. Wait for the particle beam to draw. In the present specification, "(meth) acrylate" means acrylate and methacrylate. In the present specification, "(meth)acrylic acid" means acrylic acid and methacrylic acid. In the present specification, "(meth)acrylonitrile" means an acryloyl group and a methacryloyl group. In the present specification, "(meth)acrylamide" means acrylamide and methacrylamide. In the present specification, "(meth)acrylic acid" means acrylic acid and methacrylic acid. In the present specification, "monomer" has the same meaning as "monomer". The monomer differs from the oligomer and the polymer and refers to a compound having a weight average molecular weight of 2,000 or less. In the present specification, the polymerizable compound means a compound containing a polymerizable group, and may be a monomer or a polymer. A polymerizable group refers to a group that participates in a polymerization reaction.

[Curable composition] The curable composition of the present invention contains a compound containing a group having a polymerization inhibiting ability and a thiol group, a polymerizable compound, a photopolymerization initiator, and a color former. According to the above-described configuration, the curable composition of the present invention can provide a cured film having excellent storage stability and suppressing generation of residue in the unexposed portion and having an excellent pattern shape (hereinafter, excellent storage stability and suppression) The effect of residue generation, suppression of undercut, and/or suppression of broadening in the unexposed portion is also referred to as "the effect of the present invention". In the following, the structural difference between the curable composition described in Patent Document 1 and the curable composition of the present invention is compared with the effect of the present invention on the curable composition of the present invention. The mechanism of speculation is explained.

Recently, a light-shielding property is required for a cured film used for a color filter and/or a solid-state imaging element. Therefore, a material having a light-shielding property such as a large amount of a coloring agent is blended in the curable composition for forming the cured film. On the other hand, when the curable composition as described above is exposed, light is difficult to be formed in the composition. In the middle transmission, the deeper the light is hard to reach, the harder it is. As a result, undercut is easily generated in the obtained pattern. As a result of examining the curable composition described in Patent Document 1, the inventors have confirmed that the polyfunctional thiol compound is used as a chain transfer agent in a radical polymerization process after exposure, whereby light is used. The deep radicals that are difficult to reach cause a radical polymerization reaction, which helps to suppress the above undercut. However, on the other hand, the above-mentioned polyfunctional thiol compound diffuses not only in the deep portion where light is hard to reach but also in the other direction, so that the width of the pattern is called larger than the desired width (so-called "wide"). s reason. In other words, for example, it has been clarified that when a curable composition layer is formed on a support using a curable composition and is exposed to a pattern for development, chain transfer occurs in the horizontal direction (direction parallel to the support). And causes the width of the pattern to widen. In particular, it has been confirmed that the amount of light exposure of the surface of the curable composition layer is rich, and thus radical polymerization is remarkably generated in the horizontal direction (direction parallel to the support).

Further, the polyfunctional thiol compound not only causes chain transfer of radicals generated during exposure but also causes chain transfer by radicals generated by heat. Therefore, the curable composition containing the above polyfunctional thiol compound tends to have poor storage stability (thermal stability under storage). In addition, when the pre-baking step (heating step before exposure) which is performed before the exposure using the curable composition layer containing the curable composition of the above polyfunctional thiol compound is observed, the unexposed portion is heated by heat. The diffusion of the generated radicals also becomes easy to harden and is liable to cause development residue.

On the other hand, in order to suppress the occurrence of the above-mentioned widening and development residue, and to improve the storage stability, and to use a polymerization inhibitor at the same time, when the amount of the polymerization inhibitor is large, the problem of storage stability and widening can be solved. However, it is impossible to suppress the generation of undercut and development residue. On the other hand, when the amount of the polymerization inhibitor is small, various problems caused by the above-mentioned polyfunctional thiol compound cannot be suppressed.

The present inventors have overcome the above-mentioned Patent Document 1 by including a compound containing a group having a polymerization inhibiting ability and a thiol group (hereinafter also referred to as "the compound of the present invention") in the curable composition. Problems. The compound of the present invention is characterized in that it has a thiol group which is useful as a chain transfer agent in one molecule and a group having a polymerization inhibiting ability which is helpful as a polymerization inhibitor. The curable composition of Patent Document 1 containing a polyfunctional thiol group and a polymerization inhibitor respectively does not necessarily mean that a sufficient amount of polymerization inhibitor exists in a region where the concentration of the polyfunctional thiol group is high, that is, it cannot suppress the heat generation. Unnecessary free radical polymerization. On the other hand, the curable composition containing the compound of the present invention can suppress radical polymerization by heat by the above-described structural features, in other words, it is excellent in storage stability and suppresses generation of development residue. Further, it has been confirmed that the curable composition of the present invention can simultaneously suppress undercut and broaden. In the compound containing a group having a polymerization inhibiting ability and a thiol group, the number of groups having a polymerization inhibiting ability / (the number of thiol groups + the number of groups having a polymerization inhibiting ability)] When x100 is from 1 to 50%, preferably from 3 to 30%, more preferably from 8 to 15%, it is possible to suppress the broadening and remarkably suppress the undercut.

Hereinafter, various components contained in the curable composition of the present invention will be described in detail.

[Compound containing a group having a polymerization inhibiting ability and a thiol group] The curable composition contains a compound containing a group having a polymerization inhibiting ability and a thiol group. In the present specification, a compound containing a group having a polymerization inhibiting ability and a thiol group means a group having a group having a polymerization inhibiting ability and a thiol group (that is, a group represented by -SH) in the same molecule.

The group having a polymerization inhibiting ability is not particularly limited as long as it has a polymerization inhibiting ability, and for example, a known polymerization inhibitor (for example, a radical polymerization inhibitor) is derivatized into a monovalent group. As a method of the above-described derivatization, for example, a method of extracting one hydrogen atom contained in a polymerization inhibitor as a monovalent group can be mentioned. Here, the polymerization inhibitor refers to a compound having a polymerization initiator or a radical generated in a polymerizable monomer capable of trapping the radical before causing a growth reaction, and has a function of inhibiting polymerization. The polymerization inhibitor is not particularly limited, and examples thereof include a phenol compound (phenolic polymerization inhibitor), a thioether polymerization inhibitor, an amine polymerization inhibitor, a phosphite polymerization inhibitor, and a nitroso polymerization inhibitor. And N-oxyl radical compounds. More specifically, the compounds shown below are mentioned. A group having a polymerization inhibiting ability is derived by extracting any hydrogen atom in the polymerization inhibitor shown below.

[Chemical Formula 1]

In addition, as a polymerization inhibitor, a compound represented by the following formula (IH-1) and a compound represented by the formula (IH-2) are also more specifically mentioned.

[Chemical Formula 2]

In the formula (IH-1), R ₁ to R ₅ each independently represent a hydrogen atom or a substituent. The substituent may, for example, be an alkyl group, an alkenyl group, a hydroxyl group, a diphenylethylenedione, an amine group, an aryl group, an alkoxy group, a carboxyl group, an alkoxycarbonyl group or a fluorenyl group. R ₁ to R ₅ may be bonded to each other to form a ring. Among them, a group having a polymerization inhibiting ability is formed by extracting a hydrogen atom of any of R ₁ to R ₅ of the formula (IH-1) or a hydrogen atom of the substituent. Among them, any one of R ₁ to R ₅ in the formula (IH-1) represents a hydrogen atom, and it is preferred to extract the hydrogen atom to form a group having a polymerization inhibiting ability. Further, a substituent represented by R ₁ to R ₅ (for example, an alkyl group, an alkenyl group, a diphenylethylenedione, an amine group, an aryl group, an alkoxy group, an alkoxycarbonyl group or a fluorenyl group) may be further substituted The group (preferably the substituent W described later) is substituted.

R ₁ to R ₅ in the formula (IH-1), a hydrogen atom, an alkyl group having 1 to 5 carbon atoms (for example, an ethyl group and a third butyl group), and an alkoxy group having 1 to 5 carbon atoms (for example) An alkenyl group having a carbon number of 2 to 4 (e.g., a vinyl group), a phenyl group or a diphenylethylenedione is preferred. Here, at least one of R ₁ and R ₅ is selected from an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, a phenyl group and a diphenylethylene group. Any of the ketone groups is preferred. Further, R ₂ to R ₄ are preferably a hydrogen atom, and it is preferred to extract a hydrogen atom of R ₃ to form a group having a polymerization inhibiting ability.

In the following, the compound represented by the formula (IH-1) is not particularly limited, and examples thereof include the following. Further, among the following compounds, it is preferred to extract a hydrogen atom at a carbon atom at the position marked with *.

[Chemical Formula 3]

[Chemical Formula 4]

In the formula (IH-2), W represents an alkylene group. The number of carbon atoms contained in the alkylene group is not particularly limited, and 4 to 5 is preferred. Further, in the compound represented by the formula (IH-2), a 5-membered ring or a 6-membered ring containing W and N (nitrogen atom) is preferably formed. The alkylene group represented by W may have a substituent (preferably a substituent W described later, more preferably an alkyl group). As the compound represented by the formula (IH-2), a compound represented by the following formula (IH-2-1) is preferred.

[Chemical Formula 5]

In the formula (IH-2-1), R ₁₁ to R ₁₆ each independently represent a hydrogen atom, a halogen atom or a monovalent organic group, or R ₁₁ and R ₁₂ , R ₁₃ and R ₁₄ , R ₁₅ and R _{16 are} also independently One carbonyl group may be formed together with the carbon to which the bond is bonded. In addition, any one of R ₁₁ to R ₁₆ of the formula (IH-2-1) represents a hydrogen atom, and a group having a polymerization inhibiting ability is formed by extracting the hydrogen atom.

The monovalent organic group means an alkyl group, a hydroxyl group, or -NR ₁₇ R ₁₈ (wherein R ₁₇ and R ₁₈ each independently represent a hydrogen atom or an alkyl group), an aryl group, an alkoxy group, a carboxyl group, an aryloxy group, or O(C=O)R ₁₉ , -NH(C=O)R ₂₀ (R ₁₉ and R ₂₀ each independently represent a hydrogen atom, an alkyl group or an aryl group), an aminomethyl sulfonyl group, a cyano group or a cis group. A enediminoimine group. Further, an alkyl group, an amine group, an aryl group, an alkoxy group, a carboxyl group, an aryloxy group, an aminomethyl fluorenyl group, and a maleimide group represented by R ₁₁ to R ₁₆ may also be substituted by a substituent. (Replacement is preferably a substituent W described later).

R ₁₁ to R ₁₆ in the formula (IH-2-1) represent a hydrogen atom, a hydroxyl group, and -NR ₁₇ R ₁₈ (R ₁₇ and R ₁₈ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. .), an alkyl group having 1 to 5 carbon atoms (for example, a methyl group or an ethyl group), an aryl group having 6 to 10 carbon atoms, and an alkoxy group having 1 to 5 carbon atoms (for example, a methoxy group and an ethoxy group) An aryloxy group having 6 to 10 carbon atoms, -O(C=O)R ₁₉ and -NH(C=O)R ₂₀ (R ₁₉ and R ₂₀ each independently represent a hydrogen atom and an alkyl group having 1 to 5 carbon atoms; Or a carbonyl group having 6 to 10 carbon atoms, or R ₁₁ and R ₁₂ , R ₁₃ and R ₁₄ , or R ₁₅ and R ₁₆ may form a carbonyl group together with the carbon to be bonded. . Among them, a hydrogen atom of R ₁₁ to R ₁₆ is preferred (that is, a compound represented by the formula (IH-2-1) is a 2,2,6,6-tetramethylacridine 1-oxyl radical. Preferably, it is preferred to extract a hydrogen atom of R ₁₃ or R ₁₄ to form a group having a polymerization inhibiting ability.

The group having a polymerization inhibiting ability, wherein, from the viewpoint of the effect of the present invention being more excellent, it is selected from the group consisting of a compound containing a phenol compound (preferably a compound represented by the formula (IH-1)) A compound having a valence group derived from any one of the compounds represented by the formula (IH-2) is preferred, and is selected from the group consisting of a compound containing a phenol compound and a compound represented by the formula (IH-2-1). Further, a compound-derived one-valent group is more preferable, and a valent group derived from a phenol-based compound or a 2,2,6,6-tetramethylacridinium 1-oxyl radical-4-yl group is further preferably further. It is particularly preferred that a monovalent group derived from a compound represented by the formula (IH-1) is used, and 3,5-di-tert-butyl-4-hydroxyphenyl group is most preferred.

The compound containing a group having a polymerization inhibiting ability and a thiol group is more excellent in the effect of the present invention (in particular, from the viewpoint of remarkably suppressing undercut), the value R1 represented by the following formula (1) It is preferably 1 to 50%, more preferably 3 to 30%, and still more preferably 8 to 15%. Formula (1): R1 = [number of groups having polymerization inhibition ability / (number of thiol groups + number of groups having polymerization inhibition ability)] × 100

Here, the "number of thiol groups" and "the number of groups having a polymerization inhibiting ability" mean "average number", respectively, and R1 can be based on a peak measured by NMR (nuclear magnetic resonance). The area ratio (integral intensity ratio) is calculated.

Among the compounds containing a group having a polymerization inhibiting ability and a thiol group, a molecular weight of 500 or more is preferable, and specifically, a molecular weight of 500 to 5,000 is preferable, and more preferably 500 to 3,000.

The compound containing a group having a polymerization inhibiting ability and a thiol group is preferably a compound represented by the following formula (1X) from the viewpoint of the effect of the present invention being more excellent. (a compound represented by the formula (1X))

[Chemical Formula 6] General formula (1X)

In the formula (1X), n represents an integer of 2 or more, 3 to 6 is preferable, and 4 is more preferable. A represents an n-valent group, and R represents a hydrogen atom or a monovalent group represented by the following formula (2X). In the compound represented by the formula (1X), the value R1 represented by the above formula (1) exceeds 0%, and the value R2 represented by the following formula (2) exceeds 0%.

[Chemical Formula 7] General formula (2X)

In the formula (2X), L represents a divalent linking group, Q represents a group having the above polymerization inhibiting ability, and * represents a bonding site with a sulfur atom. Further, in the general formula (2X), when a plurality of L and Q are present, the plurality of L and the plurality of Qs may be the same or different.

Formula (2): R2 = [number of thiol groups / (number of thiol groups + number of groups having polymerization inhibition ability)] × 100

In the formula (1X), n represents an integer of 2 or more, and A represents an n-valent group. Among them, as the compound represented by the formula (1X), a compound represented by the following formula (3X) is preferred.

T-(ZSR) _n general formula (3X)

In the formula (3X), n and R have the same meanings as n and R in the above formula (1X). T represents an n-valent group (n is an integer of 2 or more). T is preferably a carbon atom, a halogen atom, a sulfur atom, an oxygen atom, a nitrogen atom, a group consisting of a carbon atom-oxygen atom-carbon atom, and a carbon atom-oxygen atom-carbon atom-oxygen atom-carbon atom. A group, an n-valent aliphatic hydrocarbon ring, an n-valent aromatic hydrocarbon ring or an n-valent heterocyclic ring are preferred. Further, the "group consisting of a carbon atom - an oxygen atom - a carbon atom" means that W of the general formula (Y13) described later is 1 and La is an oxygen atom, and "from a carbon atom - an oxygen atom - a carbon atom - an oxygen The group consisting of an atom and a carbon atom means that W of the general formula (Y13) described later is 2 and La is an oxygen atom. The number of carbon atoms contained in the aliphatic hydrocarbon ring is preferably from 3 to 15, more preferably from 3 to 10, still more preferably from 5 to 10. The number of carbon atoms contained in the aromatic hydrocarbon ring is preferably from 6 to 18, more preferably from 6 to 14, and further preferably from 6 to 10. The heterocyclic ring is preferably a 5- to 7-membered ring having at least one N atom, O atom, S atom or Se atom in the ring structure, and more preferably a 5- to 6-membered ring.

Examples of T include a group represented by the following general formulae (Y1) to (Y14). Further, in each formula, * represents a bonding position with a divalent linking group represented by Z. In addition, the above-mentioned T "carbon atom" means that T is a group represented by the following general formula (Y6), and the above T is "deuterium atom" means that T is a group represented by the following general formula (Y10). The above-mentioned "sulfur atom" means that T is a group represented by the following formula (Y8), and the above-mentioned T is "oxygen atom" means that T is a group represented by the following formula (Y9), and the above T is a "nitrogen atom" means that T is a group represented by the following formula (Y11). In addition, the "n-valent aliphatic hydrocarbon ring" is a group represented by the following formula (Y12), and the "n-valent aromatic hydrocarbon ring" is, for example, a group represented by the following formula (Y7). The "n-valent heterocyclic ring" is, for example, a group represented by the following general formulae (Y3) to (Y5). Further, in the group represented by the formula (Y13), C ^L represents a carbon atom or a ruthenium atom, and W represents 1-4. Further, L _a is not particularly limited as long as it is a divalent linking group. Examples of the divalent linking group include -O-, -S-, -NR ^a -, -CO-, and an alkylene group (may be one of a cyclic, a branched, and a linear chain). An alkenyl group, an alkynylene group, an aryl group, a heteroaryl group or a divalent group formed by combining the same. R ^a may, for example, be a hydrogen atom, an alkyl group (preferably a linear or branched alkyl group having 1 to 10 carbon atoms), or a halogen atom (preferably a fluorine atom, a chlorine atom, a bromine atom or an iodine atom). And an aryl group (preferably an aryl group having 6 to 20 carbon atoms). Further, in the group represented by the formula (Y14), C ^L represents a carbon atom or a ruthenium atom, and R ^a represents a substituent (for example, an alkyl group).

[Chemical Formula 8]

[Chemical Formula 9]

In the formula (3X), Z represents a divalent linking group. A plurality of Zs may be the same or different. Z is not particularly limited, and examples thereof include -O-, -S-, -NR ^a -, -CO-, and an alkylene group (which may be any of a cyclic, branched, and linear chain). An alkenyl group, an alkynylene group, an extended aryl group, a heteroaryl group or a divalent group obtained by combining the same. R ^a may, for example, be a hydrogen atom, an alkyl group (preferably a linear or branched alkyl group having 1 to 10 carbon atoms), or a halogen atom (preferably a fluorine atom, a chlorine atom, a bromine atom or an iodine atom). And an aryl group (preferably an aryl group having 6 to 20 carbon atoms).

In the general formula (1X) and the general formula (3X), n is not particularly limited as long as it is an integer of 2 or more. Further, the upper limit thereof is not particularly limited, and an integer of 15 or less is preferable. Among them, from the viewpoint of more excellent effects of the present invention and developability, 2 to 10 are preferable, 2 to 6 is more preferable, 3 to 6 is further more preferable, and 4 is particularly preferable.

In the formula (2X), L represents a divalent linking group. L is not particularly limited and means that it is selected from any one selected from the group consisting of an alkylene group, an extended aryl group, an ether group, an ester group, a thioester group, a decylamino group, a urethane group, and a urea group. A combination of two or more types.

The number of carbon atoms in the alkylene group represented by L ₁ is not particularly limited, and from the viewpoint of the effect of the present invention being more excellent, 1 to 10 is preferable, and 1 to 6 is more preferable. The alkylene group may be any of a linear chain, a branched chain, and a cyclic chain. Further, the alkylene group may be substituted by a substituent (substituent W (other than alkyl group) described later is preferred). Examples of the above alkylene group include -CH ₂ -, -CH ₂ CH ₂ -, -nCH ₂ CH ₂ CH ₂ -, -iCH ₂ CH ₂ CH ₂ -, -nCH ₂ CH ₂ CH ₂ CH ₂ -, And -nCH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ -.

The number of carbon atoms in the extended aryl group represented by L is not particularly limited, and from the viewpoint of the effect of the present invention being more excellent, 6 to 30 is more preferable, and 6 to 18 is more preferable. The aryl group may have a single ring structure or a condensed ring structure (fused ring structure) of two or more ring-condensed rings. Further, the alkylene group may be substituted by a substituent (the substituent W described later is preferred). Examples of the above-mentioned extended aryl group include two hydrogen atoms extracted from a phenyl group, a naphthyl group, an anthracenyl group, an anthracenyl group, a phenanthryl group, and a fluorenyl group to form a divalent group, a phenyl group, and the like, and a phenyl group or a phenyl group. The stretching of the naphthyl group is preferred, and the stretching of the phenyl group is more preferred.

Wherein, L-based one-CH ₂ - or two or more adjacent -CH ₂ - may be independently substituted by an ether group, an ester group or a decyl group, and the alkyl group having 1 to 10 carbon atoms is good.

In the numerical value R2 represented by the above formula (2), from the viewpoint that the effect of the present invention is more excellent, 50 to 99% is preferable, 70 to 97% is more preferable, and 85 to 92% is further more preferable.

The compound containing a group having a polymerization inhibiting ability and a thiol group is not particularly limited, and examples thereof include the following compounds. In the following compounds, R represents any one selected from the group consisting of a hydrogen atom and a group of a monovalent group represented by the formula (2X), and the value R1 represented by the above formula (1) and the above formula (2) The expressed value R2 is greater than 0%.

[Chemical Formula 10]

Among the compounds containing a group having a polymerization inhibiting ability and a thiol group, a compound represented by the following formula (1) is preferred from the viewpoint of the effect of the present invention being more excellent.

(Compound represented by the formula (1)) Hereinafter, the compound represented by the formula (1) will be described in detail.

[Chemical Formula 11]

In the formula (1), m represents 0, 1, or 2. In the formula (1), a plurality of L ₁ each independently represent a group selected from the group consisting of an alkylene group, an extended aryl group, an ether group, an ester group, a thioester group, a decylamino group, a urethane group, and Any one or a combination of two or more of the group of urea groups. The number of carbon atoms in the alkylene group represented by L ₁ is not particularly limited, and from the viewpoint of the effect of the present invention being more excellent, 1 to 10 is preferable, 1 to 6 is more preferable, and 1 to 3 is further more. good. The alkylene group may be any of a linear chain, a branched chain, and a cyclic chain. Further, the alkylene group may be substituted by a substituent (substituent W (other than alkyl group) described later is preferred). Examples of the above alkylene group include -CH ₂ -, -CH ₂ CH ₂ -, -nCH ₂ CH ₂ CH ₂ -, -iCH ₂ CH ₂ CH ₂ -, -nCH ₂ CH ₂ CH ₂ CH ₂ - and -nCH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ -etc.

The number of carbon atoms in the extended aryl group represented by L ₁ is not particularly limited, and from the viewpoint of more excellent effects of the present invention, 6 to 30 is more preferable, and 6 to 18 is more preferable. The aryl group may have a single ring structure or a condensed ring structure (fused ring structure) of two or more ring-condensed rings. Further, the alkylene group may be substituted by a substituent (the substituent W described later is preferred). Examples of the above-mentioned extended aryl group include two hydrogen atoms extracted from a phenyl group, a naphthyl group, an anthracenyl group, an anthracenyl group, a phenanthryl group, and a fluorenyl group to form a divalent group, a phenyl group, and the like, and a phenyl group or a phenyl group. The stretching of the naphthyl group is preferred, and the stretching of the phenyl group is more preferred.

Among them, as L ₁ , an alkylene group is preferred, and a carbon number of 1 to 10 is preferred, 1 to 6 is more preferred, and 1 to 3 is further preferred.

In the formula (1), a plurality of Q ₁ each independently represent a hydrogen atom or a group represented by the formula (2). Further, in the following general formula (2), * represents a bonding site with a sulfur atom.

[Chemical Formula 12]

In the formula (2), L ₂ represents a group selected from the group consisting of an alkylene group, an extended aryl group, an ether group, an ester group, a thioester group, a decylamino group, a urethane group, and a ureido group. One or a combination of two or more. The definition and preferred form of the alkylene group and the extended aryl group represented by L ₂ are the same as those of the above formula (2X).

Wherein, as L ₂ , 1 -CH ₂ - or 2 or more adjacent -CH ₂ - may be independently substituted by an ether group, an ester group or a decyl group, and a C 1-10 alkyl group It is better.

Q ₂ is a compound selected from the group consisting of a phenol-based compound (a preferred one derived from a compound represented by the formula (IH-1)) and a compound represented by the following formula (IH-2) (2, 2) Any one of the compounds of the group of 6,6-tetramethylacridine 1-oxyl radicals is preferred to derive a monovalent group. Further, the above-mentioned monovalent group represented by Q ₂ has the same meaning as the above-mentioned group having a polymerization inhibiting ability, and the preferred embodiment is also the same.

In the general formula (1), when a plurality of L ₂ and Q ₂ are present, the plurality of L ₂ and the plurality of Q ₂ may be the same or different.

Further, in the general formula (1), the numerical value R3 represented by the following formula (3) and the numerical value R4 represented by the following formula (4) are each greater than 0%. Formula (3): R3 = [number of Q ₂ / (number of thiol groups + number of Q ₂ )] × 100 Formula (4): R4 = [number of thiol groups / (number of thiol groups + Q The number of ₂ )] × 100 The value R3 represented by the above formula (3) is preferably from 1 to 50%, more preferably from 3 to 30%, more preferably from the viewpoint of the effect of the present invention being more excellent. 15% is further preferred. In the numerical value R4 represented by the above formula (4), from the viewpoint that the effect of the present invention is more excellent, 50 to 99% is preferable, 70 to 97% is more preferable, and 85 to 92% is further more preferable.

Wherein, "the number of thiol group" refers to the general formula (1) in _a coefficient Q SH group formed by the hydrogen atom, "the number of Q _2" refers to the general formula (1) in the formula ₁ Q (2) The number of Q ₂ at the time (general formula (2): -L ₂ -Q ₂ ). Moreover, the "number of thiol groups" and the "number of Q ₂ " mean "average number", respectively. The above numerical values R3 and R4 can be calculated from the area ratio (integrated intensity ratio) of the peak measured by NMR.

Specific examples of the group represented by the formula (2) are shown below, but are not limited thereto. In addition, * represents a bonding site with a sulfur atom.

[Chemical Formula 13]

The substituent W in the present specification is described. Examples of the substituent W include a halogen atom, an alkyl group (containing a cycloalkyl group, a bicycloalkyl group, and a tricycloalkyl group), an alkenyl group (containing a cycloalkenyl group and a bicycloalkenyl group), an alkynyl group, and an aryl group. , heterocyclic group (also known as heterocyclic group), cyano group, hydroxy group, nitro group, carboxyl group, alkoxy group, aryloxy group, decyloxy group, heterocyclic oxy group, decyloxy group, amine methoxy group , alkoxycarbonyloxy, aryloxycarbonyloxy, amine (containing anilino), ammonium, amidino, aminomethyloxy, alkoxycarbonylamino, aryloxycarbonylamino, Aminesulfonylamino, alkyl or arylsulfonylamino, fluorenyl, alkylthio, arylthio, heterocyclic thio, sulfonyl, sulfo, alkyl or arylsulfinyl , alkyl or arylsulfonyl, fluorenyl, aryloxycarbonyl, alkoxycarbonyl, aminomethylindenyl, aryl or heterocyclic azo, imine, phosphino, phosphinyl, phosphine oxide Alkoxy, phosphinylamino, phosphonium, methoxyalkyl, decyl, ureido, boronic acid (-B(OH) ₂ ), phosphate (-OPO(OH) ₂ ), sulfate (- OSO ₃ H) and other well-known substituents . Further, the substituent W may be further substituted with a substituent W. For example, an alkyl group may also be substituted by a halogen atom.

The compound represented by the formula (1) can be synthesized by a known method. The compound represented by the formula (1) is exemplified below, but is not limited thereto.

[Table 1]

Further, the above-mentioned compound containing a group having a polymerization inhibiting ability and a thiol group can be synthesized by a known method.

The content of the compound having a group having a polymerization inhibiting ability and a thiol group in the curable composition is not particularly limited, and is, for example, 0.01 to 6% by mass based on the total solid content of the curable composition, from the present invention. From the viewpoint of more excellent effects, 0.01 to 3% by mass is more preferable, 0.2 to 2.5% by mass is more preferable, and 0.6 to 1.3% by mass is further more preferable.

Further, the compound having a group having a polymerization inhibiting ability and a thiol group may be used alone or in combination of two or more. When two or more types are used at the same time, the total is preferably in the above range.

Further, the curable composition may contain a thiol compound having no group having a polymerization inhibiting ability, in addition to the above-mentioned compound having a group having a polymerization inhibiting ability and a thiol group.

[Polymerizable Compound] The curable composition contains a polymerizable compound. The content of the polymerizable compound is preferably from 1 to 40% by mass based on the total solid content of the curable composition. When the content of the polymerizable compound is from 1 to 40% by mass, the curable composition has more excellent exposure sensitivity. Further, the polymerizable compound may be used alone or in combination of two or more. When two or more kinds of polymerizable compounds are used at the same time, the total amount thereof is preferably in the above range.

The polymerizable compound is preferably one or more compounds containing an ethylenically unsaturated bond, more preferably two or more compounds, more preferably three or more, and even more preferably five or more. The upper limit is, for example, 15 or less. Examples of the group containing an ethylenically unsaturated bond include a vinyl group, a (meth)allyl group, and a (meth)acryl fluorenyl group.

The polymerizable compound may be, for example, any one of a chemical form such as a monomer, a prepolymer, an oligomer, a mixture thereof, or a polymer thereof, and a monomer is preferred. The molecular weight of the polymerizable compound is preferably from 100 to 3,000, more preferably from 250 to 1,500. 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 the monomer and the prepolymer include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) or esters thereof, guanamines. Further, as such a polymer, an ester of an unsaturated carboxylic acid and an aliphatic polyol compound, and an amide of an unsaturated carboxylic acid and an aliphatic polyamine compound, and a polymer of these are preferable. Further, an unsaturated carboxylic acid ester having a nucleophilic substituent such as a hydroxyl group, an amine group or a fluorenyl group, or an addition reaction product of a monofunctional or polyfunctional isocyanate or an epoxy group, and the above-mentioned A dehydration condensation reaction of a saturated carboxylic acid ester or a guanamine with a monofunctional or polyfunctional carboxylic acid. Further, an unsaturated carboxylic acid ester or an oxime amine containing an electrophilic substituent such as an isocyanate group or an epoxy group, a reaction product of a monofunctional or polyfunctional alcohol, an amine or a thiol, or a halogenated group or Reactants of unsaturated carboxylic acid esters or decylamines such as tosyloxyl groups and monofunctional or polyfunctional alcohols, amines or thiols are also preferred. Further, instead of the above unsaturated carboxylic acid, a compound group of a vinylbenzene derivative such as an unsaturated phosphonic acid or styrene, a vinyl ether or an allyl ether may be used. As the specific compound, the compound described in paragraphs 0095 to 0108 of JP-A-2009-288705 can also be suitably used in the present invention.

The polymerizable compound is preferably a compound containing one or more groups containing an ethylenically unsaturated bond and having a boiling point of 100 ° C or higher at normal pressure. For example, the compounds described in paragraphs 0227 to 0257 of JP-A-2013-29760 and JP-A-2008-292970 can be referred to in the specification of the present application.

As the polymerizable compound, dipentaerythritol triacrylate (commercially available, KAYARAD D-330, PET-30; manufactured by Nippon Kayaku Co., LTD.), dipentaerythritol tetraacrylate (as a commercially available product, KAYARAD D-) can also be used. 320; manufactured by Nippon Kayaku Co., LTD.), dipentaerythritol penta (meth) acrylate (commercially available, KAYARAD D-310; manufactured by Nippon Kayaku Co., LTD.), dipentaerythritol hexa(meth) acrylate Ester (as a commercial product, KAYARAD DPHA; manufactured by Nippon Kayaku Co., LTD., A-DPH-12E; manufactured by Shin-Nakamura Chemical Co., LTD.) and these (meth)acryloyl groups are via ethylene glycol residues. The structure of the propylene glycol residue (for example, SR454, SR499 commercially available from Sartomer company Inc.) is preferred. It is also possible to use these oligomer types. Further, NK ester A-TMMT (pentaerythritol tetraacrylate, manufactured by Shin-Nakamura Chemical Co., LTD.) and KAYARAD RP-1040 (manufactured by Nippon Kayaku Co., LTD.) can be used. The aspect of the preferred polymerizable 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 acid group-containing polymerizable compound, an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid is preferred, and a non-aromatic carboxylic anhydride is reacted with an unreacted hydroxyl group of the aliphatic polyhydroxy compound to have an acid group. More preferably, the polymerizable compound is further preferred, and among the esters, the aliphatic polyhydroxy compound is pentaerythritol and/or dipentaerythritol. As a commercial item, ARONIX TO-2349, M-305, M-510, M-520, etc. by TOAGOSEI CO., LTD. are mentioned, for example.

The acid value of the polymerizable compound containing an acid group is preferably from 0.1 to 40 mgKOH/g, more preferably from 5 to 30 mgKOH/g. When the acid value of the polymerizable compound is 0.1 mgKOH/g or more, the development and dissolution characteristics are good, and when it is 40 mgKOH/g or less, it is advantageous in terms of production and/or handling. Further, the photopolymerization performance is good and the curability is excellent.

The compound containing a caprolactone structure is also a preferred form of a polymerizable compound. As a compound containing a caprolactone structure, the description of paragraphs 0364 to 0382 of JP-A-2016-35068 can be referred to.

Further, as the polymerizable compound, the amino amide described in JP-A-48-41708, JP-A-53-37193, JP-A-2-332293, and JP-A-2-16765 The ester acrylate-based skeleton, which is described in JP-A-58-49860, JP-A-56-17654, JP-A-62-39417, JP-A-62-39417, and JP-A-62-39418 Amino acid group compounds are also preferred. In addition, the addition of an amine structure and/or a thioether structure in the molecule described in Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. A polymerizable compound can obtain a curable composition excellent in photosensitivity. As a commercial item, a urethane oligomer UAS-10, UAB-140 (made by Sanyo Kokusaku Pulp CO., LTD.), UA-7200 (Shin-Nakamura Chemical CO., LTD.), DPHA-40H (manufactured by Nippon Kayaku Co., LTD.), UA-306H, UA-306T, UA-306I, AH-600, T-600, and AI-600 (manufactured by KYOEISHA CHEMICAL CO., LTD).

Further, 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. Further, in the present specification, the SP value is determined by the Hoy method unless otherwise specified (HL Hoy Journal of Painting, 1970, Vol. 42, 76-118). ^Further , the SP value is shown by omitting the unit, but the unit is cal ^1/2 cm ^-3/2 .

Further, from the viewpoint of improving the development residue, the curable composition is preferably a polymerizable compound containing a cardo skeleton. The polymerizable compound containing a cardo skeleton is not limited, and examples thereof include Oncoat EX series (manufactured by NAGASE & CO., LTD.) and Ogsol (manufactured by Osaka Gas Chemicals Co., Ltd.).

[Photopolymerization initiator] The curable composition contains a photopolymerization initiator. The photopolymerization initiator is not particularly limited as long as it can initiate polymerization of the polymerizable compound, and a known photopolymerization initiator can be used. As the photopolymerization initiator, for example, it is preferred to have a sensitivity to an ultraviolet region to a visible region. Further, the polymerization initiator may be an active agent which generates a certain action with the photo-excited photosensitizer and generates a living radical, or may be an initiator which initiates cationic polymerization depending on the kind of the polymerizable compound. Further, the photopolymerization initiator preferably contains at least one compound having an extinction coefficient of at least about 50 moles in the range of about 300 nm to 800 nm (more preferably 330 nm to 500 nm).

The content of the photopolymerization initiator is preferably from 1 to 15% by mass based on the total solid content of the curable composition. When it is in the above range, 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 kinds of photopolymerization initiators are used at the same time, the total amount thereof is preferably in the above range.

In addition, the content of the photopolymerization initiator is preferably from 1 to 100 times by mass based on the content of the compound having a group having a polymerization inhibiting ability and a thiol group, and is more excellent in the effect of the present invention. From the viewpoint of viewpoint, 2.5 to 35 times is more preferable, and 2.5 to 25 times is further preferable.

Examples of the photopolymerization initiator include a halogenated hydrocarbon derivative (for example, a triazine skeleton, a oxadiazole skeleton, etc.), a mercaptophosphine compound such as a mercaptophosphine oxide, or a hexaarylbisimidazole. An anthracene compound such as an anthracene derivative, an organic peroxide, a sulfur compound, a ketone compound, an aromatic onium salt, a ketoxime ether, an aminoacetophenone compound, and p-hydroxyacetophenone. Examples of the halogenated hydrocarbon compound containing a triazine skeleton include a compound described in J. Lin et al., Bull. Chem. Soc. Japan, 42, 2924 (1969), and a compound described in British Patent No. 1,388,492. The compound described in Japanese Patent Publication No. 53-133428, the compound described in the specification of German Patent No. 3337024, and the compound described in J. Org. Chem.; 29, 1527 (1964) by FC Schaefer et al., JP-A-62-58241 The compound described in the publication, the compound described in JP-A-H05-281728, the compound described in JP-A-H05-34920, and the compound described in the specification of U.S. Patent No. 4,212,976.

Further, from the viewpoint of exposure sensitivity, it is selected from the group consisting of a trihalomethyltriazine compound, a diphenylethylenedione dimethyl ketal compound, an α-hydroxyketone compound, an α-amino ketone compound, a mercaptophosphine compound, Phosphine oxide compound, metallocene compound, hydrazine compound, triaryl imidazole dimer, terpenoid, benzothiazole compound, benzophenone compound, acetophenone compound and its derivative, cyclopentadiene-benzene-iron Compounds of the complexes and salts thereof, halogenated methyl oxadiazole compounds, and 3-aryl substituted coumarin compounds are preferred.

Wherein, a trihalomethyltriazine compound, an α-aminoketone compound, a mercaptophosphine compound, a phosphine oxide compound, an anthraquinone compound, a triallyl imidazole dimer, an anthraquinone compound, a benzophenone compound or an acetophenone More preferably, the compound is at least one compound selected from the group consisting of a trihalomethyltriazine compound, an α-aminoketone compound, an anthraquinone compound, a triallyl imidazole dimer, and a benzophenone compound. good.

In particular, when a curable composition is used for the production of a light-shielding film, since it is necessary to form a fine pattern into a clear shape, it is important to perform not only the curability but also the development of the residue in the unexposed portion. From this viewpoint, it is particularly preferable to use a ruthenium compound as a photopolymerization initiator. In particular, when a fine pattern is formed, stepwise exposure is used for exposure for curing, but the exposure machine may be damaged by halogen, and it is necessary to suppress the addition amount of the photopolymerization initiator to be low. Therefore, in consideration of these aspects, when a fine pattern is formed, it is particularly preferable to use a ruthenium compound as a photopolymerization initiator. As a specific example of the photopolymerization initiator, for example, paragraphs 0265 to 0268 of JP-A-2013-29760 can be referred to, and the contents are incorporated in the specification of the present application.

As the photopolymerization initiator, a hydroxyacetophenone compound, an aminoacetophenone compound, and a mercaptophosphine compound can also be preferably used. More specifically, for example, an aminoacetophenone-based initiator described in JP-A-10-291969 and a mercaptophosphine-based initiator described in Japanese Patent No. 4,258,899 can be used. As the hydroxyacetophenone compound, IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, and IRGACURE-127 (trade names: all manufactured by BASF Corporation) can be used. As the aminoacetophenone compound, IRGACURE-907, IRGACURE-369 or IRGACURE-379EG (trade name: all manufactured by BASF Corporation) which is a commercial item can be used. As the aminoacetophenone compound, a compound described in Japanese Laid-Open Patent Publication No. 2009-191179, which has an absorption wavelength and a long-wavelength source such as 365 nm or 405 nm, can also be used. As the mercaptophosphine compound, IRGACURE-819 or DAROCUR-TPO (trade name: all manufactured by BASF Corporation) which is a commercial item can be used.

<肟 compound> As a photopolymerization initiator, a ruthenium compound (an oxime-based initiator) is more preferably mentioned. As a photopolymerization initiator, a curable composition containing a ruthenium compound has more excellent exposure sensitivity. Further, since the ruthenium compound has high sensitivity and high polymerization efficiency, it is possible to harden the curable composition layer irrespective of the concentration of the colorant, and it is easy to design the concentration of the colorant to be high, which is preferable. Specific examples of the ruthenium compound include the compounds described in JP-A-2001-233842, the compounds described in JP-A-2000-80068, and the compounds described in JP-A-2006-342166. Examples of the hydrazine compound include 3-benzylideneoxyimidobutan-2-one, 3-ethyloxyiminobutane-2-one, and 3-propoxy oxyimine. Butyral-2-one, 2-ethoxymethoxyiminopentan-3-one, 2-benzylideneoxyimido-1-phenylpropan-1-one, 2-benzylformamide Oxyimido-1-phenylpropan-1-one, 3-(4-toluenesulfonyloxy)iminobutan-2-one, and 2-ethoxycarbonyloxyimido- 1-phenylpropan-1-one and the like. Also, JCS Perkin II (1979) PP.1653-1660, JCS Perkin II (1979) PP. 156-162, Journal of Photopolymer Science and Technology (1995) PP. 202-232, and Japanese specials are also mentioned. The compound described in each of the publications of JP-A-2006-342166, and JP-A-2006-342166, and JP-A-2006-342166. Among the commercially available products, IRGACURE-OXE01 (manufactured by BASF Corporation), IRGACURE-OXE02 (manufactured by BASF Corporation), IRGACURE-OXE03 (manufactured by BASF Corporation), or IRGACURE-OXE04 (manufactured by BASF Corporation) can also be preferably used. In addition, it is also possible to use TR-PBG-304 (manufactured by Changzhou Strong Electronic New Material Co., Ltd.), ADEKA ARKLS NCI-831 and ADEKA ARKLS NCI-930 (manufactured by ADEKA CORPORATION) or N-1919 (including carbazole oxime ester light) Starting agent (made by ADEKA CORPORATION)).

In addition, as the ruthenium compound other than the above, a compound described in JP-A-2009-519904, in which a carbazole is bonded to the N-position of the carbazole, and a hetero-substituent in the diphenyl ketone site, can be used. The compound described in the Japanese Patent Publication No. 2010-15025, and the ketone oxime described in Japanese Laid-Open Patent Publication No. 2009-131189 A compound described in Japanese Patent No. 7556910, which contains a triazine skeleton and an anthracene skeleton in the same molecule, and has a large absorption at 405 nm and has excellent sensitivity to a g-ray source, as described in JP-A-2009-221114. Compound; For example, paragraphs 0274 to 0275 of Japanese Laid-Open Patent Publication No. 2013-29760 can be preferably referred to in the specification of the present application. Specifically, as the hydrazine compound, a compound represented by the following formula (OX-1) is preferred. Further, the ruthenium compound in which the N-O bond of the ruthenium compound is (E) may be used, or the ruthenium compound of the (Z) form may be used, or a mixture of the (E) form and the (Z) form may be used.

[Chemical Formula 14]

In the formula (OX-1), R and B each independently represent a monovalent substituent, A represents a divalent organic group, and Ar represents an aryl group. As the substituent represented by R in the general formula (OX-1), a monovalent non-metal atomic group is preferred. The monovalent non-metal atomic group may, for example, be an alkyl group, an aryl group, a decyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a heterocyclic group, an alkylthiocarbonyl group or an arylthiocarbonyl group. Further, these groups may have one or more substituents. Further, the aforementioned substituent may be further substituted with another substituent. The substituent may, for example, be a halogen atom, an aryloxy group, an alkoxycarbonyl group or an aryloxycarbonyl group, a decyloxy group, a decyl group, an alkyl group or an aryl group. As the substituent represented by B in the general formula (OX-1), an aryl group, a heterocyclic group, an arylcarbonyl group or a heterocyclic carbonyl group is preferred. These groups may have one or more substituents. The substituent may be exemplified as the substituent. As the divalent organic group represented by A in the general formula (OX-1), an alkylene group, a cycloalkylene group or an extended alkynyl group having 1 to 12 carbon atoms is preferred. These groups may have one or more substituents. The substituent may be exemplified as the substituent.

As the photopolymerization initiator, a ruthenium compound containing a fluorine atom can also be used. Specific examples of the ruthenium compound containing a fluorine atom include the compounds described in JP-A-2010-262028, and the compounds 24 and 36 to 40 described in JP-A-2014-500852; Compound (C-3) described in the publication -164471; This content is incorporated in this specification.

As the photopolymerization initiator, compounds represented by the following general formulae (1) to (4) can also be used.

[Chemical Formula 15]

[Chemical Formula 16]

In the 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 a carbon number of 7 to 30. The aralkyl group, when R ¹ and R ² are a phenyl group, the phenyl groups may be bonded to each other to form a fluorenyl group, and R ³ and R ⁴ each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, and a carbon number of 6 An aryl group of ～30, an aralkyl group having 7 to 30 carbon atoms or a heterocyclic group having 4 to 20 carbon atoms, and X represents a direct bond or a carbonyl group.

Formula ^{(2), R 1, R 2, 1} , R 2, R ³ and R ⁴ are the same meaning as the general formula R (1) in R ³ and R ^4, R ⁵ represents -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 An atom or a hydroxyl group, and R ⁶ represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms or a heterocyclic group having 4 to 20 carbon atoms, and X represents a direct bond. Or a carbonyl group, a represents an integer of 0-4.

In the formula (3), R ¹ represents an alkyl group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group having 4 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms or an aralkyl group having 7 to 30 carbon atoms; 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 aralkyl group having 7 to 30 carbon atoms or a heterocyclic group having 4 to 20 carbon atoms, and X. Indicates a direct bond or a carbonyl group.

Formula (4), R ^{1, 1,} R ³ and R ⁴ are the same meaning as the general formula R (3) in R ³ and R ^4, R ⁵ represents ^{-R 6, -OR 6, -SR 6} , -COR ⁶ , -CONR ⁶ R ⁶ , -NR ⁶ COR ⁶ , -OCOR ⁶ , -COOR ⁶ , -SCOR ⁶ , -OCSR ⁶ , -COSR ⁶ , -CSOR ⁶ , -CN, halogen atom or hydroxyl group, R ⁶ The alkyl group having 1 to 20 carbon atoms, the aryl group having 6 to 30 carbon atoms, the aralkyl group having 7 to 30 carbon atoms or the heterocyclic group having 4 to 20 carbon atoms, X represents a direct bond or a carbonyl group, and a represents 0. An integer of ~4.

In the above formula (1) and formula (2), R ¹ and R ² are each independently a methyl group, an ethyl group, a n-propyl group, an isopropyl 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. It is preferred that X is a direct bond. In the above formulae (3) and (4), R ^{1 is} each independently a methyl group, an ethyl group, a n-propyl group, an isopropyl 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. It is preferred that X is a direct bond. Specific examples of the compound represented by the formula (1) and the formula (2) include, for example, the compounds described in paragraphs 0076 to 0079 of JP-A-2014-137466. This content is incorporated in this specification.

Specific examples of the ruthenium compound which can be preferably used in the curable composition are shown below.

[Chemical Formula 17]

The ruthenium compound is preferably one having a maximum absorption wavelength in a wavelength region of 350 nm to 500 nm, more preferably having a maximum absorption wavelength in a wavelength region of 360 nm to 480 nm, and further preferably having a higher absorbance at 365 nm and 405 nm. From the viewpoint of sensitivity, the molar absorptivity of the cerium compound at 365 nm or 405 nm is preferably from 1,000 to 300,000, more preferably from 2,000 to 300,000, still more preferably from 5,000 to 200,000. The molar absorption coefficient of the compound can be preferably measured by a known method, for example, by an ultraviolet-visible spectrophotometer (Cary-5 spctrophotometer manufactured by Varian Co., Ltd.) using ethyl acetate at a concentration of 0.01 g/L. The photopolymerization initiator can be used in combination of two or more kinds as needed.

[Colorant] The curable composition contains a colorant. The colorant is at least one selected from the group consisting of pigments and dyes. The content of the colorant is preferably 55% by mass or more based on the total solid content of the curable composition, and more preferably 60% by mass or more. When the content of the coloring agent is 55% by mass or more, the pattern shape of the cured film obtained by curing the curable composition is more excellent. In addition, the upper limit of the content of the coloring agent is not particularly limited, and is usually preferably 80% by mass or less based on the total solid content of the curable composition. When the content of the colorant is at most the upper limit value, the curable composition has more excellent coatability.

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

(Inorganic Pigment) The inorganic pigment is not particularly limited, and a known inorganic pigment can be used. Examples of the inorganic pigment include zinc white, lead white, zinc antimony white, titanium oxide, chromium oxide, iron oxide, precipitated barium sulfate and barite powder, lead red, iron oxide red, chrome yellow, and zinc yellow (zinc). Yellow one, zinc yellow two), ultramarine blue, Prussian blue (potassium iron ferrocyanide) zircon gray, yellow, chrome titanium yellow, chrome green, peacock color, Victoria green, iron blue (not related to Prussian blue) , vanadium zirconium blue, chrome tin red, manganese red, orange red and so on. Further, the black inorganic pigment may be a metal oxide containing one or two or more metal elements selected from the group consisting of Co, Cr, Cu, Mn, Ru, Fe, Ni, Sn, Ti, and Ag. , metal nitride.

Carbon black, titanium black, metal pigment, and the like (hereinafter, also referred to as "black pigment") are considered as an inorganic pigment from the viewpoint of obtaining a curable composition capable of forming a cured film having a high optical density even when the content is small. ) is better. The metal pigment may, for example, be a metal containing one or two or more metal elements selected from the group consisting of Nb, V, Co, Cr, Cu, Mn, Ru, Fe, Ni, Sn, Ti, and Ag. Oxide or metal nitride. The inorganic pigment preferably contains at least one selected from the group consisting of titanium nitride, titanium oxynitride, tantalum nitride, vanadium nitride, a metal pigment containing silver or tin, and a metal pigment containing silver and tin. It is more preferable to contain at least one selected from the group consisting of titanium nitride, titanium oxynitride, tantalum nitride, and vanadium nitride. Further, as the inorganic pigment, carbon black can also be used. Specific examples of the carbon black include inorganic pigments such as C.I. Pigment Black 7 which are commercially available products, but are not limited thereto.

In the curable composition, in addition to the pigment described as a black pigment, a pigment having infrared absorbing property can also be used. As the pigment having infrared absorbing property, a tungsten compound, a metal boride or the like is preferable, and among them, a tungsten compound is preferable from the viewpoint of excellent light blocking properties in the wavelength of the infrared region. From the viewpoint of excellent light transmittance in the light absorption wavelength region and the visible light region of the photopolymerization initiator related to the curing efficiency by exposure, a tungsten compound is preferable.

These pigments may be used in combination of two or more kinds, and may be used together with the dye described later. In order to adjust the color tone and to improve the light-shielding property in a desired wavelength region, for example, a color pigment such as red, green, yellow, orange, purple, or blue or a dye as described later may be mixed with a black or infrared light-shielding pigment. kind. It is preferred to mix a red pigment or a dye, or a violet pigment or dye with a black or infrared light-blocking pigment, and it is more preferable to mix the red pigment with a black or infrared light-shielding pigment. Further, a near-infrared ray absorbing agent or an infrared ray absorbing agent described later may be added.

The black pigment preferably contains titanium black and/or ruthenium oxynitride. Titanium black contains black particles of titanium atoms. Low-order titanium oxide, titanium oxynitride or titanium nitride is preferred. The titanium black particles can be modified as needed in order to improve dispersibility, suppress cohesiveness, and the like. The coating can be carried out by cerium oxide, titanium oxide, cerium oxide, aluminum oxide, magnesium oxide or zirconium oxide, and can also be treated with a water-repellent substance as disclosed in JP-A-2007-302836. Titanium black is typically titanium black particles, and it is preferred that each of the particles has a smaller primary particle diameter and an average primary particle diameter. The bismuth oxynitride is also the same. Specifically, it is preferred that the average primary particle diameter is in the range of 10 nm to 45 nm.

Further, the average primary particle diameter of the pigment can be measured by a transmission electron microscope (TEM). As the transmission electron microscope, for example, a transmission microscope HT7700 manufactured by Hitachi High-Technologies Corporation can be used. The maximum length of the particle image obtained by the transmission electron microscope (Dmax: the maximum length of the two points on the contour of the particle image) and the maximum length vertical length (DV-max: two straight lines parallel to the maximum length) When the image is sandwiched, the shortest length between the two straight lines is vertically connected, and the multiplied average value (Dmax × DV - max) 1/2 is taken as the particle diameter. The particle diameter of 100 particles was measured by this method, and the arithmetic mean value thereof was defined as the average particle diameter, and was used as the average primary particle diameter of the pigment.

The specific surface area of titanium black and lanthanum oxynitride is not particularly limited, and the water repellency after surface treatment of titanium black and lanthanum oxynitride has a predetermined property by a BET (Brunauer, Emmett, Teller) method. is 5m ² / g or more and 150m ² / g or less is preferred, 20m ² / g or more and 120m ² / g or less is more preferred. Examples of commercially available products of titanium black include titanium blacks 10S, 12S, 13R, 13M, 13M-C, 13R, 13R-N, 13M-T (trade name, manufactured by Mitsubishi Materials Corporation), and Tilack D (products). Name, manufactured by Ako Kasei Co., Ltd., titanium nitride 50 nm (trade name, manufactured by Wako Pure Chemical Industries, Ltd.), and the like.

As the coloring agent, titanium oxynitride, titanium nitride or cerium oxynitride is preferably used, and titanium nitride or cerium oxynitride is more preferable, and cerium oxynitride is preferable from the viewpoint that the obtained cured film is more excellent in moisture resistance. It is further preferred. This is considered to be hydrophobic.

Further, it is also preferable to contain titanium black as a dispersion containing titanium black and Si atoms. In this embodiment, the titanium black is contained as a dispersion in the curable composition, and the content ratio (Si/Ti) of the Si atom to the Ti atom in the dispersion is preferably 0.05 or more in terms of mass. More preferably, it is 0.05 to 0.5, and further preferably 0.07 to 0.4. In the above-mentioned dispersion, both the state in which titanium black is primary particles and the state in which aggregates (secondary particles) are present are included. In order to change the content ratio (Si/Ti) of the dispersion (for example, 0.05 or more), the following method can be used. First, a dispersion is obtained by dispersing titanium oxide and cerium oxide particles by a disperser, and the dispersion is subjected to a reduction treatment at a high temperature (for example, 850 to 1000 ° C), whereby titanium black particles are used as a main component. It also contains a dispersion of Si and Ti. The above reduction treatment can also be carried out in an atmosphere of a reducing gas such as an amine. TTO-51N (trade name, manufactured by Ishihara Sangyo Kaisha, Ltd.), etc. are mentioned as a titanium oxide. As a commercial item of the cerium oxide particle, AEROSIL (registered trademark) 90, 130, 150, 200, 255, 300, 380 (trade name, manufactured by Evonik Japan Co., Ltd.), etc. are mentioned. A dispersing agent can also be used in the dispersion of the titanium oxide and the cerium oxide particles. The dispersing agent can be mentioned in the column of the dispersing agent mentioned later. The above dispersion can also be carried out in a solvent. Examples of the solvent include water and an organic solvent. It can be mentioned in the column of the organic solvent mentioned later. Titanium black having a ratio (Si/Ti) of, for example, 0.05 or more can be produced, for example, by the method described in paragraph [0005] and paragraphs [0016] to [0021] of JP-A-2008-266045.

By adjusting the content ratio (Si/Ti) of Si atoms and Ti atoms in the dispersion containing titanium black and Si atoms to a preferred range (for example, 0.05 or more), a curable composition containing the dispersion is used. When the cured film is formed, the residue derived from the curable composition outside the region where the cured film is formed is reduced. Further, the residue includes a component derived from a curable composition such as titanium black particles or a resin component. Although the reason for the reduction of the residue is not clear, the above-mentioned dispersion has a tendency to become a small particle diameter (for example, a particle diameter of 30 nm or less), and the component of the dispersion containing Si atoms is increased, thereby The adsorption of the membrane to the substrate is reduced. It is inferred that this phenomenon contributes to improvement in development removability of an uncured curable composition (particularly, titanium black) when a cured film is formed. Since titanium black is excellent in light-shielding property of light in a wide range of wavelengths from ultraviolet light to infrared light, the above-mentioned dispersion containing titanium black and Si atoms (content ratio (Si/Ti) is 0.05 or more in mass conversion). The cured film formed by the above is preferable to exhibit excellent light blocking properties. In addition, the content ratio (Si/Ti) of the Si atom to the Ti atom in the dispersion can be, for example, the method (1-1) or the method (1-2) described in paragraph 0033 of JP-A-2013-249417. Make measurements. When it is judged whether the content ratio (Si/Ti) of the Si atom and the Ti atom in the dispersion is 0.05 or more, the content of the dispersion contained in the cured film obtained by curing the curable composition can be utilized in Japan. Method (2) described in paragraph 0035 of Japanese Patent Publication No. 2013-249417.

Among the dispersions containing titanium black and Si atoms, titanium black can be used as described above. In the dispersion, one or two or more kinds of composite oxides such as Cu, Fe, Mn, V, and Ni, cobalt oxide, iron oxide, and carbon black may be combined with titanium black in order to adjust dispersibility, coloring property and the like. Black pigment such as aniline black is used. In this case, it is preferred that the dispersion containing titanium black accounts for 50% by mass or more of all the dispersions. In the dispersion, in order to adjust the light-shielding property or the like, other coloring agents (organic pigments and/or dyes, etc.) may be used together with titanium black as needed within the range which does not impair the effects of the present invention. Hereinafter, the material used when introducing Si atoms into the dispersion will be described. When Si atoms are introduced into the dispersion, a Si-containing substance such as ruthenium dioxide may be used. Examples of the cerium oxide which can be used include precipitated cerium oxide, smoky cerium oxide, colloidal cerium oxide, and synthetic cerium oxide. These may be appropriately selected and used. Further, when the particle diameter of the cerium oxide particles is smaller than the film thickness at the time of forming the cured film, the light-shielding property is further excellent. Therefore, it is preferable to use fine-particle type cerium oxide as the cerium oxide particles. In addition, as an example of the particulate type of cerium oxide, for example, cerium oxide described in paragraph 0039 of JP-A-2013-249417, the contents of which are incorporated herein by reference.

Further, as the pigment, a tungsten compound or a metal boride can also be used. Hereinafter, the tungsten compound and the metal boride will be described in detail. A tungsten compound and/or a metal boride can be used in the curable composition. The tungsten compound and the metal boride are relatively high in absorption with respect to infrared rays (light having a wavelength of about 800 to 1200 nm) (that is, light blocking property (shielding property) with respect to infrared rays), and absorption is low with respect to visible light. Infrared shielding material. Therefore, the curable composition contains a tungsten compound and/or a metal boride, and can form a pattern having high light-shielding property in the infrared region and high light transmittance in the visible light region. The tungsten compound and the metal boride are less absorbed for light having a shorter wavelength than the visible region used for exposure of a high-pressure mercury lamp, KrF, ArF or the like for forming an image. Therefore, an excellent pattern is obtained by combining the above-described polymerizable compound, photopolymerization initiator, and alkali-soluble resin described later, and in the pattern formation, the development residue can be more preferably suppressed.

The tungsten compound is preferably a tungsten oxide-based compound, a tungsten boride-based compound, or a tungsten sulfide-based compound, and a tungsten oxide-based compound represented by the following general formula (composition formula) (I) is preferable. M _x W _y O _z (I) M represents a metal, W represents tungsten, and O represents oxygen. 0.001 ≤ x / y ≤ 1.1 2.2 ≤ z / y ≤ 3.0

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

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

When the x/y ratio is 0.001 or more, infrared rays can be sufficiently shielded, and by the x/y system being 1.1 or less, it is possible to more reliably prevent the formation of an impurity phase in the tungsten compound. When z/y is 2.2 or more, the chemical stability of the material can be further improved, and by z/y being 3.0 or less, infrared rays can be sufficiently shielded.

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

The tungsten compound is preferably fine particles. The average primary particle diameter of the tungsten fine particles is preferably 800 nm or less, more preferably 400 nm or less, and further preferably 200 nm or less. Since the average primary particle diameter is in this range, the tungsten fine particles are less likely to block visible light due to light scattering, so that the light transmittance in the visible light region can be made more reliable. The average primary particle diameter is preferably as small as possible from the viewpoint of avoiding light scattering. However, the average primary particle diameter of the tungsten fine particles is usually 1 nm or more from the viewpoint of ease of handling during production and the like.

Two or more kinds of tungsten compounds can be used.

The tungsten compound can be obtained as a commercial product. When the tungsten compound is, for example, a tungsten oxide-based compound, the tungsten oxide-based compound can be obtained by heat-treating the tungsten compound in an inert gas atmosphere or a reducing gas atmosphere (see Japanese Patent). Bulletin No. 4096205). The tungsten oxide-based compound can also be obtained as, for example, a dispersion of tungsten fine particles such as YMF-02 manufactured by Sumitomo Metal Mining Co., Ltd.

As the metal boride, lanthanum boride may be mentioned (LaB _6), praseodymium boride (PrB _6), neodymium boride (NdB _6), cerium boride (CeB _6), yttrium boride (YB _6), boride Titanium (TiB ₂ ), zirconium boride (ZrB ₂ ), hafnium boride (HfB ₂ ), vanadium boride (VB ₂ ), tantalum boride (TaB ₂ ), chromium boride (CrB, CrB ₂ ), boride One or two or more kinds of molybdenum (MoB ₂ , Mo ₂ B ₅ , MoB) and tungsten boride (W ₂ B ₅ ), and lanthanum boride (LaB ₆ ) are preferred.

Metal boride-based fine particles are preferred. 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. Since the average primary particle diameter is in this range, the metal boride fine particles are less likely to block visible light due to light scattering, so that the light transmittance in the visible light region can be made more reliable. From the viewpoint of avoiding light scattering, the average primary particle diameter is preferably as small as possible, but the average primary particle diameter of the metal boride fine particles is usually 1 nm or more from the viewpoint of ease of handling during production and the like.

Two or more kinds of metal borides can be used.

The metal boride can be obtained as a commercial product, and can also be obtained, for example, as a dispersion of metal boride fine particles such as KHF-7 manufactured by Sumitomo Metal Mining Co., Ltd.

(Titanium Nitride-Containing Particles) As the inorganic pigment, titanium nitride-containing particles can also be used. When producing titanium 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 methods, a thermal plasma method is preferable from the viewpoint of a small amount of impurities being mixed, an angle at which the particle diameter is easily matched, and an angle at which productivity is high. Examples of the method of generating the thermal plasma include DC arc discharge, multi-phase arc discharge, high-frequency (RF) plasma, and mixed plasma, etc., and high-frequency plasma with less impurities mixed from the electrodes is used. good. As a specific production method of the titanium nitride-containing fine particles by the thermal plasma method, for example, titanium powder is evaporated by high-frequency thermal plasma, nitrogen is introduced into the device as a carrier gas, and titanium is cooled by a cooling process. The powder is nitrided to synthesize a method containing titanium nitride particles. Further, the thermal plasma method is not limited to the above.

The method for producing the titanium nitride-containing particles is not particularly limited, and the production method described in paragraphs <0037> to <0089> of International Publication No. 2010/147098 can be referred to. For example, it can be manufactured as follows, that is, in place of the Ag powder of International Publication No. 2010/147098, a component containing Fe and/or a component containing Si described later is used, and the component and the titanium powder material (titanium particles) are mixed as The raw material is used to produce titanium nitride-containing particles contained in the curable composition.

The titanium powder material (titanium particles) used in the production of the titanium nitride-containing particles is preferably of high purity. The titanium powder material is not particularly limited, and those having a purity of the titanium element of 99.99% or more are preferable, and those having a purity of 99.999% or more are more preferable.

The titanium powder material (titanium particles) used in the production of the titanium nitride-containing particles may contain atoms other than titanium atoms. Other atoms which may be contained in the titanium powder material include, for example, Fe atoms and Si atoms. When the titanium powder material contains Fe atoms, the content of Fe atoms is preferably more than 0.001% by mass based on the total mass of the titanium powder material. When the titanium powder material contains Si atoms, the content of Si atoms is preferably more than 0.002% by mass and less than 0.3% by mass based on the total mass of the titanium powder material, more preferably 0.01 to 0.15% by mass, and still more preferably 0.02 to 0.1% by mass. good. When the content of Si atoms exceeds 0.002% by mass, the pattern formation property of the cured film is further improved. By the content of Si atoms being less than 0.3% by mass, the polarity of the outermost layer of the titanium nitride-containing particles obtained is more stabilized. From this, it is considered that the dispersing agent when the titanium nitride-containing particles are dispersed is optimized for the adsorptivity of the titanium nitride-containing particles, and the undispersed material containing the titanium nitride particles is reduced, thereby suppressing the effect of generating particles. The water content of the titanium powder material (titanium particles) used in the production of the titanium nitride-containing particles is preferably less than 1% by mass based on the total mass of the titanium powder material, more preferably less than 0.1% by mass, and substantially not included. Further preferred.

By obtaining the titanium nitride-containing particles by the thermal plasma method, the diffraction angle 2θ (described later in detail) derived from the peak of the (200) plane when the CuKα ray is used as the X-ray source can be easily adjusted to more than 42.6°. And the range of 43.5 ° or less.

The method of containing the Fe atom by the titanium nitride-containing particles is not particularly limited, and examples thereof include a method of introducing Fe atoms at the stage of obtaining titanium particles (titanium powder) used as a raw material of the titanium nitride-containing particles. . More specifically, when titanium is produced by a reduction (Kroll) method or the like, a material containing Fe atoms such as stainless steel (SUS) is used as a reaction container, or a material for a press machine and a pulverizer for crushing titanium is used. If Fe atoms are contained, Fe atoms can be adhered to the surface of the titanium particles. When a thermal plasma method is used in the production of titanium nitride-containing particles, components such as Fe particles and Fe oxide are added in addition to titanium particles as a raw material, and these are nitrided by a thermal plasma method. The titanium nitride-containing particles contain Fe atoms. The Fe atoms contained in the titanium nitride-containing particles may be ions, metal compounds (including complex compounds), intermetallic compounds, alloys, oxides, composite oxides, nitrides, nitrogen oxides, sulfides, and sulfur oxides. Any form is included. The Fe atoms contained in the titanium nitride-containing particles may exist as impurities at inter-lattice positions, or may exist as impurities in the amorphous state at the grain boundaries.

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 based on the total mass of the titanium nitride-containing particles. Among them, 0.01 to 0.2% by mass is more preferable, and 0.02 to 0.1% by mass is further more preferable. The content of Fe atoms in the titanium nitride-containing particles can be measured by ICP (Inductively Coupled Plasma) luminescence spectrometry.

The titanium nitride-containing particles further preferably contain Si atoms (germanium atoms). Thereby, the pattern formability of the cured film is further improved. The reason why the pattern formability is improved by containing Si atoms is considered to be the same as the above-described Fe atoms. The content of Si atoms in the titanium nitride-containing particles is preferably more than 0.002% by mass and less than 0.3% by mass based on the total mass of the titanium nitride-containing particles, more preferably 0.01 to 0.15% by mass, and still more preferably 0.02 to 0.1% by mass. Preferably. The content of Si atoms in the titanium nitride-containing particles can be measured by the same method as the above Fe atoms.

The method of containing Si atoms in the titanium nitride-containing particles is not particularly limited, and examples thereof include a method of introducing Si atoms at the stage of obtaining the titanium particles (titanium powder) used as a raw material containing titanium nitride particles, and the like. . More specifically, when titanium is produced by a reduction method or the like, a material containing Si atoms is used as a reaction container, or a material containing a Si atom is used as a material for a press machine and a pulverizer for crushing titanium. The Si atoms are attached to the surface of the titanium particles. When a thermal plasma method is used in the production of titanium nitride-containing particles, components such as Si particles and Si oxide are added in addition to titanium particles as a raw material, and these are nitrided by a thermal plasma method. The titanium nitride-containing particles contain Si atoms. The Si atoms contained in the titanium nitride-containing particles may be ions, metal compounds (including complex compounds), intermetallic compounds, alloys, oxides, composite oxides, nitrides, nitrogen oxides, sulfides, and sulfur oxides. Any form is included. The Si atoms contained in the titanium nitride-containing particles may exist as impurities at inter-lattice positions, or may exist as impurities in the amorphous state at the grain boundaries.

The content of the titanium atom (Ti atom) in the titanium nitride-containing particles is preferably from 10 to 85% by mass, more preferably from 15 to 75% by mass, even more preferably from 20 to 70% by mass based on the total mass of the titanium nitride-containing particles. Further preferred. The content of Ti atoms in the titanium nitride-containing particles can be measured by ICP emission spectrometry. The content of the nitrogen atom (N atom) in the titanium nitride-containing particles is preferably from 3 to 60% by mass, more preferably from 5 to 50% by mass, even more preferably from 10 to 40% by mass, based on the total mass of the titanium nitride-containing particles. Further preferred. The content of the nitrogen atom can be analyzed by an inert gas fusion thermal conductivity method. The titanium nitride-containing particles contain titanium nitride (TiN) as a main component, and are usually formed when oxygen is mixed during synthesis and when the particle diameter is small. However, a part of oxygen may be contained by oxidation of the surface of the particles or the like. atom. The content of the oxygen atom in the titanium nitride-containing particles is preferably from 1 to 40% by mass, more preferably from 1 to 35% by mass, even more preferably from 5 to 30% by mass, based on the total mass of the titanium nitride-containing particles. The content of oxygen atoms can be analyzed by an inert gas fusion infrared absorption method.

The titanium nitride-containing particles have a specific surface area of preferably 5 to 100 m ² /g, more preferably 10 to 60 m ² /g, from the viewpoint of dispersion stability and light-shielding property. 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. The composite fine particles are particles in which titanium nitride particles are combined with metal fine particles or in a state of being highly dispersed. Here, "composite" means that the particles are composed of two components of titanium nitride and metal, and the "highly dispersed state" means that the titanium nitride particles and the metal particles are individually present, and the particles of a small amount of components are not aggregated and uniform. And dispersed in the same way. The metal fine particles are not particularly limited, and examples thereof include copper, silver, gold, platinum, vanadium, nickel, tin, cobalt, ruthenium, osmium, iridium, osmium, manganese, molybdenum, tungsten, ruthenium, osmium, and calcium. At least one of titanium, tantalum, niobium and lead, and alloys thereof. Wherein at least one selected from the group consisting of copper, silver, gold, platinum, palladium, nickel, tin, cobalt, rhodium and ruthenium, and alloys thereof are preferably selected from the group consisting of copper, silver, gold, platinum, and tin, and At least one of these alloys is more preferred. Silver is preferred from the viewpoint of further excellent moisture resistance. The content of the metal fine particles in the titanium nitride-containing particles is preferably 5 to 50% by mass, more preferably 10 to 30% by mass, based on the total mass of the titanium nitride-containing particles.

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

When the X-ray diffraction spectrum of the titanium compound is measured by using the CuKα ray as an X-ray source, the peak having the strongest intensity, with respect to TiN, the peak derived from the (200) plane appears in the vicinity of 2θ=42.5°, and the TiO is derived from (200). The peak of the surface appears near 2θ=43.4°. On the other hand, although it is not the strongest peak, regarding the anatase type TiO ₂ , a peak derived from the (200) plane is observed in the vicinity of 2θ=48.1°, and in the vicinity of 2θ=39.2° in the rutile type TiO ₂ . A peak derived from the (200) plane was observed. Thereby, the more the crystal state containing a large amount of oxygen atoms, the more the peak position shifts toward the high angle side with respect to 42.5°.

From the viewpoint of the temporal stability of the particles, the diffraction angle 2θ derived from the peak of the (200) plane of the titanium nitride-containing particles is more preferably 42.6° and less than 43.5°, and is excellent in the process margin at the time of production. In view of the above, 42.7° or more and less than 43.5° is more preferable, and from the viewpoint of excellent reproducibility of particle properties, 42.7° or more and less than 43.4° is further preferable. When titanium oxide TiO ₂ is contained as a subcomponent, the peak derived from anatase TiO ₂ (101) appears as a peak with the strongest intensity, and appears at a peak of 2θ=25.3°, and is derived from the peak of rutile-type TiO ₂ (110). Now 2θ = 27.4°. However, since TiO ₂ is white, it is a factor which reduces the light-shielding property of a black matrix, and it is preferable to fall to the extent which it is not observed as a peak.

The crystallite size constituting the titanium nitride-containing particles can be obtained by the half width of the X-ray diffraction peak, and is calculated by the Scherrer formula.

As the crystallite size, 20 nm or more is preferable, and 20 to 50 nm is more preferable. 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 has a blue to blue-violet color having a peak wavelength of 475 nm or less, and can obtain both high light-shielding property and ultraviolet light sensitivity. Black matrix. When the crystallite size is 20 nm or more, the ratio of the surface of the active particles to the volume of the particles becomes small, which is a good balance, and the titanium nitride-containing particles are more excellent in heat resistance and/or durability.

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

The method for producing the metal-containing nitride particles containing the atom A is not particularly limited, and a known method can be used. When the metal nitride-containing particles are produced, a gas phase reaction method is usually used, and specific examples thereof include an electric furnace method and a thermal plasma method. Among these methods, a thermal plasma method is preferable from the viewpoint of a small amount of impurities being mixed, an angle at which the particle diameter is easily matched, and an angle at which productivity is high. The specific production method of the metal-containing nitride particles by the thermal plasma method is, for example, a metal particle production apparatus (the same apparatus as the "black composite particle production apparatus" described later). The metal fine particle manufacturing apparatus includes, for example, a plasma torch that generates hot plasma, a material supply device that supplies metal raw material powder into the plasma torch, a chamber that includes a cooling function, and a cyclone that classifies the generated metal fine particles and A recovery unit for recovering metal particles. In the present specification, the metal fine particles mean particles containing a metal element having a primary particle diameter of 20 nm to 40 μm.

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

<Dye> As a dye, for example, JP-A-64-90403, JP-A-64-91102, JP-A-1-94301, JP-A-6-11614, and Japan US Pat. No. 2, 592, 207, U.S. Patent No. 4,808, 510, U.S. Patent No. 5, 568, 920, U.S. Patent No. 5, 560, 950, U.S. Patent No. 5, 505, 950, Japanese Patent Laid-Open No. Hei 5- 333 207, Japanese Patent Laid-Open No. Hei 6-35183, and Japanese Patent Laid-Open No. Hei 6-51115 The pigment disclosed in Japanese Laid-Open Patent Publication No. Hei 6-194928 or the like. If it is distinguished as a chemical structure, a pyrazole azo compound, a pyrrolemethylene compound, a aniline azo compound, a triphenylmethane compound, an anthraquinone compound, a stilbene compound or an oxophthalate (Oxonol) can be used. A compound, a pyrazolotriazole azo compound, a pyridone azo compound, a cyanine compound, a phenothiazine compound, a pyrrolopyrazole-imine compound, or the like. As the dye, a dye multimer can also be used. The compound described in JP-A-2011-041925, and JP-A-2013-041097 is exemplified as the dye-polymer. As a commercially available product, a polymerizable dye having a polymerizable property in the molecule can be used. For example, an RDW series manufactured by Wako Pure Chemical Industries, Ltd. can be mentioned.

<Infrared Absorber> The colorant may further contain an infrared absorbing agent. The infrared absorbing agent means a compound having absorption in a wavelength region in the infrared region (preferably having a wavelength of 650 to 1300 nm). The infrared ray absorbing agent is preferably a compound having a maximum absorption wavelength in a wavelength region of a wavelength of 675 to 900 nm. Examples of the coloring agent having such a spectral characteristic include a pyrrolopyrrole compound, a copper compound, a cyanine compound, a phthalocyanine compound, an iminium compound, a thiol complex compound, and a transition metal oxide compound. A squaraine compound, a naphthalocyanine compound, a quartetene compound, a dithiol metal complex compound, a ketoxime compound, and the like. As the phthalocyanine compound, the naphthalocyanine compound, the iminium compound, the cyanine compound, the squaraine compound, and the ketoxime compound, the compound disclosed in paragraphs 0010 to 0081 of JP-A-2010-111750 can be used. In the manual. The cyanine compound can be referred to, for example, "Functional Coloring, Daewon Shinshin / Matsugata Ken / Kita Echiro Jiro / Hiratsuka Hiroshi, kodansha Scientific Ltd.", which is incorporated herein by reference.

As the coloring agent having the above-mentioned spectral characteristics, the compound disclosed in paragraphs 0004 to 0016 of JP-A-2007-164729, and/or the compound disclosed in paragraphs 0027 to 0062 of JP-A-2002-146254 can be used. A near-infrared ray absorbing particle containing a crystallite containing an oxide of Cu and/or P and having a number average agglomerated particle diameter of 5 to 200 nm, as disclosed in paragraphs 0034 to 0067 of JP-A-2011-164583.

The compound having a maximum absorption wavelength in a wavelength region of a wavelength of 675 to 900 nm is preferably at least one selected from the group consisting of a cyanine compound, a pyrrolopyrrole compound, a squarylium compound, a phthalocyanine compound, and a naphthalocyanine compound. . The infrared absorbing agent is preferably a compound which dissolves 1% by mass or more in water at 25 ° C, and more preferably dissolves 10% by mass or more of the compound in water at 25 ° C. Solvent resistance is optimized by using such a compound. The pyrrolopyrrole compound can be referred to in paragraphs 0049 to 0062 of JP-A-2010-222557, which is incorporated herein by reference. The cyanine compound and the squarylium compound can be referred to paragraphs 0022 to 0063 of the International Publication No. 2014/088063, paragraphs 0053 to 0118 of the International Publication No. 2014/030628, and paragraphs 0028 to 0074 of JP-A-2014-59550. Paragraphs 0013 to 0091 of the International Publication No. 2012/169447, paragraphs 0019 to 0033 of JP-A-2015-176046, and paragraphs 0053 to 0099 of JP-A-2014-63144, and JP-A-2014-52431 Paragraphs 0085 to 0150, paragraphs 0076 to 0124 of JP-A-2014-44301, paragraphs 0045 to 0078 of JP-A-2012-8532, and paragraphs 0027 to 0067 of JP-A-2015-172102, Japan. Paragraphs 0029 to 0067 of the Japanese Patent Publication No. 2015-172004, paragraphs 0029 to 0085 of JP-A-2015-40895, paragraphs 0022 to 0036 of JP-A-2014-126642, and paragraph 0011 of JP-A-2014-148567 ～0017, paragraphs 0010 to 0025 of JP-A-2015-157893, paragraphs 0013 to 0026 of JP-A-2014-095007, paragraphs 0013 to 0047 of JP-A-2014-80487, and JP-A-2013- 227403 Publication in paragraphs 0007 to 0028, etc., the content is incorporated in the present specification.

The infrared absorbing agent is preferably at least one selected from the group consisting of compounds represented by the following general formulae 1 to 3. Formula 1 [Chemical Formula 18] In the formula 1, A ¹ and A ² each independently represent an aryl group, a heteroaryl group or a group represented by the following formula 1-A. Formula 1-A [Chemical Formula 19] In the formula 1-A, Z ^1A represents a non-metal atomic group forming a nitrogen-containing hetero ring, R ^2A represents an alkyl group, an alkenyl group or an aralkyl group, d represents 0 or 1, and a wavy line represents a linking bond. Formula 2 [Chemical Formula 20] In the formula 2, R ^1a and R ^1b each independently represent an alkyl group, an aryl group or a heteroaryl group, and R ² to R ⁵ each independently represent a hydrogen atom or a substituent, and R ² and R ³ , R ⁴ and R ^{5 respectively.} Rings may be bonded to form a ring, and R ⁶ and R ⁷ each independently represent a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group, a -BR ^A R ^B or a metal atom, and R ^A and R ^B each independently represent a hydrogen 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 . Formula 3 [Chemical Formula 21] In the formula 3, Z ¹ and Z ² are each independently a non-metal atomic group forming a nitrogen-containing heterocyclic ring which may be a condensed ring of 5 or 6 members, and R ¹⁰¹ and R ¹⁰² each independently represent an alkyl group, an alkenyl group or an alkyne group. a group, an aralkyl group or an aryl group, L ¹ represents a methine chain containing an odd number of methine groups, a and b are each independently 0 or 1, and when a is 0, a carbon atom and a nitrogen atom are bonded by a double bond. When b is 0, a carbon atom and a nitrogen atom are bonded by a single bond. When a moiety represented by Cy is a cation moiety, X ¹ represents an anion, and c represents a number required to maintain a balance of charges, in which Cy is When the site indicated is an anion moiety, X ¹ represents a cation, and c represents a number required to maintain the balance of charges. When the charge of the moiety represented by Cy in the formula is neutralized in the molecule, c is 0.

<Pigment Derivative> The curable composition may contain a pigment derivative. The pigment derivative is preferably a compound having a structure in which a part of the organic pigment is substituted with an acidic group, a basic group or an phthalimine methyl group. As the pigment derivative, a pigment derivative having an acidic group or a basic group is preferred from the viewpoint of dispersibility and dispersion stability of the colorant. It is especially preferred that the pigment derivative has a basic group. The combination of a resin (dispersant) and a pigment derivative to be described later is preferably a combination of a dispersant which is an acidic dispersant and a pigment derivative which has a basic group.

Examples of the organic pigment constituting the pigment derivative include a dioxopyrrolopyrrole pigment, an azo pigment, a phthalocyanine pigment, an anthraquinone pigment, a quinacridone pigment, and a dioxazine pigment. Examples include a purple ring ketone pigment, an anthraquinone pigment, a thioindole pigment, an isoporphyrin pigment, an isoindolinone pigment, a quinophthalone pigment, a smectite pigment, and a metal complex pigment. As the acidic group which the pigment derivative has, a sulfonic acid group or a carboxylic acid group or a salt thereof is preferred, a carboxylic acid group or a sulfonic acid group is more preferable, and a sulfonic acid group is further preferable. As the basic group of the pigment derivative, an amine group is preferred, and a tertiary amino group is more preferred.

When the curable composition contains a pigment derivative, the content of the pigment derivative is preferably from 1 to 30% by mass, more preferably from 3 to 20% by mass, based on the mass of the pigment. The pigment derivative may be used singly or in combination of two or more.

[Optional Component] <Solvent> The curable composition preferably contains a solvent. Examples of the solvent include water and an organic solvent. It is preferred that the curable composition contains an organic solvent. When the curable composition contains a solvent, the solid content of the curable composition is preferably 10 to 40% by mass. When the solid content of the curable composition is at least the lower limit value, the viscosity is low and the coatability is optimized. Moreover, the stability over time is optimized by lowering the concentration of the compound having higher reactivity. In addition, when the solid content of the curable composition is at most the upper limit value, the viscosity is kept at a low temperature, and the coatability is optimized. Moreover, the coloring agent having a heavier specific gravity is less likely to settle and the stability over time is optimized.

(Organic solvent) When the curable composition contains an organic solvent, the content of the organic solvent is preferably from 60 to 90% by mass based on the total mass of the curable composition. Further, the organic solvent may be used singly or in combination of two or more. When two or more organic solvents are used at the same time, the total amount thereof is preferably in the above range.

The organic solvent is not particularly limited, and examples thereof include acetone, methyl ethyl ketone, cyclohexane, dichloroethane, tetrahydrofuran, toluene, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and ethylene glycol dimethyl ether. , propylene glycol monomethyl ether, propylene glycol monoethyl ether, acetamidine acetone, 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 alum , γ-butyrolactone, ethyl acetate, butyl acetate, methyl lactate and ethyl lactate.

When two or more organic solvents are contained, it is selected from the group consisting of methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, and diethylene glycol. Dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclopentanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol Two or more of the group of monomethyl ether and propylene glycol monomethyl ether acetate is preferable.

(Water) The curable composition may contain water. The water may be intentionally added, or may be inevitably 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 based on the total mass of the curable composition. When the content of water is within the above range, pinholes are suppressed from occurring when the cured film is formed, and the moisture resistance of the cured film is improved.

<Dispersant> The curable composition preferably contains a dispersant. The dispersant helps to increase the dispersibility of the colorant. In the present specification, the dispersant is a component different from the binder resin described later.

When the curable composition contains a dispersing agent, the content of the dispersing agent is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and even more preferably 5% by mass or more, based on the total solid content of the curable composition. 11% by mass or more is particularly preferable, 17% by mass or more is most preferable, 50% by mass or less is more preferable, and 30% by mass or less is more preferable, and 22% by mass or less is more preferable. When the content of the dispersant is 17% by mass or more, the pattern shape of the cured film obtained by curing the curable composition is more excellent. The dispersing agent may be used alone or in combination of two or more. When two or more kinds of dispersing agents are used at the same time, the total amount is preferably in the above range.

As the dispersing agent, for example, a known pigment dispersing agent can be appropriately selected and used. Among them, a polymer compound is preferred. The dispersing agent may, for example, be a polymer dispersing agent (for example, polyamine amine and a salt thereof, a polycarboxylic acid and a salt thereof, a high molecular weight unsaturated acid ester, a modified polyurethane, a modified polyester, Modified poly(meth)acrylate, (meth)acrylic copolymer, naphthalenesulfonic acid formaldehyde condensate), polyoxyethylene alkyl phosphate, polyoxyethylene alkylamine, and pigment derivative. The polymer compound can be further classified into a linear polymer, a terminal modified polymer, a graft polymer, and a block polymer depending on its structure.

(Polymer Compound) The polymer compound is adsorbed on the surface of the dispersion such as a colorant (for example, an inorganic pigment), and functions to prevent re-agglomeration of the dispersion. Therefore, it is preferable to include a terminal-modified polymer, a graft polymer, and a block polymer which are fixed to the surface of the pigment.

The polymer compound preferably contains a structural unit containing a graft chain. In addition, in this specification, the meaning of "structural unit" is the same as "repeating unit". The polymer compound containing such a structural unit containing a graft chain has a solubility with a solvent by a graft chain, and is a dispersibility of a coloring agent such as a black pigment and dispersion stability after a lapse (time stability) Excellent. Further, by the presence of the graft chain, the polymer compound containing the structural unit containing the graft chain has affinity with the polymerizable compound or other resin which can be used. As a result, residue is less likely to occur in alkali development. When the graft chain becomes long, the steric repellency effect is improved, and the dispersibility of a black pigment or the like is improved. On the other hand, when the graft chain is too long, the adsorption force to a coloring pigment such as a black pigment is lowered, and the dispersibility of a black pigment or the like tends to decrease. Therefore, it is preferred that the number of atoms other than the hydrogen atom in the graft chain is from 40 to 10,000, and the number of atoms other than the hydrogen atom is preferably from 50 to 2,000, and the number of atoms other than the hydrogen atom is from 60 to 500. good. Here, the graft chain means the root of the main chain of the copolymer (the atom bonded to the main chain from the branch branched in the main chain) to the end of the group branched from the main chain.

The graft chain preferably contains a polymer structure, and examples of the polymer structure include a poly(meth)acrylate structure (for example, a poly(meth)acrylic acid structure), a polyester structure, and a polyamine group. Acid ester structure, polyurea structure, polyamine structure and polyether structure. In order to improve the interaction between the graft chain and the solvent, and thereby improve the dispersibility of the black pigment or the like, the graft chain contains a group selected from the group consisting of a polyester structure, a polyether structure, and a poly(meth)acrylate structure. At least one of the graft chains is preferred, and at least one of the graft chains having a polyester structure or a polyether structure is more preferred.

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

AA-6 (trade name, TOAGOSEI CO., LTD.), AA can be used as a commercially available macromonomer suitable for use in synthesizing a polymer compound, corresponding to a structural unit containing a graft chain contained in a polymer compound. -10 (trade name, manufactured by TOAGOSEI CO., LTD.), AB-6 (trade name, manufactured by TOAGOSEI CO., LTD.), AS-6 (trade name, manufactured by TOAGOSEI CO., LTD.), AN-6 (trade name, manufactured by TOAGOSEI CO., LTD.), AW-6 (trade name, manufactured by TOAGOSEI CO., LTD.), AA-714 (trade name, manufactured by TOAGOSEI CO., LTD.), AY-707 (product) Manufactured by TOAGOSEI CO., LTD., AY-714 (trade name, manufactured by TOAGOSEI CO., LTD.), AK-5 (trade name, manufactured by TOAGOSEI CO., LTD.), AK-30 (trade name, Manufactured by TOAGOSEI CO., LTD., AK-32 (trade name, manufactured by TOAGOSEI CO., LTD.), Blemmer PP-100 (trade name, manufactured by NOF CORPORATION.), Blemmer PP-500 (trade name, NOF CORPORATION. Manufactured, Blemmer PP-800 (trade name, manufactured by NOF CORPORATION.), Blemmer PP-1000 (trade name, manufactured by NOF CORPORATION.), Blemmer 55-PET-800 (trade name, NOF CORPORATION. Manufactured, 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.). Among them, AA-6 (trade name, manufactured by TOAGOSEI CO., LTD.), AA-10 (trade name, manufactured by TOAGOSEI CO., LTD.), and AB-6 (trade name, manufactured by TOAGOSEI CO., LTD.) are used. AS-6 (trade name, manufactured by TOAGOSEI CO., LTD.), AN-6 (trade name, manufactured by TOAGOSEI CO., LTD.), and Blemmer PME-4000 (trade name, manufactured by NOF CORPORATION) are preferable. .

The dispersant preferably contains at least one structure selected from the group consisting of polymethyl acrylate, polymethyl methacrylate, and a cyclic or chain polyester. The dispersant preferably contains at least one structure selected from the group consisting of polymethyl acrylate, polymethyl methacrylate, and chain polyester. It is further preferred that 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 dispersing agent may be one in which the above structure is contained in one dispersing agent, or may be one in which a plurality of such structures are contained in one dispersing agent. Here, the polycaprolactone structure means a structure containing a ring-opening structure of ε-caprolactone as a repeating unit. The polyvalerolactone structure refers to a structure containing a ring-opening structure for δ-valerolactone as a repeating unit. Specific examples of the dispersant containing a polycaprolactone structure include those in which the following formula (1) and the following formula (2) have 5 and k. Further, specific examples of the dispersant containing the polyvalerolactone structure include those in which the following formula (1) and the following formula (2) have 4 and k. Specific examples of the dispersant containing a polymethyl acrylate structure include those in the following formula (4) wherein X ⁵ is a hydrogen atom and R ⁴ is a methyl group. Further, specific examples of the dispersant containing a polymethyl methacrylate structure include those in which the X ⁵ in the following formula (4) is a methyl group and R ⁴ is a methyl group.

In the structural unit containing a graft chain, the structural unit containing a graft chain preferably contains a structural unit represented by any one of the following general formulae (1) to (4), and contains the following The structural unit represented by the formula (1A), the following general formula (2A), the following general formula (3A), the following general formula (3B), and the following (4) is more preferable.

[Chemical Formula 22]

In the general formulae (1) to (4), W ¹ , W ² , W ³ and W ⁴ each independently represent an oxygen atom or NH. It is preferred that W ¹ , W ² , W ³ and W ⁴ are oxygen atoms. In the general formulae (1) to (4), X ¹ , X ² , X ³ , X ⁴ and X ⁵ each independently represent a hydrogen atom or a monovalent organic group. X ¹ , X ² , X ³ , X ⁴ and X ⁵ are each independently a hydrogen atom or an alkyl group having 1 to 12 carbon atoms from the viewpoint of limitation in terms of synthesis, and each independently is a hydrogen atom. Or a methyl group is more preferred, and a methyl group is further preferred.

In the general formulae (1) to (4), Y ¹ , Y ² , Y ³ and Y ⁴ each independently represent a divalent linking group, and the structure of the linking group is not particularly limited. Specific examples of the divalent linking group represented by Y ¹ , Y ² , Y ³ and Y ⁴ include the following (Y-1) to (Y-21) linking groups and the like. In the structures shown below, A and B respectively indicate the bonding sites. Among the structures shown below, (Y-2) or (Y-13) is more preferable from the viewpoint of ease of synthesis.

[Chemical Formula 23]

In the general formulae (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, and specific examples thereof include an alkyl group, a hydroxyl group, an alkoxy group, an aryloxy group, a heteroaryloxy group, an alkyl sulfide group, an aryl sulfide group, and a heteroaryl sulfide group. And amine groups and the like. Among these, as the organic group represented by Z ¹ , Z ² , Z ³ and Z ⁴ , in particular, from the viewpoint of improvement in dispersibility, those having a steric repulsion effect are preferable, and each independently has a carbon number of 5 to 24. More preferably, the alkyl group or the alkoxy group is 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. good. Further, the alkyl group contained in the alkoxy group may be any of a linear chain, a branched chain, and a cyclic chain.

In the general formulae (1) to (4), n, m, p and q are each independently an integer of from 1 to 500. In the general formulae (1) and (2), j and k each independently represent an integer of 2 to 8. From the viewpoints of stability and developability of the curable composition, j and k in the general formulae (1) and (2) are preferably an integer of 4 to 6, and most preferably 5.

In the formula (3), R ³ represents a branched or linear alkylene group, a alkylene group having 1 to 10 carbon atoms is preferred, and an alkylene group having 2 or 3 carbon atoms is more preferred. When p is from 2 to 500, a plurality of R ³ may be the same or different from each other. In the formula (4), R ⁴ represents a hydrogen atom or a monovalent organic group, and the monovalent organic group is not particularly limited in structure. As R ⁴ , a hydrogen atom, an alkyl group, an aryl group and a heteroaryl group are preferable, and a hydrogen atom or an alkyl group is more preferable. When R ⁴ is an alkyl group, 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 is preferable as the alkyl group. More preferably, the linear alkyl group having 1 to 20 is a linear alkyl group having 1 to 6 carbon atoms. In the general formula (4), when q is from 2 to 500, a plurality of X ⁵ and R ^{4 in the} graft copolymer may be the same or different from each other.

The polymer compound can contain two or more structural units containing a graft chain having different structures. In other words, the molecular structure of the polymer compound may include structural units represented by the general formulae (1) to (4) having different structures, and in the general formulae (1) to (4), n, m, When p and q each represent an integer of 2 or more, in the general formulae (1) and (2), a structure in which j and k are different from each other in the side chain, and the general formula (3) and the general formula (4) may be included. In the numerator, a plurality of R ³ , R ⁴ and X ⁵ may be the same or different from each other.

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

[Chemical Formula 24]

In the general formula ^{(1A), X 1, Y} 1, Z 1 and n are as defined in the general formula X (1) is ^1, Y ^1, Z ¹ and n, respectively, preferred ranges are also the same. In the general formula ^{(2A), X 2, Y} 2, Z 2 and m meaning the general formula X (2) is ^2, Y ^2, Z ^2, and the same m, the preferred range is also the same.

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

[Chemical Formula 25]

In the general formula (3A) or ^{(3B), X 3, Y} 3, Z 3 and p are the meanings of the general formula X (3) is ^3, Y ^3, Z ³ and the same p, preferred ranges are also the same.

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

In the polymer compound, the structural unit containing a graft chain (for example, a structural unit represented by the above formula (1) to formula (4)) is 2 to 90 in terms of mass, based on the total mass of the polymer compound. The range of % is preferably included, preferably in the range of 5 to 30%. When the structural unit containing a graft chain is contained in this range, the dispersibility of a black pigment is high, and the developability at the time of formation of a cured film is favorable.

- Hydrophobic structural unit It is preferable that the polymer compound contains a hydrophobic structural unit which is different from the structural unit containing a graft chain (that is, does not correspond to a structural unit containing a graft chain). In the present specification, the hydrophobic structural unit does not have a structural unit of an acid group (for example, a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, a phenolic hydroxyl group, or the like).

The hydrophobic structural unit is preferably a structural unit derived from a compound (monomer) having a ClogP value of 1.2 or more, and is preferably a structural unit derived from a compound having a ClogP value of 1.2 to 8. Thereby, the effect of the present invention can be more reliably exhibited.

The ClogP value is a value calculated by the program "CLOGP" available from Daylight Chemical Information System, Inc. This program provides the value of "calculating logP" calculated by the fragmentapproach of Hansch, Leo (see below). Fragmentapproach divides the chemical structure into partial structures (fragments) according to the chemical structure of the compound, and allocates the logP contribution of the fragment in total to estimate the logP value of the compound. The details are described in the following documents. In this specification, the ClogP value indicates the value calculated by the program CLOGP v4.82. AJ Leo, Comprehensive Medicinal Chemistry, Vol.4, C. Hansch, PG Sammnens, JB Taylor and CA Ramsden, Eds., p.295, Pergamon Press, 1990 C. Hansch & AJ Leo. SUbstituent Constants For Correlation Analysis in Chemistry and Biology. John Wiley & Sons. AJ Leo. Calculating logPoct from structure. Chem. Rev., 93, 1281-1306, 1993.

logP represents the common logarithm of the partition coefficient P (Partition Coefficient), which is a quantitative numerical value indicating how the organic compound is distributed in the equilibrium of the oil (usually 1-octanol) and water 2-phase system. Expression. logP = log (Coil / Cwater) wherein 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. If the value of logP increases with a plus of 0, it means that the oil solubility increases. If the absolute value decreases, the water solubility increases and is negatively correlated with the water solubility of the organic compound. The parameters of the hydrophilicity of the organic compound are estimated to be widely used.

The polymer compound is preferably one or more structural units selected from the structural units derived from the monomers represented by the following general formulae (i) to (iii) as the hydrophobic structural unit.

[Chemical Formula 26]

In the general formulae (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 or a bromine atom) or an alkane having 1 to 6 carbon atoms. Base (for example, methyl, ethyl, propyl, etc.). R ¹ , R ² and R ³ are each preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom or a methyl group. The R ² and R ³ hydrogen atoms are particularly preferred. X represents an oxygen atom (-O-) or an imido group (-NH-), and an oxygen atom is preferred.

L is a single bond or a divalent linking group. Examples of the divalent linking group include a divalent aliphatic group (for example, an alkyl group, a substituted alkyl group, an extended alkenyl group, a substituted alkenyl group, an extended alkynyl group, a substituted alkynyl group), and a divalent group. An aromatic group (for example, an aryl group, a substituted aryl group), a divalent heterocyclic group, an oxygen atom (-O-), a sulfur atom (-S-), an imido group (-NH-), a substituted sub An amine group (-NR ³¹ - wherein R ³¹ is an aliphatic group, an aromatic group or a heterocyclic group), a carbonyl group (-CO-), a combination thereof, and the like.

The divalent aliphatic group may have a cyclic structure or a branched structure. The aliphatic group has preferably 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, and still more preferably 1 to 10 carbon atoms. The aliphatic group may be an unsaturated aliphatic group, or may be a saturated aliphatic group, and a saturated aliphatic group is preferred. Also, the aliphatic group may have a substituent. Examples of the substituent include a halogen atom, an aromatic group, and a heterocyclic group.

The divalent aromatic group has preferably 6 to 20 carbon atoms, more preferably 6 to 15 carbon atoms, and further preferably 6 to 10 carbon atoms. 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 has a 5-membered or 6-membered ring as a heterocyclic ring. The heterocyclic ring may be condensed with other heterocyclic rings, aliphatic rings or aromatic rings. The heterocyclic group may have a substituent. Examples of the substituent include a halogen atom, a hydroxyl group, an oxo group (=O), a thio group (=S), an imido group (=NH), and a substituted imido group (=NR ³² , wherein R ³² is an aliphatic group, an aromatic group or a heterocyclic group), an aliphatic group, an aromatic group or a heterocyclic group.

A L-based single bond, an alkylene group or a divalent linking group having an oxygen-extended alkyl structure is preferred. The oxygen-extended alkyl structure is preferably an oxygen-extended ethyl structure or an oxygen-extended propyl structure. L may comprise a polyoxyalkylene structure having a repeating structure containing two or more oxygen-extended alkyl groups. As the polyoxyalkylene structure, a polyoxyalkylene structure or a polyoxyalkylene structure is preferred. The polyoxyalkylene structure is represented by -(OCH ₂ CH ₂ ) _n -, n is an integer of 2 or more, and an integer of 2 to 10 is more preferable.

Examples of Z include an aliphatic group (for example, an alkyl group, a substituted alkyl group, an unsaturated alkyl group, and a substituted unsaturated alkyl group), and an aromatic group (for example, an aryl group, a substituted aryl group, an extended aryl group, and a substituted group). Aryl), heterocyclic group or a combination of these. The group may include an oxygen atom (-O-), a sulfur atom (-S-), an imido group (-NH-), a substituted imido group (-NR ³¹ -, wherein R ³¹ is an aliphatic group , an aromatic group or a heterocyclic group), a carbonyl group (-CO-).

The aliphatic group may have a cyclic structure or a branched structure. The aliphatic group has preferably 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, and still more preferably 1 to 10 carbon atoms. The aliphatic group further includes a cyclic hydrocarbon group and a crosslinked cyclic hydrocarbon group, and examples of the cyclic hydrocarbon group include a dicyclohexyl group, a perhydronaphthyl group, a biphenyl group, and a 4-cyclohexylphenyl group. Examples of the crosslinked cyclic hydrocarbon ring include pinane, bornane, norpinane, norbornane, and bicyclooctane ring (bicyclo[2.2.2]. 2-ring hydrocarbon ring such as octane ring and bicyclo [3.2.1] octane ring, etc., homobledane, adamantane, tricyclo[5.2.1.0 ^{2 , 6} ]decane and tricyclo[4.3. 1.1 ^{2 , 5} ] a non-cyclic hydrocarbon ring such as undecane ring, and a tetracyclic ring [4.4.0.1 ^{2 , 5} .1 ^{7 , 10} ] dodecane and perhydro-1,4-methylene-5,8 a 4-ring hydrocarbon ring such as a methylene naphthalene ring. The cross-linked cyclic hydrocarbon ring further includes a condensed cyclic hydrocarbon ring, for example, perhydronaphthalene (decahydronaphthalene), perhydrohydroquinone, perhydrophenanthrene, perhydrohydroquinone, perhydrohydroquinone, perhydrohydroquinone, and perhydroindole ring. The isocondensation has a plurality of fused rings of 5-8 membered cycloalkane rings. An aliphatic based saturated aliphatic group is preferred as compared with the unsaturated aliphatic group. Also, the aliphatic group may have a substituent. Examples of the substituent include a halogen atom, an aromatic group, and a heterocyclic group. Among them, the aliphatic group does not have an acid group as a substituent.

The aromatic group has preferably 6 to 20 carbon atoms, more preferably 6 to 15 carbon atoms, and further preferably 6 to 10 carbon atoms. Further, 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. Among them, the aromatic group does not have an acid group as a substituent.

The heterocyclic group preferably has a 5-membered or 6-membered ring as a heterocyclic ring. The heterocyclic ring may be condensed with other heterocyclic rings, aliphatic rings or aromatic rings. The heterocyclic group may have a substituent. Examples of the substituent include a halogen atom, a hydroxyl group, an oxo group (=O), a thio group (=S), an imido group (=NH), and a substituted imido group (=NR ³² , wherein R ³² is an aliphatic group, an aromatic group or a heterocyclic group), an aliphatic group, an aromatic group and a heterocyclic group. Among them, the heterocyclic group does not have an acid group as a substituent.

In the above formula (iii), R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom or a bromine atom), and an alkyl group having 1 to 6 carbon atoms (for example). , methyl, ethyl, propyl, etc.), Z or LZ. Here, the meanings of L and Z are the same as those of L and Z in the above. As R ⁴ , R ⁵ and R ⁶ , a hydrogen atom or an alkyl group having 1 to 3 carbon atoms is preferred, and a hydrogen atom is more preferred.

As a monomer represented by the above formula (i), R ¹ , R ² and R ³ are a hydrogen atom or a methyl group, L is a single bond or an alkyl group or a divalent linking group having an oxygen-extended alkyl structure, A compound wherein X is an oxygen atom or an imine group, and Z is an aliphatic group, a heterocyclic group or an aromatic group is preferred. As the monomer represented by the above formula (ii), a compound wherein R ¹ is a hydrogen atom or a methyl group, L is an alkylene group, and Z is an aliphatic group, a heterocyclic group or an aromatic group is preferable. Further, as the monomer represented by the above formula (iii), a compound wherein 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 preferred.

Examples of the representative compound represented by the general formulae (i) to (iii) include a radically polymerizable compound selected from the group consisting of acrylates, methacrylates, and styrenes. In addition, examples of the representative compounds represented by the general formulae (i) to (iii) can be referred to the compounds described in paragraphs 0089 to 0093 of JP-A-2013-249417, which are incorporated herein by reference.

In the polymer compound, the hydrophobic structural unit is preferably contained in the range of 10 to 90% in terms of mass, and more preferably in the range of 20 to 80%, based on the total mass of the polymer compound. A sufficient pattern formation can be achieved in the above range.

・Functional group capable of interacting with the coloring agent The polymer compound can introduce a functional group that can interact with a coloring agent such as a black pigment. Among them, the polymer compound further preferably contains a structural unit containing a functional group capable of forming an interaction with a coloring agent such as a black pigment. Examples of the functional group that can interact with the colorant such as the black pigment include an acid group, a basic group, a coordinating group, and a reactive functional group. When the polymer compound contains an acid group, a basic group, a coordinating group or a reactive functional group, each includes a structural unit containing an acid group, a structural unit containing a basic group, and a structural unit containing a coordinating group. Or a structural unit containing a reactive group is preferred. In particular, the polymer compound further contains an alkali-soluble group such as a carboxylic acid group as an acid group, whereby the polymer compound can be provided with developability for pattern formation by alkali development. In other words, by introducing an alkali-soluble group into the polymer compound, the polymer compound which is a dispersing agent which contributes to the dispersion of a coloring agent such as a black pigment is alkali-soluble in the curable composition. The curable composition containing such a polymer compound is excellent in light-shielding property of the exposed portion, and the alkali developability of the unexposed portion is improved. Further, since the polymer compound contains a structural unit containing an acid group, the polymer compound is easily integrated with a solvent and the coating property tends to be improved. It is presumed that the acid group in the structural unit containing an acid group easily interacts with a coloring agent such as a black pigment, and the polymer compound stably disperses a coloring agent such as a black pigment, and a polymer compound in which a coloring agent such as a black pigment is dispersed. The viscosity of the polymer compound is lowered, and the polymer compound itself is easily dispersed stably.

Wherein, 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, but contains a structural unit of an alkali-soluble group as an acid group. It is a structural unit different from the above hydrophobic structural unit (that is, does not correspond to the above hydrophobic structural unit).

Examples of the acid group which is a functional group capable of interacting with a coloring agent such as a black pigment include a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, or a phenolic hydroxyl group, and a carboxylic acid group, a sulfonic acid group, and a phosphoric acid group. At least one of the groups is preferable, and the carboxylic acid group is more preferable in view of the fact that the coloring agent such as a black pigment has a good adsorption force and the dispersibility of the colorant is high. That is, the polymer compound preferably has 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 two or more kinds of structural units containing an acid group. The polymer compound may or may not contain a structural unit having an acid group. When it is contained, the content of the structural unit having an acid group is preferably 5 to 80% by mass based on the total mass of the polymer compound. From the viewpoint of damage of image strength by alkali development, 10 to 60% is more preferable.

The functional group capable of interacting with a coloring agent such as a black pigment, that is, a basic group, for example, a primary amino group, a secondary amino group, a tertiary amino group, a heterocyclic ring containing an N atom, and a guanamine group, etc. A tertiary amine group is preferred from the viewpoint that the coloring agent such as a pigment has a good adsorptivity and a high dispersibility of the pigment. The polymer compound can contain one or two or more kinds of these basic groups. The polymer compound may contain a structural unit containing a basic group or may not be contained, but when it is contained, the content of the structural unit containing a basic group is preferably 0.01 to 50% by mass based on the total mass of the polymer compound. From the viewpoint of suppressing the deterioration of developability, 0.01 to 30% is more preferable.

Examples of the functional group capable of interacting with a coloring agent such as a black pigment, that is, a coordinating group and a reactive functional group, for example, an ethyl ethoxycarbonyl group, a trialkoxycarbyl group, Isocyanate groups, acid anhydrides, ruthenium chloride, and the like. From the viewpoint of a good adsorption force against a coloring agent such as a black pigment and a high dispersibility of the pigment, an ethenethyloxy group is preferred. The polymer compound may have one or two or more kinds of such groups. The polymer compound may contain a structural unit containing a coordinating group or a structural unit containing a reactive functional group, or may not contain, but when contained, the content of the structural unit is converted by mass relative to the polymer compound. The total mass is preferably from 10 to 80%, and from the viewpoint of suppressing the development resistance, 20 to 60% is more preferable.

When the polymer compound further contains a functional group capable of interacting with a coloring agent such as a black pigment in addition to the graft chain, the polymer group may be a functional group that can interact with a coloring agent such as various black pigments, and is not particularly limited. How the functional groups are introduced, and the polymer compound preferably contains one or more structural units selected from the structural units derived from the monomers represented by the following general formulae (iv) to (vi).

[Chemical Formula 27]

In the general formulae (iv) to (vi), R ¹¹ , R ¹² and R ¹³ each independently represent a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom or a bromine atom) or a carbon number of 1 to 6; Alkyl (eg, methyl, ethyl, propyl, etc.). In the general formulae (iv) to (vi), R ¹¹ , R ¹² and R ¹³ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and each independently is a hydrogen atom or a methyl group. For better. In the formula (iv), R ¹² and R ¹³ are each preferably a hydrogen atom.

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

L ₁ in the general formula (iv) to the general formula (v) represents a single bond or a divalent linking group. Examples of the divalent linking group include a divalent aliphatic group (for example, an alkyl group, a substituted alkyl group, an extended alkenyl group, a substituted alkenyl group, an extended alkynyl group, and a substituted alkynyl group), Valence of aromatic groups (for example, extended aryl and substituted aryl), divalent heterocyclic, oxygen (-O-), sulfur (-S-), imino (-NH-), A substituted imine bond (-NR ^{31 '} - wherein R ^{31 '} is an aliphatic group, an aromatic group or a heterocyclic group), a carbonyl bond (-CO-), and the like.

The divalent aliphatic group may have a cyclic structure or a branched structure. The aliphatic group has preferably 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, and still more preferably 1 to 10 carbon atoms. An aliphatic based saturated aliphatic group is preferred as compared with the unsaturated aliphatic group. Also, the aliphatic group may have a substituent. Examples of the substituent include a halogen atom, a hydroxyl group, an aromatic group, and a heterocyclic group.

The divalent aromatic group has preferably 6 to 20 carbon atoms, more preferably 6 to 15 carbon atoms, and further preferably 6 to 10 carbon atoms. The aromatic group may have a substituent. Examples of the substituent include a halogen atom, a hydroxyl group, an aliphatic group, an aromatic group, and a heterocyclic group.

The divalent heterocyclic group preferably has a 5-membered or 6-membered ring as a heterocyclic ring. The heterocyclic ring may be condensed with other heterocyclic rings, aliphatic rings or aromatic rings. The heterocyclic group may have a substituent. Examples of the substituent include a halogen atom, a hydroxyl group, an oxo group (=O), a thio group (=S), an imido group (=NH), and a substituted imido group (=NR ³² , wherein R ³² is an aliphatic group, an aromatic group or a heterocyclic group), an aliphatic group, an aromatic group and a heterocyclic group.

The L ₁ -based single bond, alkylene group or divalent linking group having an oxygen-extended alkyl structure is preferred. The oxygen-extended alkyl structure is preferably an oxygen-extended ethyl structure or an oxygen-extended propyl structure. L ₁ may comprise a polyoxyalkylene structure having a repeating structure containing two or more oxygen-extended alkyl groups. As the polyoxyalkylene structure, a polyoxyalkylene structure or a polyoxyalkylene structure is preferred. The polyoxyalkylene structure is represented by -(OCH ₂ CH ₂ ) _n -, n is an integer of 2 or more, and an integer of 2 to 10 is more preferable.

In the general formulae (iv) to (vi), Z ₁ represents a functional group which can interact with a coloring agent such as a black pigment other than the graft chain, and a carboxylic acid group and a tertiary amino group are preferred, and the carboxylic acid group is Better.

In the 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 or a bromine atom), and an alkyl group having 1 to 6 carbon atoms (for example, methyl, ethyl and propyl, etc.), - Z ₁ or L ₁ -Z _1. Wherein, L ₁ and Z ₁ meaning the same as the above L ₁ and Z _1, preferred embodiments are also the same. R ¹⁴ , R ¹⁵ and R ¹⁶ each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and more preferably a hydrogen atom.

As a monomer represented by the formula (iv), R ¹¹ , R ¹² and R ¹³ are each independently a hydrogen atom or a methyl group, L ₁ is an alkylene group or a divalent linking group having an oxygen-extended alkyl structure, A compound wherein X ₁ is an oxygen atom or an imido group and Z ₁ is a carboxylic acid group is preferred. As the monomer represented by the formula (v), a compound wherein 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 is preferable. As the monomer represented by the formula (vi), R ¹⁴ , R ¹⁵ and R ¹⁶ are each independently a hydrogen atom or a methyl group, L ₁ is a single bond or an alkyl group, and Z ₁ is a carboxylic acid group. good.

Representative examples of the monomer (compound) represented by the general formula (iv) to the formula (vi) are shown below. Examples of the monomer include a reaction of methacrylic acid, crotonic acid, isocrotonic acid, a compound having an addition polymerizable double bond and a hydroxyl group in the molecule (for example, 2-hydroxyethyl methacrylate), and succinic anhydride. a reaction product of a compound containing an addition polymerizable double bond and a hydroxyl group with phthalic anhydride, a compound containing an addition polymerizable double bond and a hydroxyl group in the molecule, and a reaction product of tetrahydroxyphthalic anhydride; a reaction product of a compound containing an addition polymerizable double bond and a hydroxyl group in the molecule with trimellitic anhydride, a reaction product of a compound containing an addition polymerizable double bond and a hydroxyl group in the molecule with pyromellitic anhydride, acrylic acid, an acrylic acid dimer, and acrylic acid Oligomers, maleic acid, itaconic acid, fumaric acid, 4-vinylbenzoic acid, vinyl phenol, and 4-hydroxybenzyl acrylamide.

The content of the structural unit containing a functional group capable of interacting with a coloring agent such as a black pigment is relative to the polymer compound from the viewpoint of interaction with a coloring agent such as a black pigment, dispersion stability, and permeability to a developing solution. The total mass is preferably from 0.05 to 90% by mass, more preferably from 1.0 to 80% by mass, even more preferably from 10 to 70% by mass.

・Other structural units Further, in order to improve various properties such as image strength, the polymer compound can be further provided without impairing the effects of the present invention, and further contains a structural unit containing a graft chain, a hydrophobic structural unit, and a black pigment. The other coloring agent forms a structural unit having a different functional unit of the interacting functional group and having various functions (for example, a structural unit having a functional group having affinity with a dispersion medium used for the dispersion). As such another structural unit, a structural unit derived from a radically polymerizable compound selected from acrylonitriles and methacrylonitriles, for example, may be mentioned. One or two or more kinds of these other structural units can be used as the polymer compound, and the content thereof is preferably from 0 to 80%, more preferably from 10 to 60%, based on the total mass of the polymer compound. The content can maintain sufficient pattern formability within the above range.

- Physical properties of the polymer compound The acid value of the polymer compound is preferably in the range of 0 to 250 mgKOH/g, more preferably in the range of 10 to 200 mgKOH/g, and still more preferably in the range of 20 to 120 mgKOH/g. When the acid value of the polymer compound is 250 mgKOH/g or less, pattern peeling during development at the time of forming a cured film is more effectively suppressed. When the acid value of the polymer compound is 10 mgKOH/g or more, the alkali developability is further improved. When the acid value of the polymer compound is 20 mgKOH/g or more, sedimentation of a coloring agent such as a black pigment can be further suppressed, and the number of coarse particles can be made smaller, and the temporal stability of the curable composition can be further improved.

The acid value of the polymer compound can be calculated, for example, from the average content of the acid groups in the polymer compound. Further, a resin having a desired acid value can be obtained by changing the content of a structural unit containing an acid group as a constituent component of the polymer compound.

When the cured film is formed, the weight average molecular weight of the polymer compound is a polystyrene-converted value based on GPC (Gel Permeation Chromatography), from the viewpoint of suppression of pattern peeling during development and developability. More preferably, it is 4,000 to 300,000, more preferably 5,000 to 200,000, still more preferably 6,000 to 100,000, and particularly preferably 10,000 to 50,000. The GPC method is based on the following method, that is, using HLC-8020GPC (manufactured by TOSOH CORPORATION) as a column using TSKgel SuperHZM-H, TSKgel SuperHZ4000, TSKgel SuperHZ2000 (manufactured by TOSOH CORPORATION, 4.6 mm ID × 15 cm) as an eluent THF (tetrahydrofuran).

The polymer compound can be synthesized by a known method, and examples of the solvent used in the synthesis of the polymer compound include dichloroethane, cyclohexanone, methyl ethyl ketone, acetone, methanol, ethanol, propanol, butanol, and ethylene glycol. Monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, 1-methoxy-2-propanol, 1-methoxy-2-acetic acid propyl ester, N,N-dimethyl Mercaptoamine, N,N-dimethylacetamide, dimethyl hydrazine, toluene, ethyl acetate, methyl lactate and ethyl lactate. These solvents may be used singly or in combination of two or more.

Specific examples of the polymer compound include "DA-7301" manufactured by Kusumoto Chemicals, Ltd., "Disperbyk-101 (polyamidoamine phosphate), 107 (carboxylate), 110 (containing) manufactured by BYK Chemie Co., Ltd. Acid group copolymer), 111 (phosphate dispersant), 130 (polyamide), 161, 162, 163, 164, 165, 166, 170, 190 (polymer copolymer)", "BYK-P104, P105 (high molecular weight unsaturated polycarboxylic acid)", EFKA company "EFKA4047, 4050 ~ 4010 ~ 4165 (polyurethane type), EFKA4330 ~ 4340 (block copolymer), 4400 ~ 4402 (modified poly Acrylate), 5010 (polyester decylamine), 5765 (high molecular weight polycarboxylate), 6220 (fatty acid polyester), 6745 (phthalocyanine derivative), 6750 (azo pigment derivative), Ajinomoto Fine- "AJISPER PB821, PB822, PB880, PB881" manufactured by Techno Co., Inc., "Flowlen TG-710 (urethane oligomer)", "polyflow No. 50E, No" manufactured by Kyoeisha Chemical Co., Ltd. .300 (acrylic copolymer)", manufactured by Kusumoto Chemicals, Ltd. "disparon KS-860 873SN, 874, #2150 (aliphatic polyvalent carboxylic acid), #7004 (polyether ester), DA-703-50, DA-705, DA-725", Kao Corporation manufacture "DEMOL RN, N (naphthalenesulfonic acid) Formalin polycondensate), MS, C, SN-B (aromatic sulfonate fumarate polycondensate), "HOMOGENOL L-18 (polymer polycarboxylic acid)", "EMULGEN 920, 930, 935, 985 (polyoxygen) "Ethyl nonylphenyl ether)", "ACETAMIN86 (stearylamine acetate)", and Lubrizol Japan Limited manufacture "Solsperse 5000 (phthalocyanine derivative), 22000 (azo pigment derivative), 13240 (polyester amine), 3000, 12000, 17000, 20000, 27000 (polymer having a functional portion at the end portion), 24000, 28000, 32000, 38500 (graft copolymer)", Nikko Chemicals Co., Ltd., "NIKKOL T106 (poly) "Oxyethylene sorbitan monooleate", MYS-IEX (polyoxyethylene stearate), "HINOACT T-8000E" manufactured by Kawaken Fine Chemicals Co., Ltd., Shin-Etsu Chemical Co., Ltd. manufactures "organoorganosiloxane based polymer KP341", manufactured by Yusho Co., Ltd. "W001: cationic system boundary Active agent", polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol laurate Nonionic surfactants such as polyethylene glycol distearate and sorbitan fatty acid ester, anionic surfactants such as "W004, W005, W017", and "EFKA" manufactured by Morishita Sangyo Co., Ltd. -46, EFKA-47, EFKA-47EA, EFKA Polymer 100, EFKA Polymer 400, EFKA Polymer 401, EFKA Polymer 450", manufactured by SAN NOPCO LIMITED "Disperse Aid 6, Disperse Aid 8, Disperse Aid 15, Disperse Aid 9100" and other polymer dispersants, manufactured by ADEKA CORPORATION "ADEKA Pluronic L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, P -123", and Sano Chemical Industries, Ltd. manufacture "Ionet (trade name) S-20" and the like. Further, Acrylic base FFS-6752, Acrylic base FFS-187, Akurikyua-RD-F8, and Cyclomer P can also be used. Further, as a commercial product of the amphoteric resin, for example, DISPERBYK-130, DISPERBYK-140, DISPERBYK-142, DISPERBYK-145, DISPERBYK-180, DISPERBYK-187, DISPERBYK-191, DISPERBYK-2001 manufactured by BYK Additives & Instruments, DISERBYK-2010, DISPERBYK-2012, DISPERBYK-2025, BYK-9076, AJISPER PB821, AJISPER PB822, and AJISPER PB881 manufactured by Ajinomoto Fine-Techno Co., Inc. These polymer compounds may be used alone or in combination of two or more.

In addition, as a specific example of the polymer compound, the polymer compound described in paragraphs 0127 to 0129 of JP-A-2013-249417 can be referred to, and the contents are incorporated in the present specification.

Further, as the dispersing agent, in addition to the above-mentioned polymer compound, a graft copolymer of paragraphs 0037 to 0115 of the Japanese Patent Laid-Open Publication No. 2010-106268 (corresponding to paragraphs 0075 to 0133 of US2011/0124824) can be used. The content is incorporated in this manual. In addition, in addition to the above, it is also possible to use the side chain structure in which the acidic group is bonded via a linking group, in paragraphs 0928 to 0084 of the Japanese Patent Laid-Open Publication No. 2011-153283 (corresponding to paragraphs 0075 to 0133 of US2011/0279759). The polymer compound constituting the component is incorporated in the present specification.

<Bonding Resin> The curable composition preferably contains a binder resin. The content of the binder resin is preferably 0.1% by mass or more based on the total solid content of the curable composition, more preferably 0.3% by mass or more, more preferably 0.9% by mass or more, and particularly preferably 1.9% by mass or more, and 30% by mass. % or less is more preferable, 25% by mass or less is more preferable, 18% by mass or less is further more preferable, and 10% by mass or less is particularly preferable. When the content of the binder resin is 1.9 to 10% by mass, the pattern shape of the cured film obtained by curing the curable composition is more excellent. The binder resin may be used singly or in combination of two or more. When two or more kinds of binder resins are used at the same time, the total amount thereof is preferably within the above range.

As the binder resin, a linear organic polymer is preferably used. As such a linear organic polymer, a known one can be used arbitrarily. In order to achieve water development or weak alkaline water development, it is more preferable to select a linear organic polymer which is soluble or swellable to water or weakly alkaline water. Among them, as the binder resin, an alkali-soluble resin (a resin containing a group which promotes alkali solubility) is particularly preferable. As the binder resin, at least one group which promotes alkali solubility can be contained from a linear organic polymer and a molecule (preferably a molecule having a (meth)acrylic copolymer or a styrene copolymer as a main chain) The alkali-soluble resin is appropriately selected. From the viewpoint of heat resistance, polyhydroxystyrene resin, polyoxyalkylene resin, (meth)acrylic resin, (meth)acrylamide resin, (meth)acrylic acid/(meth)acrylonitrile The amine copolymer, the epoxy resin, and the polyimide resin are preferable, and from the viewpoint of developability control, (meth)acrylic resin, (meth)acrylamide resin, and (meth)acrylic acid/ The (meth)acrylamide copolymer and the polyimine resin are more preferable. Examples of the group that promotes alkali solubility (hereinafter, also referred to as an acid group) include a carboxyl group, a phosphoric acid group, a sulfonic acid group, and a phenolic hydroxyl group. Among them, those which are soluble in an organic solvent and can be developed by a weakly alkaline aqueous solution are preferable, and more preferably, an alkali-soluble resin containing a structural unit derived from (meth)acrylic acid is mentioned. These acid groups may be used alone or in combination of two or more.

The binder resin may, for example, be a radical polymer having a carboxylic acid group in a side chain. Examples of the radical polymer having a carboxylic acid group in the side chain include, for example, JP-A-59-44615, JP-A-54-34327, JP-A-58-12577, and JP-A-54-25957. No. 54-92723, Japanese Patent Laid-Open No. 59-53836, and Japanese Patent Laid-Open No. 59-71048. Examples of the radical polymer having a carboxylic acid group in a side chain include hydrolysis of an acid anhydride unit obtained by separately or copolymerizing a resin containing a carboxylic acid group alone or copolymerized with an acid anhydride. A semi-esterified or semi-aminated resin, an epoxy acrylate which is modified with an unsaturated monocarboxylic acid and an acid anhydride, and the like. Examples of the monomer having a carboxylic acid group include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, and 4-carboxystyrene. Further, an acidic cellulose derivative containing a carboxylic acid group in a side chain may be mentioned as an example. Examples of the acid anhydride-containing monomer include maleic anhydride and the like. Further, it is useful for adding a cyclic acid anhydride to a polymer containing a hydroxyl group. Further, an acetal-modified polyvinyl alcohol-based binder resin containing an acid group is described in each of the publications of European Patent No. 993966, European Patent No. 1204000, and Japanese Patent Laid-Open No. 2001-318463. The acetal-modified polyvinyl alcohol-based binder resin containing an acid group is excellent in a balance between film strength and developability. Further, as the water-soluble linear organic polymer, polyvinylpyrrolidone or polyethylene oxide is useful. Further, in order to increase the strength of the hardened film, a reaction product of alcohol-soluble nylon and 2,2-bis-(4-hydroxyphenyl)-propane and epichlorohydrin, that is, a polyether or the like is also useful. Further, the polyimine resin described in International Publication No. 2008/123097 is also useful.

In particular, among these, [diphenylethylenedione (meth)acrylate/(meth)acrylic acid/other addition polymerizable ethylene monomer as needed] copolymer and [(meth)acrylic acid allyl ester/ The (meth)acrylic acid is preferably excellent in the balance of film strength, sensitivity, and developability of the other addition polymerizable ethylene monomer copolymer. As a commercial item, Acrylic base FF-187, FF-426 (made by FUJIKURA KASEI CO., LTD.), Akurikyua-RD-F8 (NIPPON SHOKUBAI CO., LTD.), and DAICEL-ALLNEX LTD. are mentioned, for example. Manufacture of Cyclomer P (ACA) 230AA and the like.

In the production of the binder resin, for example, a method based on a known radical polymerization method can be applied. A person skilled in the art can easily set polymerization conditions such as temperature, pressure, type and amount of radical initiator, and type of solvent when the binder resin is produced by a radical polymerization method.

As the binder resin, a polymer comprising a structural unit containing a graft chain and a structural unit containing an acid group (alkali-soluble group) is also preferably used. The definition of the structural unit containing the graft chain is the same as that of the structural unit containing the graft chain contained in the above dispersing agent, and the preferred range is also the same. The acid group is, for example, a carboxylic acid group, a sulfonic acid group, a phosphoric acid group or a phenolic hydroxyl group, and at least one of a carboxylic acid group, a sulfonic acid group and a phosphoric acid group is preferred, and a carboxylic acid group is more preferred.

(Structural unit containing an acid group) The structural unit containing an acid group is preferably one or more structural units selected from the structural units derived from the monomers represented by the following formulas (vii) to (ix).

[Chemical Formula 28]

In the formula (vii) and the formula (viii), R ²¹ , R ²² and R ²³ each independently represent a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom or a bromine atom) or a carbon number of 1 to 6; Alkyl (eg, methyl, ethyl, propyl, etc.). In the formula (vii) and the formula (viii), R ²¹ , R ²² and R ²³ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and each independently is a hydrogen atom or a methyl group. For better. In the formula (vii), R ²¹ and R ²³ are each preferably a hydrogen atom.

X ₂ in the formula (vii) represents an oxygen atom (-O-) or an imido group (-NH-), and an oxygen atom is preferred. Y in the formula (viii) represents a methine group or a nitrogen atom.

L ₂ in the formula (vii) and the formula (viii) represents a single bond or a divalent linking group. Examples of the divalent linking group include a divalent aliphatic group (for example, an alkyl group, a substituted alkyl group, an extended alkenyl group, a substituted alkenyl group, an extended alkynyl group, and a substituted alkynyl group), Valence of aromatic groups (for example, extended aryl and substituted aryl), divalent heterocyclic, oxygen (-O-), sulfur (-S-), imino (-NH-), A substituted imine bond (-NR ^{41 '} - wherein R ^{41 '} is an aliphatic group, an aromatic group or a heterocyclic group), a carbonyl bond (-CO-), and the like.

The divalent aliphatic group may have a cyclic structure or a branched structure. The aliphatic group has preferably 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, and still more preferably 1 to 10 carbon atoms. An aliphatic based saturated aliphatic group is preferred as compared with the unsaturated aliphatic group. Also, the aliphatic group may have a substituent. Examples of the substituent include a halogen atom, a hydroxyl group, an aromatic group, and a heterocyclic group.

The divalent aromatic group has preferably 6 to 20 carbon atoms, more preferably 6 to 15 carbon atoms, and further preferably 6 to 10 carbon atoms. Further, the aromatic group may have a substituent. Examples of the substituent include a halogen atom, a hydroxyl group, an aliphatic group, an aromatic group, and a heterocyclic group.

The divalent heterocyclic group preferably has a 5-membered or 6-membered ring as a heterocyclic ring. The heterocyclic ring may be condensed with other heterocyclic rings, aliphatic rings or aromatic rings. Also, the heterocyclic group may have a substituent. Examples of the substituent include a halogen atom, a hydroxyl group, an oxo group (=O), a thio group (=S), an imido group (=NH), and a substituted imido group (=NR ⁴² , wherein R ⁴² is an aliphatic group, an aromatic group or a heterocyclic group), an aliphatic group, an aromatic group and a heterocyclic group.

A L ₂ -based single bond, an alkylene group or a divalent linking group having an oxygen-extended alkyl structure is preferred. The oxygen-extended alkyl structure is preferably an oxygen-extended ethyl structure or an oxygen-extended propyl structure. Further, L ₂ may include a polyoxyalkylene structure having a repeating structure containing two or more oxygen-extended alkyl groups. As the polyoxyalkylene structure, a polyoxyalkylene structure or a polyoxyalkylene structure is preferred. The polyoxyalkylene structure is represented by -(OCH ₂ CH ₂ ) _n -, n is an integer of 2 or more, and an integer of 2 to 10 is more preferable.

In the formula (vii) to the formula (ix), Z ₂ represents an acid group, and a carboxylic acid group is preferred.

In the formula (ix), R ²⁴ , R ²⁵ and R ²⁶ each independently represent a hydrogen atom, a halogen atom (for example, fluorine, chlorine, bromine, etc.) or an alkyl group having 1 to 6 carbon atoms (for example, a methyl group, ethyl, propyl, etc.), - Z ₂ or L ₂ -Z _2. Wherein, L _2, and the meaning is the same as Z ₂ in the above-described L ₂ and Z _2, preferred examples are also the same. R ²⁴ , R ²⁵ and R ²⁶ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom.

As a monomer represented by the formula (vii), R ²¹ , R ²² and R ²³ are each independently a hydrogen atom or a methyl group, L ₂ is an alkylene group or a divalent linking group having an oxygen-extended alkyl structure, A compound wherein X ₂ is an oxygen atom or an imido group and Z ₂ is a carboxylic acid group is preferred. Further, as a monomer of the formula (viii), a compound wherein 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 is preferable. Further, as the monomer represented by the formula (ix), a compound wherein 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 preferred.

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

The above binder resin may have one or two or more structural units containing an acid group. The content of the structural unit containing an acid group is preferably from 5 to 95% by mass based on the total mass of the above-mentioned binder resin, and from 10 to 90% from the viewpoint of suppressing damage of image strength by alkali development. Better.

<Surfactant> The curable composition preferably contains a surfactant. The surfactant helps to improve 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, more preferably 0.005 to 1.0% by mass, based on the total mass of the curable composition. The surfactant may be used singly or in combination of two or more. When two or more kinds of surfactants are used at the same time, the total amount is preferably in the above range.

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

For example, when the curable composition contains a fluorine-based surfactant, the liquid characteristics (particularly, fluidity) of the curable composition are further improved. In other words, when a film is formed 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 coatability of the coated surface is improved. Therefore, even when a film having a thickness of about several μm is formed in a small amount of liquid, a film having a small thickness unevenness can be more preferably formed, which is effective in this point.

The fluorine content in the fluorine-based surfactant is preferably from 3 to 40% by mass, more preferably from 5 to 30% by mass, still more preferably from 7 to 25% by mass. The fluorine-containing surfactant having a fluorine content in this range is effective in the uniformity of the thickness of the coating film and/or the liquid-repellent property, and the solubility in the curable composition is also good.

Examples of the fluorine-based surfactant include Megaface F171, Megaface F172, Megaface F173, Megaface F176, Megaface F177, Megaface F141, Megaface F142, Megaface F143, Megaface F144, Megaface R30, Megaface F437, Megaface F475, Megaface F479, Megaface. F482, Megaface F554, Megaface F780 (above, manufactured by DIC Corporation), Fluorad FC430, Fluorad FC431, Fluorad FC171 (above, manufactured by Sumitomo 3M Limited), Surflon S-382, Surflon SC-101, Surflon SC-103, Surflon SC- 104, Surflon SC-105, Surflon SC-1068, Surflon SC-381, Surflon SC-383, Surflon S-393, Surflon KH-40 (above, manufactured by ASAHI GLASS CO., LTD.), PF636, PF656, PF6320, PF6520, PF7002 (manufactured by OMNOVA Solutions Inc.), and the like. As the fluorine-based surfactant, a block polymer can also be used. Specific examples thereof include a compound described in JP-A-2011-89090. Further, examples of the fluorine-based surfactant include a compound (F-1) represented by the following formula. Further, in the compound (F-1), the structural units represented by (A) and (B) in the formula are 62 mol% and 38 mol%, respectively. In the structural unit represented by the general formula (B), a, b, and c satisfy the relationship of a+c=14 and b=17, respectively. Further, the weight average molecular weight of the following compound is, for example, 15311.

[Chemical Formula 29]

Specific examples of the nonionic surfactant include glycerin, trimethylolpropane, trimethylolethane, and ethoxylates and propoxylates (for example, glycerol propoxylate, glycerin). Ethoxylate, etc., polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol Dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester (Pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2, Tetronic 304, 701, 704, 901 manufactured by BASF Corporation) , 904, 150R1), Solsperse20000 (manufactured by Japan Lubrizol Corporation), and the like. Further, it is also possible to manufacture Pionin D-6112-W, NCW-101, NCW-1001, and NCW-1002 manufactured by Wako Pure Chemical Industries, Ltd. using TAKEMOTO OIL & FAT CO., LTD.

Specific examples of the cation-based surfactant include a phthalocyanine derivative (trade name: EFKA-745, manufactured by MORISHITA & CO., LTD.), and an organic siloxane polymer KP341 (Shin-Etsu Chemical Co., (manufactured by Ltd.), (meth)acrylic (co)polymer Polyflow No. 75, No. 90, No. 95 (manufactured by KYOEISHA CHEMICAL CO., LTD), W001 (manufactured by Yusho Co Ltd), and the like.

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

Examples of the anthrone-based surfactant include "Toray Silicone DC3PA", "Toray Silicone SH7PA", "Toray Silicone DC11PA", "Toray Silicone SH21PA", and "Toray Silicone SH28PA" manufactured by Dow Corning Toray Co., Ltd. "Toray Silicone SH29PA", "Toray Silicone SH30PA", "Toray Silicone SH8400", Momentive Performance Materials Inc. manufacture "TSF-4440", "TSF-4300", "TSF-4445", "TSF-4460", " "KP341", "KF6001", "KF6002" manufactured by TSF-4452", Shin-Etsu Chemical Co., Ltd., "BYK307", "BYK323", "BYK330", and the like are manufactured by BYK Chemie GmbH.

<Hydrane coupling agent> A decane coupling agent means a compound containing a hydrolyzable group and a functional group other than the molecule. Further, a hydrolyzable group such as an alkoxy group is bonded to a ruthenium atom. The hydrolyzable group means a substituent which is directly bonded to a ruthenium atom and which can form a siloxane chain bond by a hydrolysis reaction and/or a condensation reaction. Examples of the hydrolyzable group include a halogen atom, an alkoxy group, a decyloxy group, and an alkenyloxy group. When the hydrolyzable group contains a carbon atom, the carbon number is preferably 6 or less, more preferably 4 or less. An alkoxy group having 4 or less carbon atoms or an alkenyloxy group having 4 or less carbon atoms is particularly preferable. When the cured film is formed on the substrate, in order to improve the adhesion between the substrate and the cured film, the decane coupling agent does not contain a fluorine atom or a ruthenium atom (except for the ruthenium atom to which the hydrolyzable group is bonded), and it is preferable. Does not contain a fluorine atom or a ruthenium atom (excluding a ruthenium atom to which a hydrolyzable group is bonded), an alkylene group substituted by a ruthenium atom, a linear alkyl group having 8 or more carbon atoms, and a branched alkyl group having 3 or more carbon atoms The base is preferred.

The decane coupling agent preferably contains a group represented by the following formula (Z). * indicates the bonding position. In the formula (Z)*-Si-(R _Z1 ) _{3 , in the} formula (Z), R _Z1 represents a hydrolyzable group, and its definition is as described above.

The decane coupling agent preferably contains at least one type of curable functional group selected from the group consisting of a (meth) acryloxy group, an epoxy group, and an oxetanyl group. The hardenable functional group may be directly bonded to the ruthenium atom or may be bonded to the ruthenium atom via the linker. Further, as a preferred aspect of the curable functional group contained in the above decane coupling agent, a radical polymerizable group may also be mentioned.

The molecular weight of the decane coupling agent is not particularly limited, and from the viewpoint of handling properties, 100 to 1,000 are often used, and 270 or more is preferable, and 270 to 1,000 is more preferable.

One of preferred embodiments of the decane coupling agent is a decane coupling agent X represented by the formula (W). The general 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 hardenable functional group, and 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. When Lz represents a divalent linking group, examples of the divalent linking group include a halogen-substituted alkyl group, a halogen-substituted aryl group, -NR ¹² -, -CONR ^12- , -CO- , -CO ₂ -, SO ₂ NR ¹² -, -O-, -S-, -SO ₂ - or a combination of these. Wherein, at least one selected from the group consisting of an alkyl group substituted with a halogen atom having 2 to 10 carbon atoms and a halogen atom substituted with a carbon number of 6 to 12, or a group selected from the group consisting of a group comprising a combination of at least one group of -NR ¹² -, -CONR ¹² -, -CO-, -CO ₂ -, SO ₂ NR ¹² -, -O-, -S-, and SO ₂ - Preferably, a group containing a C 2-10 halogen atom which may be substituted with an alkyl group, -CO ₂ -, -O-, -CO-, -CONR ¹² - or a combination of such groups is more preferred. . Wherein R ¹² represents a hydrogen atom or a methyl group.

The decane coupling agent X may, for example, be N-β-aminoethyl-γ-aminopropyl-methyldimethoxydecane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBM-602). N-β-amine ethyl-γ-aminopropyl-trimethoxydecane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBM-603), N-β-amine ethyl-γ-aminopropyl - Triethoxy decane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBE-602), γ-aminopropyl-trimethoxydecane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBM) -903), γ-aminopropyl-triethoxydecane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBE-903), 3-methacryloxypropyltrimethoxydecane (Shin) - Manufactured by Etsu Chemical Co., Ltd., trade name: KBM-503), and epoxypropoxyoctyltrimethoxydecane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM-4803).

Other preferred aspects of the decane coupling agent include a decane coupling agent Y having at least a ruthenium atom, a nitrogen atom, a curable functional group in the molecule, and a hydrolyzable group bonded to a ruthenium atom. . The decane coupling agent Y may have at least one ruthenium atom in the molecule, and the ruthenium atom may be bonded to the following atoms or substituents. These may be the same atom, substituent, or different. The atom to be bonded and the substituent may, for example, be a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group having 1 to 20 carbon atoms, an alkenyl group, an alkynyl group, an aryl group, an amine group which may be substituted with an alkyl group and/or an aryl group, A germyl group, an alkoxy group having 1 to 20 carbon atoms, an aryloxy group or the like. The substituents may be further substituted by a mercaptoalkyl group, an alkenyl group, an alkynyl group, an aryl group, an alkoxy group, an aryloxy group, a thioalkoxy group, an amine group substituted with an alkyl group and/or an aryl group, a halogen atom, A sulfonamide group, an alkoxycarbonyl group, a decylamino group, a urea group, an ammonium group, an alkylammonium group, a carboxylic acid group or a salt thereof, a sulfo group or a salt thereof, or the like. Further, at least one hydrolyzable group is bonded to the ruthenium atom. The definition of the hydrolyzable group is as described above. The group represented by the formula (Z) may be contained in the decane coupling agent Y.

The decane 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 quaternary amine group or a ternary amine group, that is, the nitrogen atom contains at least one organic group as a substituent. The group is better. Further, the structure of the amine group may be present in the molecule in the form of a partial structure containing a nitrogen-containing hetero ring, or may be present as a substituted amine group such as aniline. Among them, examples of the organic group include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a combination thereof. These may further have a substituent, and examples of the substituent which may be introduced include a germyl group, an alkenyl group, an alkynyl group, an aryl group, an alkoxy group, an aryloxy group, a thioalkoxy group, an amine group, and a halogen atom. A sulfonylamino group, an alkoxycarbonyl group, a carbonyloxy group, a decylamino group, a urea group, an alkoxy ammonium group, an alkylammonium group, a carboxylic acid group or a salt thereof, a sulfo group or the like. Further, it is preferred that the nitrogen atom is bonded to the curable functional group via an arbitrary organic linking group. Preferred examples of the organic linking group include a substituent which can be introduced into the nitrogen atom and an organic group bonded thereto.

The definition of the hardenable functional group contained in the decane coupling agent Y is as described above, and the preferred range is also as described above. The decane coupling agent Y may have at least one or more curable functional groups in one molecule, but may contain two or more curable functional groups, from the viewpoint of sensitivity and stability. It is more preferably 2 to 20 hardening functional groups, more preferably 4 to 15 carbon atoms, and even more preferably 6 to 10 hardening functional groups in the molecule.

The molecular weight of the decane coupling agent X and the decane coupling agent Y is not particularly limited, and the above range (preferably 270 or more) is preferable.

The content of the decane coupling agent in the curable composition is preferably from 0.1 to 10% by mass, more preferably from 0.5 to 8% by mass, even more preferably from 1.0 to 6% by mass, based on the total solid content of the curable composition. good.

The curable composition may contain a single decane coupling agent alone or in combination of two or more. When the curable composition contains two or more kinds of decane coupling agents, the total amount thereof may be within the above range.

<Ultraviolet absorber> The curable composition may contain an ultraviolet absorber. Thereby, the pattern shape of the cured film can be made more excellent (fine). As the ultraviolet absorber, a salicylate-based, benzophenone-based, benzotriazole-based, substituted acrylonitrile-based or triazine-based ultraviolet absorber can be used. As a specific example, the compounds of paragraphs 0137 to 0142 of the Japanese Patent Laid-Open Publication No. 2012-068418 (corresponding to paragraphs 0251 to 0254 of US2012/0068292) can be used, and these contents can be incorporated into the present specification. . Further, a diethylamino-phenylsulfonyl-based ultraviolet absorber (manufactured by DAITO CHEMICAL CO., LTD., trade name: UV-503) or the like can also be preferably used. The ultraviolet absorbing agent may, for example, be a compound exemplified in paragraphs 0134 to 0148 of JP-A-2012-32556. The content of the ultraviolet absorber is preferably 0.001 to 15% by mass, more preferably 0.01 to 10% by mass, even more preferably 0.1 to 5% by mass, based on the total solid content of the curable composition.

[Method for Producing Curable Composition] The method for producing the curable composition is not particularly limited, and the following mixing step is preferred. Moreover, it is more preferable to include a standing step and/or a filtering step. Hereinafter, preferred embodiments will be described in detail for each step.

<Mixing Step> The mixing step is a step of obtaining a curable composition by mixing the above components by a known mixing method (for example, a stirrer, a homogenizer, a high-pressure emulsifier, a wet pulverizer, and a wet disperser). In the mixing step, the components constituting the curable composition may be blended at one time, or may be sequentially blended after dissolving or dispersing the components in an organic solvent. Further, the order of input and the working conditions at the time of blending are not particularly limited. Also, the mixing step may comprise the step of making a dispersion.

(Step of Producing Dispersion) The step of preparing a dispersion is a step of mixing a colorant, a dispersant, and a solvent, and dispersing the colorant by the above method to prepare a dispersion. The curable composition can be produced by mixing the remaining components with the prepared dispersion. In the step of producing the above dispersion liquid, as the mechanical force for dispersing the pigment, compression, pressing, impact, cutting, cavitation, and the like may be mentioned. Specific examples of such processes include bead milling, sand mixing, roll milling, high-speed impeller, sanding, jet mixing, high-pressure wet micronization, and ultrasonic dispersion. In addition, the actual comprehensive data of the dispersion technology and industrial application centered on the suspension technology (solid/liquid dispersion system) and the "disintegration technology" will be properly used. Process and dispersing machine described in the "Publishing and Publishing Center of the Collection and Management Development Center, October 10, 1978". Further, in the step of producing the above dispersion liquid, the finening treatment of the pigment by the salt milling step can be performed. The raw materials, the equipment, the processing conditions, and the like used in the salt milling step can be, for example, those described in JP-A-2015-194521 and JP-A-2012-046629. Further, the method for producing a curable composition preferably comprises the step of obtaining the coloring agent by a thermal plasma method. The step of obtaining the colorant is carried out before mixing the above components.

<Standing Step> The above coloring agent may be subjected to the following standing step before being supplied to the mixing step or the step of preparing the dispersion. In the standing step, the coloring agent obtained by the thermal plasma method is not exposed to the atmosphere after its manufacture, but is left in a sealed container in which the oxygen concentration is controlled, and is allowed to stand for a predetermined period of time (12 to 72 hours is preferable, 12 The step of -48 hours is more preferred, and 12 to 24 hours is further preferred). At this time, the content of moisture in the sealed container is preferably controlled.

In this case, the oxygen (O ₂ ) concentration and the moisture content in the sealed container are preferably 100 ppm by mass or less, more preferably 10 ppm by mass or less, and still more preferably 1 ppm by mass or less. The oxygen (O ₂ ) concentration and the moisture content in the sealed container can be adjusted by adjusting the oxygen concentration and the amount of moisture in the inert gas supplied to the sealed container. As the inert gas, nitrogen gas and argon gas are preferably used, and among them, nitrogen gas is more preferable. When the above-described standing step is performed, the surface and the grain boundary of the colorant become stable. Thereby, it is possible to suppress the occurrence of pinholes of the cured film obtained by curing the curable composition.

<Filtering Step> The filtration step is a step of filtering the curable composition produced by the above mixing step by a filter. In the filtration step, foreign matter can be removed from the curable composition and/or defects can be reduced. The filter can be used without particular limitation as long as it is used for filtration purposes or the like. For example, a fluororesin such as PTFE (polytetrafluoroethylene), a polyamide resin such as nylon, or a polyolefin resin such as polyethylene or polypropylene (PP) (including high density and ultrahigh molecular weight) may be used. filter. Among these raw materials, polypropylene (containing high-density polypropylene) and nylon are preferred. The filter has a pore diameter of about 0.1 to 7.0 μm, preferably 0.2 to 2.5 μm, more preferably 0.2 to 1.5 μm, and even more preferably 0.3 to 0.7 μm. By setting it as this range, it is possible to suppress the filtration clogging of the pigment, and to reliably remove fine foreign matter such as impurities and aggregates contained in the pigment. When using filters, different filters can be combined. At this time, the filtration by the first filter may be performed only once or twice or more. When two or more filters are combined for different filters, it is preferable that the pore diameter after the second time is the same as or larger than the pore diameter of the first filtration. Further, a first filter having a different pore diameter within the above range may be combined. The aperture here can be referred to the filter manufacturer's nominal value. As a commercially available filter, for example, it can be selected from various filters supplied by NIHON PALL LTD., ADVANTEC TOYO KAISHA, LTD., Nihon Entegris K.K. (formerly Mykrolis Corpration) or KITZ MICRO FILTER CORPORATION. The second filter can be formed using the same material or the like as the first filter described above. The second filter preferably has a pore diameter of from 0.2 to 10.0 μm, preferably from 0.2 to 7.0 μm, more preferably from 0.3 to 6.0 μm.

[Container] The hardenable composition can be temporarily stored in a container until it is used. The container for storing the curable composition is not particularly limited, and a known container can be used. As a container for storing a curable composition, it is preferable that the degree of cleanliness in the container is high and the elution of impurities is small. For example, it is also possible to use a commercially available user for semiconductor applications. Specific examples of the container that can be used include a "clean bottle" series manufactured by AICELLO CHEMICAL CO., LTD., and a "pure bottle" manufactured by KODAMA PLASTICS Co., Ltd., but are not limited thereto. For example, it is also preferable to use a multi-layered bottle in which the inner wall of the container is composed of six kinds of resins and has a six-layer structure or a multi-layered bottle in which the inner wall of the container is composed of six kinds of resins and has a seven-layer structure. The container described in JP-A-2015-123351 is exemplified as the container.

[Cured film] The cured film is obtained by hardening the above curable composition. A colorant is contained in the cured film. The cured film is suitably used as a light-shielding film, and specifically, it is suitable as a light-shielding film of the peripheral portion of the light-receiving portion of the image sensor.

When the cured film is used as a light-shielding film in the peripheral portion of the light-receiving portion of the image sensor, the following is preferable. The film thickness of the light-shielding film is not particularly limited, and from the viewpoint of the effect of the present invention which is more excellent in the light-shielding film, it is preferably 0.2 to 50 μm, more preferably 0.3 to 10 μm, and more preferably 0.3. ～5 μm is further preferred. The size of the light-shielding film (the length of one side of the light-shielding film provided around the light-receiving portion of the sensor) is preferably 0.001 to 10 mm, and more preferably 0.05 to 7 mm, from the viewpoint that the light-shielding film has an excellent effect of the present invention. Preferably, 0.1 to 3.5 mm is further preferred.

[Method for Producing Cured Film] Next, a method for producing a cured 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, exposure step, and development step. The curable composition layer forming step: a step of forming a curable composition layer using a curable composition. Exposure step: a step of exposing the above-mentioned curable composition layer into a pattern. Developing step: a step of developing the cured composition layer after exposure (in other words, developing and removing the unexposed portion) to form a cured film.

Specifically, the curable composition is applied onto the substrate directly or via another layer to form a curable composition layer (curable composition layer forming step), exposed through a predetermined mask pattern, and irradiated only by light. The coating film is partially cured (exposure step), and development is carried out by a developing solution (developing step), whereby a cured film can be produced. Hereinafter, each step described above will be described.

<Step of Forming Curable Composition Layer> The step of forming the curable composition layer is a step of forming a curable composition layer on a support (hereinafter also referred to as "substrate"). Among them, a coating step of applying a curable composition to a support to form a curable composition layer is preferable, and a curable composition is directly applied onto the support to form a curable composition layer on the support. The coating step is better. Examples of the substrate include an alkali-free glass, a soda glass, a Pyrex (registered trademark) glass, a quartz glass, and a photoelectric conversion element for a solid imaging element, etc., which are used for a liquid crystal display device or the like. A substrate (for example, a fluorene ketone substrate or the like), a CCD substrate, a CMOS substrate, or the like. Further, in order to improve adhesion to the upper layer, prevent diffusion of substances, or planarize the surface of the substrate, an undercoat layer may be provided on the substrates as needed.

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

In addition, when a black matrix-containing color filter for a solid-state image sensor is used, the coating film thickness of the curable composition is preferably from 0.35 to 1.5 μm, and from 0.40 μm to 1.0 μm, from the viewpoint of resolution. good.

The curable composition applied to the substrate is usually dried at 70 to 110 ° C for 2 to 4 minutes. Thereby, a hardenable composition layer can be formed.

<Exposure Step> The exposure step is a step of exposing the curable composition layer (coating film) formed in the step of forming the curable composition layer through the mask, and partially curing only the coating film irradiated with light. The exposure is preferably performed by irradiation with active light or radiation, and in particular, ultraviolet rays such as g-rays, h-rays, and i-rays can be preferably used. Further, as the light source, a high pressure mercury lamp is preferred. As the exposure amount is not particularly limited, 200 ~ 1500mJ / cm ² is preferred, 200 ~ 1000mJ / cm ² is more preferably, 200 ~ 500mJ / cm ² is further preferred. When the exposure amount is within the above range, the method for producing a cured film has more excellent stability and productivity. Further, from the viewpoint of improving the resolution, in the formation of a light-shielding film for a solid-state image sensor, exposure by an i-ray stepper is preferred.

<Developing Step> The developing step is a step of developing the exposed hardenable composition layer. It is possible to develop and remove the unexposed portion by the developing step and obtain a patterned cured film. The method for producing the cured film includes a developing step and a washing step described below. In the developing step, an alkali developing treatment (developing step) is performed to dissolve the unexposed portion of the light in the exposure step in the aqueous alkali solution. Thereby, only the portion which has been photohardened (the portion of the coating film which is irradiated with light) remains. When a black matrix-containing light-shielding color filter for a solid-state image sensor is produced as a developer, it is preferable that the organic alkali developer such as a circuit of the substrate is not damaged. The development temperature is usually 20 to 30 ° C, and the development time is 20 to 90 seconds.

Examples of the alkaline aqueous solution include inorganic developing solutions and organic developing solutions. Examples of the inorganic developer include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, sodium citrate or sodium metasilicate, and the concentration thereof is 0.001 to 10% by mass, preferably 0.01 to ～. 1% by mass of an alkaline aqueous solution. Examples of the organic developing solution include ammonia water, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine or 1,8-. An organic basic compound such as diazabicyclo-[5.4.0]-7-undecene is dissolved in an alkaline aqueous solution having a concentration of 0.001 to 10% by mass, preferably 0.01 to 1% by mass. In the alkaline aqueous solution, for example, an appropriate amount of a water-soluble organic solvent such as methanol or ethanol, and/or a surfactant may be added. Further, as the developing method, for example, a spin-on immersion development, a shower development method, or the like can be used.

<Cleaning Step> The washing step is a step of washing (rinsing) the developed hardenable composition layer by pure water or the like. The cleaning method is not particularly limited, and a known cleaning method can be used.

Further, the method for producing a cured film may include a baking step after the above-described development step, and a hardening step of performing a full-surface exposure to the cured film.

[Solid-State Imaging Device and Solid-State Imaging Device] The solid-state imaging device and the solid-state imaging device according to the embodiment of the present invention include the cured film described above. The solid-state imaging device is not particularly limited as long as it contains a cured film. For example, a light-receiving region constituting a solid-state imaging device (CCD image sensor, CMOS image sensor, etc.) is provided on the substrate. The plurality of light-receiving elements including a photodiode and a polycrystalline germanium are provided on the light-receiving element forming surface side of the support (for example, a portion other than the light-receiving portion and/or a color adjusting pixel) or the opposite side of the forming surface. Hardened film. The solid-state image pickup device contains the above solid-state image pickup element.

A configuration example of a solid-state imaging device and a solid-state imaging device will be described with reference to Figs. 1 to 2 . In addition, in FIGS. 1 to 2, in order to clearly understand each part, the ratio of the thickness and/or the width of each structure is partially exaggerated regardless of the actual. As shown in FIG. 1, the solid-state imaging device 100 includes a rectangular solid-state imaging element 101, and a transparent cover glass 103 that is held above the solid-state imaging element 101 and seals the solid-state imaging element 101. Further, a lens layer 111 is superposed on the cover glass 103 via a spacer 104. The lens layer 111 is composed of a support 113 and a lens material 112. The lens layer 111 may be a structure in which the support body 113 is integrally formed with the lens material 112. When stray light is incident on the peripheral region of the lens layer 111, the effect of condensing the lens material 112 is weakened due to the diffusion of light, and the light reaching the imaging unit 102 is reduced. Also, noise caused by stray light is generated. Therefore, the peripheral layer region of the lens layer 111 is provided with a light shielding film 114 to shield light. The cured film of the embodiment of the present invention can also be used as the light shielding film 114 described above.

The solid-state imaging device 101 photoelectrically converts an optical image formed by the imaging unit 102 that is the light-receiving surface thereof, and outputs it as an image signal. The solid-state imaging element 101 includes a laminated substrate 105 in which two substrates are stacked. The laminated substrate 105 includes a rectangular wafer substrate 106 and a circuit substrate 107 having the same size, and a circuit substrate 107 is laminated on the back surface of the wafer substrate 106.

The material used as the substrate of the wafer substrate 106 is not particularly limited, and a known material can be used.

An imaging unit 102 is provided at a central portion of the surface of the wafer substrate 106. Further, when stray light is incident on the peripheral portion of the imaging unit 102, a dark current (noise) is generated from the circuit in the peripheral region, and thus the peripheral portion is provided with the light shielding film 115 to shield the light. The cured film of the embodiment of the present invention can also be used as the light shielding film 115.

A plurality of electrode pads 108 are provided on the surface edge of the wafer substrate 106. The electrode pad 108 is electrically connected to the imaging unit 102 via a signal line (a bonding wire) (not shown) provided on the surface of the wafer substrate 106.

External connection terminals 109 are provided on the back surface of the circuit board 107 at substantially lower positions of the electrode pads 108. Each of the external connection terminals 109 is connected to the electrode pad 108 via a through electrode 110 that vertically penetrates the laminated substrate 105. Further, each of the external connection terminals 109 is connected to a control circuit for controlling driving of the solid-state imaging device 101 and an image processing circuit for performing image processing on an image pickup signal output from the solid-state imaging device 101 via a wiring (not shown).

As shown in FIG. 2, the imaging unit 102 is configured by each of the light receiving elements 201, the color filters 202, and the microlenses 203 provided on the substrate 204. The color filter 202 has a blue pixel 205b, a red pixel 205r, a green pixel 205g, and a black matrix 205bm. The cured film of the embodiment of the present invention can also be used as the black matrix 205bm.

As the material of the substrate 204, the same material as the wafer substrate 106 described above can be used. A p-hole layer 206 is formed on the surface layer of the substrate 204. In the p-hole layer 206, a light-receiving element 201 including an n-type layer and generating signal charges by photoelectric conversion is formed in a square lattice shape.

On one side of the light receiving element 201, a vertical transfer path 208 including an n-type layer is formed via the read gate portion 207 of the surface layer of the p hole layer 206. Further, on the other side of the light receiving element 201, a vertical transfer path 208 belonging to an adjacent pixel is formed via the element isolation region 209 including the p-type layer. The read gate portion 207 is for reading a channel region of the signal charge accumulated in the light receiving element 201 to the vertical transfer path 208.

On the surface of the substrate 204, a gate insulating film 210 including an ONO (Oxide-Nitride-Oxide) film is formed. A vertical transfer electrode 211 including polycrystalline germanium or amorphous germanium is formed on the gate insulating film 210 so as to cover the vertical transfer path 208, the read gate portion 207, and the element isolation region 209 substantially directly above. The vertical transfer electrode 211 functions as a drive electrode that drives the vertical transfer path 208 to perform charge transfer and drives the read gate portion 207 to read the read electrode of the signal charge. The signal charge is sequentially transferred from the vertical transfer path 208 to a horizontal transfer path and an output unit (floating diffusion amplifier) (not shown), and then output as a voltage signal.

A light shielding film 212 is formed on the vertical transfer electrode 211 so as to cover the surface thereof. The light shielding film 212 has an opening at a position directly above the light receiving element 201, and shields other areas from light. The cured film of the embodiment of the present invention can also be used as the light shielding film 212. The light-shielding film 212 is provided with a transparent intermediate layer including an insulating film 213 containing BPSG (borophospho silicate glass), an insulating film (passivation film) 214 containing P-SiN, and a planarizing film 215 containing a transparent resin or the like. . A color filter 202 is formed on the intermediate layer.

[Black matrix] The black matrix contains the cured film of the embodiment of the present invention. The black matrix is sometimes included in a color filter, a solid-state imaging element, and a liquid crystal display device. Examples of the black matrix include those described above in the black edge of the peripheral portion of the display device such as a liquid crystal display device, and a grid-like and/or stripe-shaped black portion between red, blue, and green pixels; A dot pattern and/or a line black pattern for light-shielding of a TFT (thin film transistor). The definition of the black matrix is described in, for example, Takino Taiping, "Liquid Dictionary for Liquid Crystal Display Manufacturing Devices", Second Edition, NIKKAN KOGYO SHIMBUN, LTD., 1996, p. 64. Since the black matrix improves display contrast and, in the case of a liquid crystal display device using an active matrix driving method of a thin film transistor (TFT), the image quality is lowered due to prevention of current leakage of light, and thus has high light blocking property (optical density OD) It is preferably 3 or more.

The method for producing the black matrix is not particularly limited, and can be produced by the same method as the method for producing the cured film described above. Specifically, a curable composition layer is applied to a substrate to form a curable composition layer, and exposure and development are performed to produce a patterned cured film (black matrix). Further, as the film thickness of the cured film used as the black matrix, 0.1 to 4.0 μm is preferable.

The material of the substrate is not particularly limited, and a transmittance of 80% or more with respect to visible light (wavelength: 400 to 800 nm) is preferable. Specific examples of such a material include glass such as soda lime glass, alkali-free glass, quartz glass, and borosilicate glass; plastics such as polyester resin and polyolefin resin; and the like, from chemical resistance. From the viewpoint of properties and heat resistance, alkali-free glass or quartz glass or the like is preferable.

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

A color filter containing a black matrix (cured film) can be produced by using the above-described curable composition of the present invention, and can be produced, for example, by the following method. First, a coating film (resin composition layer) containing a resin composition of a pigment corresponding to each colored pixel of the color filter is formed in an opening portion of a pattern-shaped black matrix formed on a substrate. In addition, the resin composition for each color is not particularly limited, and a known resin composition can be used. However, the curable composition of the embodiment of the present invention is preferably used. Next, the resin composition layer is exposed through a photomask having a pattern corresponding to the opening of the black matrix. Next, after the unexposed portion is removed by the development process, baking is performed, whereby colored pixels can be formed in the opening portion of the black matrix. For example, a series of operations are performed using a resin composition containing each of red, green, and blue pigments, whereby a color filter having red, green, and blue pixels can be manufactured.

[Liquid Crystal Display Device] The liquid crystal display device of the embodiment of the present invention contains a cured film. The liquid crystal display device includes a cured film, and is not particularly limited, and examples thereof include a color filter including a black matrix (cured film).

The liquid crystal display device of the present embodiment includes, for example, a pair of substrates disposed opposite to each other and a liquid crystal compound sealed between the substrates. The above substrate has been described as a substrate for a black matrix.

Specific examples of the liquid crystal display device include, for example, a polarizing plate/substrate/color filter/transparent electrode layer/alignment film/liquid crystal layer/alignment film/transparent electrode layer/TFT (Thin) from the user side. Film Transistor) A laminate of components/substrate/polarizer/backlight unit.

In addition, the liquid crystal display device of the embodiment of the present invention is not limited to the above, and is described, for example, in "Electronic display device (Zoosuke Sasaki, Kogyo Chosakai Publishing Co., Ltd., 1990)", "Display" A liquid crystal display device such as the device (Ibuki Shunzhang, Industrial Book Co., Ltd. issued in Heisei). Further, for example, a liquid crystal display device described in "Second-generation liquid crystal display technology (edited by Uchida Takao, Kogyo Chosakai Publishing Co., Ltd., 1994)" is exemplified.

[Infrared Sensor] The infrared sensor according to the embodiment of the present invention contains the cured film described above. The infrared sensor of the above embodiment will be described with reference to Fig. 3 . In the infrared sensor 300 shown in FIG. 3, the reference numeral 310 denotes a solid-state imaging element. The imaging region provided on the solid-state imaging device 310 is combined with an infrared absorption filter 311 and a color filter 312 according to an embodiment of the present invention. The infrared absorption filter 311 transmits light in a visible light region (for example, light having a wavelength of 400 to 700 nm) and shields light in an infrared region (for example, light having a wavelength of 800 to 1300 nm, and light having a wavelength of 900 to 1200 nm is preferable, and wavelength A film having a light of 900 to 1000 nm is more preferable, and a cured film of an embodiment of the present invention can be used by using an infrared ray absorbing agent (as an infrared ray absorbing agent as described above) as a coloring agent. The color filter 312 is a color filter formed with pixels that transmit or absorb light of a specific wavelength in the visible light region, for example, using a filter in which pixels of red (R), green (G), and blue (B) are formed. A coloror or the like, the aspect of which has been described. A resin film 314 (for example, a transparent resin film or the like) capable of transmitting light of a wavelength transmitted through the infrared ray transmission filter 313 is disposed between the infrared ray transmission filter 313 and the solid state imaging device 310. The infrared transmission filter 313 is a filter that has visible light shielding properties and transmits infrared light of a specific wavelength, and can use a coloring agent (for example, a ruthenium compound and/or a dibenzofuran compound) containing light that absorbs a visible light region, and infrared absorption. A cured film of an embodiment of the present invention (for example, a pyrrolopyrrole compound, a phthalocyanine compound, a naphthalocyanine compound, or a polymethine compound). The infrared transmission filter 313 preferably shields light having a wavelength of 400 to 830 nm and transmits light having a wavelength of 900 to 1300 nm. The microlens 315 is disposed on the incident light hν side of the color filter 312 and the infrared ray transmission filter 313. A planarization film 316 is formed to cover the microlens 315. In the embodiment shown in FIG. 3, the resin film 314 is disposed, but the infrared transmission filter 313 may be formed instead of the resin film 314. That is, the infrared transmission filter 313 can be formed on the solid-state imaging element 310. In the embodiment shown in FIG. 3, the film thickness of the color filter 312 is the same as the film thickness of the infrared ray transmission filter 313, but the film thickness of both may be different. In the embodiment shown in FIG. 3, the color filter 312 is disposed on the side of the incident light hν from the infrared absorption filter 311, but the infrared absorption filter 311 and the color filter 312 may be replaced, and the infrared absorption filter may be used. The 311 is disposed closer to the incident light hν side than the color filter 312. Further, in the embodiment shown in Fig. 3, the infrared absorption filter 311 and the color filter 312 are adjacently stacked, but the two filters are not necessarily adjacent to each other, and other layers may be provided therebetween. According to the infrared sensor, since the image information can be read in at the same time, it is possible to perform motion sensing or the like of the object of the recognition detecting operation. Further, since the distance information can be acquired, it is also possible to perform photography including an image of 3D information.

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

Further, the above-mentioned cured film is suitable for portable devices such as personal computers, tablet computers, mobile phones, smart phones, and digital cameras; OA (Office Automation) devices such as multifunction printers and scanners; surveillance cameras and bar code readers. Industrial equipment such as ATM (automated teller machine), high-speed camera, and equipment with personal authentication function for face image authentication; camera equipment for vehicles; endoscope, capsule endoscope and catheter Medical camera equipment; biosensors, biosensors, military surveillance cameras, stereo map cameras, meteorological and oceanographic cameras, terrestrial resource surveillance cameras, and astronomical and deep space targets for the universe The optical filter and the light shielding member and the light shielding film of the optical filter and the module used in an aerospace device such as an exploration camera are further suitable for the antireflection member and the antireflection film.

The cured film can also be used for applications such as a micro LED (Light Emitting Diode) and a micro OLED (Organic Light Emitting Diode). The cured film is suitable for a member that imparts a light-shielding function or an anti-reflection function in addition to the optical filter and the optical film used in the micro LED and the micro OLED. Examples of the micro LED and the micro OLED include those described in JP-A-2015-500562 and JP-A-2014-533890.

The above-mentioned cured film is suitable as an optical filter and an optical film used in a quantum dot display. Further, it is suitable as a member for imparting a light blocking function and an antireflection function. Examples of the quantum dot display include U.S. Patent Application Publication No. 2013/0335677, 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. Recorder. [Examples]

Hereinafter, the present invention will be described in more detail based on examples. The materials, the amounts, the ratios, the processing contents, the processing steps, and the like shown in the following examples can be appropriately changed without departing from the gist of the invention. Therefore, the scope of the invention should not be construed as being limited by the embodiments shown below. Further, in the following examples, "parts" and "%" are mass references unless otherwise specified.

[Preparation of a curable composition containing a black coloring agent] Each of the components 1 to 9 shown below was mixed and stirred, and each of the curable properties of the examples and comparative examples shown in the following Tables 9 to 11 was obtained. Composition. In addition, the final solid content of each of the curable compositions was adjusted to the solid content concentration (described in the column of "organic solvent") in Tables 9 to 11 by the organic solvent described in the table.

Hereinafter, first, various components blended in the curable composition will be described.

1. A compound containing a group having a polymerization inhibiting ability and a thiol group As a compound containing a group having a polymerization inhibiting ability and a thiol group, the following enumerators are used. Hereinafter, a synthesis method of a compound containing a group having a polymerization inhibiting ability and a thiol group will be described by taking a synthesis method of the compound (C)-B-3-4 as an example. [Synthesis of Compound (C)-B-3-4]

(Synthesis Example-1) Synthesis of 3,5-di-t-butyl-4-hydroxydiphenylethylenedione acrylate In a 500 ml three-necked flask, 2,6-di-t-butyl-4- 35.45 g of (hydroxymethyl)phenol, 19.1 g of pyridine and 177 g of N,N-dimethylacetamide were stirred in an ice bath. Next, 20.36 g of acrylonitrile chloride was added dropwise to the system, and the obtained reaction liquid was warmed to room temperature and stirred for 4.5 hours. Then, 300 ml of 1N hydrochloric acid was added to the reaction liquid, and the mixture was extracted with 300 ml of ethyl acetate, and the organic phase was extracted by washing with 750 ml of saturated brine. Next, 12 g of a crude product was obtained by drying the obtained organic phase with sodium sulfate and concentrating the filtrate obtained after the filtration operation under reduced pressure. Purification by a silica gel column gave 10.9 g (yield: 25%) of 3,5-di-t-butyl-4-hydroxydiphenylethanedione acrylate as a target product.

(Synthesis Example-2) Synthesis of Compound (C)-B-3-4 In a 50 ml flask, neopentyl alcohol tetrakis(3-mercaptopropionate) (manufactured by Tokyo Chemical Industry Co., Ltd.) was added. 2.03 g of 3,5-di-t-butyl-4-hydroxydiphenylethanedione acrylate and 12.5 g of ethanol were stirred at room temperature. After stirring, 312 mg of triethylamine was added to the mixture, followed by stirring at room temperature for 30 minutes. Then, 20 ml of 1N hydrochloric acid and 20 ml of water were added to the system, and extracted with 40 ml of ethyl acetate. Then, the obtained organic phase was washed with water (40 ml), and concentrated under reduced pressure to give Compound (C)-B-3-44.55 g (yield: 83.5%). The structure of the compound (C)-B-3-4 is shown in Table 4. In the compound (C)-B-3-4, R which is bonded to a sulfur atom represents a hydrogen atom (corresponding to Ra in the table) or 3,5-di-t-butyl-4-hydroxybenzyloxycarbonylethyl group. (equivalent to Rb in the table). That is, when R is a hydrogen atom, it forms a thiol group together with a sulfur atom. Further, when R is a 3,5-di-t-butyl-4-hydroxybenzyloxycarbonylethyl group, the 3,5-di-tert-butyl-4-hydroxyphenyl group corresponds to a group having a polymerization inhibiting ability. group. In the compound (C)-B-3-4, the "number of thiol groups" and the "number of groups having a polymerization inhibiting ability" were identified as the average based on the area ratio (integrated intensity ratio) of the peaks measured by NMR. As a result, it was confirmed that the number of thiol groups was 3.6, and the number of 3,5-di-tert-butyl-4-hydroxyphenyl group corresponding to a group having a polymerization inhibiting ability was 0.4. Further, for the other "compounds having a group having a polymerization inhibiting ability and a thiol group" shown below, "the number of thiol groups" and "the group having a polymerization inhibiting ability" are also determined by the same method. number".

[Compound (C)-B-1-1 to Compound (C)-B-1-3] Compound (C)-B-1-1 to Compound (C)-B-1-3 were synthesized by the following : The raw material thiol (neopentitol tetrakis(3-mercaptopropionate) (manufactured by Tokyo Chemical Industry Co., Ltd.)) of (Synthesis Example-2) was changed to tetraethylene glycol bis(3-mercaptopropionic acid) Ester), and the amount of addition of 3,5-di-t-butyl-4-hydroxydiphenylethanedione acrylate was changed. Hereinafter, the structures of the obtained compound (C)-B-1-1 to the compound (C)-B-1-3 are shown in Table 2. Further, in the following formula, R which is bonded to a sulfur atom represents a hydrogen atom (corresponding to Ra in the table) or 3,5-di-t-butyl-4-hydroxybenzyloxycarbonylethyl (equivalent to a table) In the Rb). That is, when R is a hydrogen atom, it forms a thiol group together with a sulfur atom. Further, when R is a 3,5-di-t-butyl-4-hydroxybenzyloxycarbonylethyl group, the 3,5-di-tert-butyl-4-hydroxyphenyl group corresponds to a group having a polymerization inhibiting ability. group. Further, the number of the thiol groups in the compound (C)-B-1-1 to the compound (C)-B-1-3 and the number of groups having a polymerization inhibiting ability are shown in the table.

[Chemical Formula 30]

[Table 2]

[Compound (C)-B-2-1 to Compound (C)-B-2-3] Compound (C)-B-2-1 to Compound (C)-B-2-3 were synthesized by the following : The raw material thiol (neopentitol tetrakis(3-mercaptopropionate) (manufactured by Tokyo Chemical Industry Co., Ltd.)) (synthesis example-2) was changed to trimethylolpropane tris(3-mercapto) Propionate), and the addition amount of 3,5-di-t-butyl-4-hydroxydiphenylethanedione acrylate was changed. The structures of the obtained compound (C)-B-2-1 to the compound (C)-B-2-3 are shown in Table 3. Further, in the following formula, R which is bonded to a sulfur atom represents a hydrogen atom (corresponding to Ra in the table) or 3,5-di-t-butyl-4-hydroxybenzyloxycarbonylethyl (equivalent to a table) In the Rb). That is, when R is a hydrogen atom, it forms a thiol group together with a sulfur atom. Further, when R is a 3,5-di-t-butyl-4-hydroxybenzyloxycarbonylethyl group, the 3,5-di-tert-butyl-4-hydroxyphenyl group corresponds to a group having a polymerization inhibiting ability. group. Further, the number of the thiol group in the compound (C)-B-2-1 to the compound (C)-B-2-3 and the number of groups having a polymerization inhibiting ability are shown in the table.

[Chemical Formula 31]

[table 3]

[Compound (C)-B-3-1 to Compound (C)-B-3-6] Compound (C)-B-3-1 to Compound (C)-B-3-6 by modification (Synthesis Example) -2) The amount of 3,5-di-t-butyl-4-hydroxydiphenylethanedione acrylate added is synthesized. The structures of the obtained compound (C)-B-3-1 to the compound (C)-B-3-6 are shown in Table 4. Further, in the following formula, R which is bonded to a sulfur atom represents a hydrogen atom (corresponding to Ra in the table) or 3,5-di-t-butyl-4-hydroxybenzyloxycarbonylethyl (equivalent to the table). Rb). That is, when R is a hydrogen atom, it forms a thiol group together with a sulfur atom. Further, when R is a 3,5-di-t-butyl-4-hydroxybenzyloxycarbonylethyl group, the 3,5-di-tert-butyl-4-hydroxyphenyl group corresponds to a group having a polymerization inhibiting ability. group. Further, the number of the thiol group in the compound (C)-B-3-1 to the compound (C)-B-3-6 and the number of groups having a polymerization inhibiting ability are shown in the table.

[Chemical Formula 32]

[Table 4]

[Compound (C)-B-4-1 to Compound (C)-B-4-3] Compound (C)-B-4-1 to Compound (C)-B-4-3 were synthesized by the following manner : The raw material thiol (neopentitol tetrakis(3-mercaptopropionate) (manufactured by Tokyo Chemical Industry Co., Ltd.)) (synthesis example-2) was changed to dipentaerythritol hexa(3-fluorenyl) Propionate), and the addition amount of 3,5-di-t-butyl-4-hydroxydiphenylethanedione acrylate was changed. The structures of the obtained compound (C)-B-4-1 to the compound (C)-B-4-3 are shown in Table 5. Further, in the following formula, R which is bonded to a sulfur atom represents a hydrogen atom (corresponding to Ra in the table) or 3,5-di-t-butyl-4-hydroxybenzyloxycarbonylethyl (equivalent to the table). Rb). That is, when R is a hydrogen atom, it forms a thiol group together with a sulfur atom. Further, when R is a 3,5-di-t-butyl-4-hydroxybenzyloxycarbonylethyl group, the 3,5-di-tert-butyl-4-hydroxyphenyl group corresponds to a group having a polymerization inhibiting ability. group. Further, the number of the thiol group in the compound (C)-B-4-1 to the compound (C)-B-4-3 and the number of groups having a polymerization inhibiting ability are shown in the table.

[Chemical Formula 33]

[table 5]

[Compound (C)-B-5-1 to Compound (C)-B-5-3] Compound (C)-B-5-1 to Compound (C)-B-5-3 were synthesized in the following manner : The raw material thiol (neopentitol tetrakis(3-mercaptopropionate) (manufactured by Tokyo Chemical Industry Co., Ltd.)) (synthesis example-2) was changed to tripentaerythritol poly(3-mercapto group) Propionate), and the addition amount of 3,5-di-t-butyl-4-hydroxydiphenylethanedione acrylate was changed. The structures of the obtained compound (C)-B-5-1 to the compound (C)-B-5-3 are shown in Table 6. Further, in the following formula, R which is bonded to a sulfur atom represents a hydrogen atom (corresponding to Ra in the table) or 3,5-di-t-butyl-4-hydroxybenzyloxycarbonylethyl (equivalent to the table). Rb). That is, when R is a hydrogen atom, it forms a thiol group together with a sulfur atom. Further, when R is a 3,5-di-t-butyl-4-hydroxybenzyloxycarbonylethyl group, the 3,5-di-tert-butyl-4-hydroxyphenyl group corresponds to a group having a polymerization inhibiting ability. group. Further, the number of the thiol group in the compound (C)-B-5-1 to the compound (C)-B-5-3 and the number of groups having a polymerization inhibiting ability are shown in the table.

[Chemical Formula 34]

[Table 6]

Compound (C)-T-3-1 to Compound (C)-T-3-3] (Synthesis Example-3) 2-((((2,2,6,6-tetramethyl acridine 1-oxyl) Synthesis of ethyl radical-4-yl)oxy)carbonyl)amino)ethyl acrylate In a 300 ml three-necked flask, 19.7 g of propylene glycol monomethyl ether acetate was added to Karenz AOI (manufactured by Showa Denko Co., Ltd.). 73.5 g, and 19.7 g of 4-hydroxy TEMPO (TEMPO: 2,2,6,6-tetramethylacridine 1-oxyl), and the obtained mixture was stirred at 70 °C. Next, 0.231 g of NEOSTANN U-600 (manufactured by NITTO DENKO CORPORATION) was added to the mixture, followed by further heating and stirring at 70 ° C for 3.5 hours. After returning the obtained reaction liquid to room temperature, 350 ml of water was added to the reaction liquid, and ethyl acetate (140 ml) was added thereto for extraction. The organic phase was dried over magnesium sulfate, and the filtrate obtained after filtration was concentrated under reduced pressure. Purification by a silica gel column to obtain 2-((((2,2,6,6-tetramethyl acridine 1-oxyl)-4-yl)oxy)carbonyl)amino)acrylic acid as a target product Ethyl ester 21 g (yield: 79.7%).

Compound (C)-T-3-1 to Compound (C)-T-3-3 were synthesized by the following raw material (3,5-di-t-butyl group of (Synthesis Example-2)) -4-hydroxydiphenylethylenedione acrylate) was changed to 2-(((2,2,6,6-tetramethylacridinyl 1-oxyl-4-yl)oxy)carbonyl)amine Base) ethyl acrylate and change the amount added. The structures of the obtained compound (C)-T-3-1 to the compound (C)-T-3-3 are shown in Table 7. Further, in the following formula, R which is bonded to a sulfur atom represents a hydrogen atom (corresponding to Ra in the table) or ((((2,2,6,6-tetramethylacridine-1-oxyl radical-4) -yl)oxy)carbonyl)amino)ethoxycarbonylethyl (corresponding to Rb in the table). That is, when R is a hydrogen atom, it forms a thiol group together with a sulfur atom. Further, when R is (((2,2,6,6-tetramethylacridin-1-oxymethyl-4-yl)oxy)carbonyl)amino)amino)ethoxycarbonylethyl, 2, The 2,6,6-tetramethylacridine 1-oxyl radical-4-yl group corresponds to a group having a polymerization inhibiting ability. Further, the number of the thiol group in the compound (C)-T-3-1 to the compound (C)-T-3-3 and the number of groups having a polymerization inhibiting ability are shown in the table.

[Chemical Formula 35]

[Table 7]

2. Colorant Dispersion Liquid [Preparation of Colorant Dispersion Liquid 1 (Titanium Black) and Colorant Dispersion Liquid 2 (TiN)] <Colorant> It was produced by the following method for blending into a colorant dispersion liquid to be described later. Each colorant.

<<Production of Titanium Black A-1>>>> Titanium oxide MT-150A (trade name: manufactured by TAYCA CORPORATION) having an average particle diameter of 15 nm was weighed to 100 g, and a BET (Brunauer, Emmett, Teller) specific surface area of 300 m ² /g was used. The cerium oxide particles AEROSIL 300 (registered trademark) 300/30 (manufactured by Evonik Japan Co., Ltd.) weighed 25 g, and weighed 100 g of Disperbyk 190 (trade name: manufactured by BYK Chemie GmbH), and added these to ion-exchanged water 71 g. Medium, thereby obtaining a mixture. Thereafter, MAZERSTAR KK-400W was produced using KURABO, and the mixture was subjected to treatment for 30 minutes at a revolution speed of 1,360 rpm and a rotation speed of 1047 rpm, whereby a uniform aqueous mixture solution was obtained. The aqueous solution mixture was filled in a quartz vessel, and heated to 920 ° C in an oxygen atmosphere using a small rotary kiln (manufactured by MOTOYAMA CO., LTD.). Then, the atmosphere in the small rotary kiln was replaced with nitrogen, and the ammonia gas flow was conducted at 100 mL/min for 5 hours at the same temperature, thereby performing a nitriding reduction treatment. The powder recovered after completion of the mash was pulverized to obtain a titanium black containing a Si atom and having a powder specific surface area of 73 m ² /g (including a dispersion of titanium black particles and Si atoms) (hereinafter, referred to as "titanium" Black A-1").

<<Titanium nitride-containing particles (TiN-1)>> First, Ti particles (manufactured by TOHO TECHNICAL SERVICE CO., LTD.) were subjected to plasma treatment in Ar gas, thereby performing Ti nanoparticle. Particle formation. After the Ar gas atmosphere, the O ₂ concentration of 50ppm or less, at 30 ℃ will Ti nanoparticles after the plasma treatment for 24 hours, the concentration of O ₂ in the embodiment becomes 100ppm O ₂ is introduced into the Ar gas atmosphere In the state of gas, it was allowed to stand at 30 ° C for 24 hours (pretreatment of Ti particles). Thereafter, the obtained Ti nanoparticles were classified by a TTSP separator manufactured by Hosokawa Micron Corporation under the conditions of a yield of 10% to obtain Ti particle powders. The average particle diameter of 100 particles was determined by arithmetic mean by observation by TEM (Transmission Electron Microscope), and the obtained primary particle diameter of the powder was 120 nm. Titanium nitride-containing particles TiN-1 were produced by a device according to the apparatus for producing a black composite fine particle shown in Fig. 1 of International Publication No. 2010/147098. Specifically, in the apparatus for producing a black composite fine particle, a high-frequency voltage of about 4 MHz and about 80 kVA is applied to the coil for high-frequency oscillation of the electric torch, and argon gas is supplied as a plasma gas from the plasma gas supply source. A mixed gas of min and nitrogen of 50 L/min produces an argon-nitrogen thermal plasma flame in the plasma torch. Further, a carrier gas of 10 L/min was supplied from a spray gas supply source of the material supply device. Then, for the Ti particles obtained as described above, Fe powder (JIP270M, manufactured by JFE STEEL CORPORATION) and Si powder (Silicon powder SI006031) were made Ti/Fe/Si=99.9/0.05/0.05 in respective mass ratios. The mixture is mixed and supplied to the pyroplasmic plasmon in the electric torch together with the argon gas as a carrier gas, so that it is evaporated in the thermal plasma inflammation, so that it is highly dispersed in the gas phase state. Further, nitrogen is 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 1000 L/min. Further, the pressure in the cyclone was set to 50 kPa, and the supply rate of each raw material from the chamber to the cyclone was set to 10 m/s (average value). Titanium nitride-containing particles TiN-1 were thus obtained.

The content of titanium (Ti) atoms, iron (Fe) atoms, and cerium (Si) atoms was measured by ICP emission spectrometry on the obtained titanium nitride-containing particles TiN-1. Further, in the ICP emission spectrometry, an ICP emission spectroscopic analyzer "SPS3000" (trade name) manufactured by Seiko Instruments Inc. was used. Further, the content of nitrogen atoms was measured by an inert gas fusion thermal conductivity method measured by an oxygen/nitrogen analyzer "EMGA-620W/C" (trade name) manufactured by HORIBA, Ltd. As a result of the above, the mass ratio of each atom contained in the titanium nitride-containing particles TiN is Ti/N/Fe/Si = 57/34/0.0030/0.0020.

The X-ray diffraction of the titanium nitride-containing TiN-1 was carried out in a standard sample holder made of aluminum, and was carried out by a wide-angle X-ray diffraction method (manufactured by Rigaku Corporation, trade name "RU-200R"). measuring. As a measurement condition, the X-ray source is set to CuKα ray, the output is set to 50 kV/200 mA, the slit system is set to 1°-1°-0.15mm-0.45mm, the measurement step size (2θ) is set to 0.02°, and the scanning speed is set. It is 2 ° / min. Further, the diffraction angle of the peak derived from the TiN (200) plane observed in the vicinity of the diffraction angle 2θ (42.6°) was measured. Further, the crystallite size of the constituent particles was obtained by the Scherrer formula from the half width of the peak derived from the (200) plane. As a result, the diffraction angle of the peak was 42.62°, and the crystallite size was 10 nm. In addition, no X-ray diffraction peak due to TiO _{2 was} observed at all.

<Preparation of the colorant dispersion liquid> The coloring agent prepared above, the dispersing agent shown below, and the organic solvent shown below were each made into the composition shown in Table 8, and the stirring machine (EUROSTAR by IKA company) was used. After mixing for 15 minutes, a mixture was obtained. Then, the obtained mixed liquid was subjected to dispersion treatment under the following conditions using NPM-Pilot manufactured by SHINMARU ENTERPRISES CORPORATION to obtain a colorant dispersion liquid.

<Dispersing agent> ・Dispersing resin 1A: A dispersing agent represented by the following formula (the numerical value of each structural unit (the numerical value of the main chain repeating unit together) is shown by the content of the structural unit [mol%%]. The numerical value of the repeating site described in the side chain together indicates the number of repetitions of the repeating site.) Further, "Mw" represents a weight average molecular weight.

[Chemical Formula 36]

<Organic solvent> ・PGMEA: propylene glycol 1-monomethyl ether 2-acetate

<<Dispersion conditions>> ・Bead diameter: φ0.05 mm, (Zirconium oxide beads manufactured by NIKKATO CORPORATION, YTZ) ・Bead filling ratio: 65 vol% ・Polishing peripheral speed: 10 m/sec ・Separator peripheral speed: 13 m/s ・The amount of the mixed liquid to be subjected to the dispersion treatment: 15 kg ・Circulating flow rate (pump supply amount): 90 kg/hour ・Processing liquid temperature: 19 to 21 ° C ・Cooling water: water ・Processing time: 22 hours or so

[Table 8]

[Preparation of Colorant Dispersion Liquid 3 (Carbon Black)] A high-viscosity dispersion treatment was carried out using a double roll using the following composition C to obtain a dispersion composition. The viscosity of the dispersion composition at this time was 70,000 mPa·s. Then, a mixture of the following composition D was added to the dispersion composition, and the mixture was stirred for 3 hours at 3000 rpm using a homogenizer. The obtained mixed solution was subjected to a microdispersion treatment for 4 hours by a disperser (trade name: DISPERMAT, GETZMANN) using a 0.3 mm zirconia bead to prepare a colorant dispersion 3. The viscosity of the mixed solution at this time was 37 mPa·s.

<Composition C> ・Carbon black (average primary particle diameter: 15 nm)······23 parts by mass ・Benzyl methacrylate/methacrylic acid (Mohr ratio=67/33) copolymer (Mw: 28000) PGMEA 45% solution ······22 parts by mass ・Dispersant (SOLSPERSE 5000 made by AstraZeneca plc)·······1.2 parts by mass

<Composition D> ・PGMEA 45% solution of benzyl methacrylate/methacrylic acid (mol ratio = 67/33) copolymer (Mw: 28000) · 22 parts by mass, solvent (PGMEA)·· ····200 parts by mass

3. Alkali-Soluble Resin In the curable composition, the following are used as the alkali-soluble resin.・Alkali-soluble resin 1: benzyl methacrylate/acrylic acid copolymer [composition ratio: benzyl methacrylate/acrylic acid copolymer = 80/20 (% by mass), Mw: 25000]

4. Polymerizable compound In the curable composition, a polymerizable compound represented by the following formula is used as the polymerizable compound.

[Chemical Formula 37]

5. Photopolymerization initiator In the curable composition, the following quinone polymerization initiator was used as a photopolymerization initiator.・Indole polymerization initiator: IRGACURE OXE-02 (manufactured by BASF) ・肟 polymerization initiator 2: ADEKA ARKLS NCI-831 (manufactured by ADEKA CORPORATION, containing nitro group.) ・肟 polymerization initiator 3 :

[Chemical Formula 38]

・肟 polymerization initiator 4:

[Chemical Formula 39]

6. Surfactant In the curable composition, the following were used as the surfactant. - Surfactant 1: A surfactant represented by the following formula (weight average molecular weight (Mw) = 15311) wherein, in the following formula, the structural units represented by (A) and (B) in the formula are 62, respectively. Moer%, 38% Mo. In the structural unit represented by the formula (B), a, b, and c satisfy the relationship of a+c=14 and b=17, respectively.

[Chemical Formula 40]

7. Comparison of polyfunctional thiols As the comparative polyfunctional thiol, a polyfunctional thiol 1 having the following structure was used.

[Chemical Formula 41]

8. Comparison of polymerization inhibitors As a polymerization inhibitor for comparison, the following types of polymerization inhibitors were used.・Polymerization inhibitor 1: 4-methoxyphenol ・Polymerization inhibitor 2: Dibutylhydroxytoluene (BHT) ・Polymerization inhibitor 3: 4-hydroxy-2,2,6,6-tetramethylpiperidine 1 -oxyl radical

9. Solvents ・PGMEA: Propylene glycol 1-monomethyl ether 2-acetate ・Cyclohexanone

[Evaluation] Each of the above curable compositions was evaluated by the following method.

[Evaluation of Storage Stability] <1. Exposure Sensitivity (Initial) of Curable Composition> Each of the curable compositions immediately after preparation was applied onto a glass substrate by spin coating, and dried to form a film thickness of 1.0. a layer of a hardening composition of μm. Regarding the conditions of the spin coating, first, spin coating was performed at a rotation speed of 300 rpm (rotation per minute) for 5 seconds, followed by spin coating at 800 rpm for 20 seconds. Further, the drying conditions were carried out at 100 ° C for 80 seconds. The coating film obtained by the above was coated with a pattern of a line and space of 1 μm by an i-ray stepwise exposure apparatus FPA-3000i5+ (manufactured by Canon Co., Ltd.) at 10 to 1600 mJ/cm ² . The exposure amount illuminates light having a wavelength of 365 nm. Then, the curable composition layer after the exposure was developed using a developing solution of 60% CD-2000 (manufactured by FUJIFILM Electronic Materials Co., Ltd.) at 25 ° C for 60 seconds to obtain a patterned cured film. Thereafter, the patterned cured film was rinsed with running water for 20 seconds, and then air-dried. In the above-described exposure step, the minimum exposure amount of the pattern line width after development in the region where the light is irradiated is 1.0 μm or more is used as the exposure sensitivity, and the exposure sensitivity is taken as the initial exposure sensitivity.

<2. Exposure Sensitivity of Curable Composition (After Time: After 30 Days at 45 ° C)> The curable composition immediately after preparation was sealed in a sealed container, and a thermostat having an internal temperature of 45 ° C was held ( Within EYELA/LTI-700), take it out after 30 days. Using the obtained curable composition, the same test as that performed using the curable composition immediately after preparation was performed, and the exposure sensitivity was determined. This is taken as the exposure sensitivity after the lapse of time.

<Evaluation> The rate of change (%) of the exposure sensitivity obtained by the following equation was calculated from the initial exposure sensitivity and the exposure sensitivity after the lapse of time. The smaller the value of the above-described variation rate (%), the more excellent the storage stability. (Formula) variation rate = [(exposure sensitivity after time - initial exposure sensitivity) / initial exposure sensitivity] × 100 In addition, in actual use, it is preferable to evaluate "3" or more, and "4" and "5" are evaluated as Has excellent performance. The results are shown in Tables 9 to 11. - Evaluation criteria - "5": The rate of change is 0% to 3%. "4": The rate of change is more than 3% and less than 6%. "3": The rate of change is over 6% and is less than 10%. "2": The rate of change is more than 10% and is 15% or less. "1": The rate of change is over 15%.

[Evaluation of the residue of the unexposed portion] In the above test <1. Exposure sensitivity (initial) of the curable composition>, the cured film obtained by the minimum exposure amount of the pattern line width after development of 1.0 μm or more is used. The glass substrates were heated in an oven at 220 ° C for 1 hour. After the cured film was heated, the number of residues present in the unexposed area (unexposed portion) in the exposure step on the glass substrate was observed by SEM (Scanning Electron Microscope, magnification: 20000 times), thereby evaluating the unexposed portion. Residue. The evaluation was performed based on the following criteria, and the results are shown in Tables 9 to 11. Further, in actual use, it is preferable to evaluate "3" or more, and "4" and "5" are evaluated as having excellent performance.

- Evaluation criteria - "5": A pattern was formed, and no residue was observed in the unexposed portion. "4": A pattern was formed, and 1 to 3 residues were observed on the sides of 1.0 μm of the unexposed portion. "3": A pattern was formed, and 4 to 10 residues were observed on the sides of 1.0 μm of the unexposed portion. "2": A pattern was formed, and 11 or more residues were observed on the sides of 1.0 μm of the unexposed portion. "1": No pattern was formed due to poor development.

[Evaluation of Pattern Edge Shape (Undercut/Width)] The pattern edge shape of the pattern-like cured film formed using each of the curable compositions was evaluated by the following method.

<Step of Forming Curable Composition Layer> A curable composition layer was formed on the tantalum wafer so that the film thickness after drying became 1.5 μm. The formation of the curable composition layer was carried out by spin coating. The number of revolutions of the spin coating was adjusted so as to be the film thickness. The applied curable composition layer was placed on a hot plate with the ruthenium wafer facing downward, and dried. The surface temperature of the hot plate was set to 100 ° C, and the drying time was set to 120 seconds.

<Exposure Step> The obtained hardenable composition layer was exposed under the following conditions. The exposure was carried out using an i-ray stepper (trade name "FPA-3000iS+", manufactured by Canon Co., Ltd.). The curable composition layer was irradiated (exposed) with a mask having a linear shape of 20 μm (width: 20 μm, length: 4 mm) at an exposure amount of 400 mJ/cm ² (irradiation time: 0.5 second).

<Developing Step> The dried curable composition layer was developed under the following conditions to obtain a patterned cured film. The dried curable composition layer was subjected to spin-on immersion development at 23 ° C for 60 seconds using a 0.3% by mass aqueous solution of tetramethylammonium hydroxide (TMAH) for 5 times to obtain a patterned cured film. Thereafter, the patterned cured film was rinsed by shower rinsing and further washed with pure water.

<Post-baking step> The patterned hardened film obtained above was heated at 220 ° C for 300 seconds using a clean oven CLH-21CDH (manufactured by Koyo Thermo Systems Co., Ltd.). Further, the heated patterned cured film was placed on a hot plate having a surface temperature of 220 ° C and heated for 300 seconds.

<Evaluation> The patterned cured film was imaged by a scanning electron microscope, and the edge shape of the 20 μm pattern cross section was evaluated by the following criteria. 1. Measurement Evaluation of Undercut Width (μm) As shown in FIG. 4, the length T of the slit at the bottom of the pattern edge portion 2 of the patterned cured film formed on the wafer 4 was measured as an undercut width. Further,, L ₁ is an exposure area corresponding to FIG. 4, L ₂ corresponds to the unexposed areas. The evaluation was performed based on the following criteria, and the results are shown in Tables 9 to 11. - Evaluation criteria - "AA": The undercut width exceeds 0 μm and is 0.25 μm or less. "A": The undercut width exceeds 0.25 μm and is 0.5 μm or less. "B": the undercut width exceeds 0.5 μm and is 1.0 μm or less. "C": The undercut width exceeds 1.0 μm.

2. Measurement Evaluation of Increased Width (μm) As shown in FIG. 5, the length P of the upper portion of the pattern edge portion 6 of the patterned cured film formed on the wafer 4 was measured. Further, in FIG. 5, L ₁ corresponds to the exposure region, L ₂ corresponding to the unexposed areas. The evaluation was performed based on the following criteria, and the results are shown in Tables 9 to 11.

- Evaluation criteria - "AA": The increased width is more than 0 μm and is 0.25 μm or less. "A": the increased width is more than 0.25 μm and is 0.5 μm or less. "B": the increased width is more than 0.5 μm and is 1.0 μm or less. "C": The width is increased by more than 1.0 μm.

Tables 9 to 11 are shown below. "PGMEA/cyclohexanone = 1/1" in the "solvent" column of the table is a mass ratio. The value of the formula (1) in the table indicates the number of groups having a polymerization inhibiting ability / (number of thiol groups + having polymerization inhibition ability) in a compound containing a group having a polymerization inhibiting ability and a thiol group The number of groups) × 100 is calculated as the value R1. The "mass ratio of photopolymerization initiator to specific compound" in the table means the mass ratio of the photopolymerization initiator to the compound containing a group having a polymerization inhibiting ability and a thiol group.

[Table 9]

[Table 10]

[Table 11]

From the results of Tables 9 to 11, it was confirmed that when the curable composition of the example was used, it was possible to obtain excellent storage stability, suppress generation of residue in the unexposed portion, and have an excellent pattern shape. Hardened film.

Further, when the respective examples 1 to 3, the examples 4 to 6, the examples 7 to 12, the examples 13 to 15, the examples 16 to 18, and the examples 19 to 21 are compared, it is confirmed that 1) When the numerical value is 1 to 50% (preferably 3 to 30%, more preferably 8 to 15%), the effects of the present invention are more excellent.

Further, from the comparison of Example 2, Example 5, Example 9, Example 14 and Example 17, it was confirmed that n is 3 to 6 (preferably 4) in the compound represented by the formula (1X). At the time, the effect of the present invention is more excellent.

Further, from the comparison of Examples 8 to 10 and Examples 19 to 21, it was confirmed that the group having the polymerization inhibiting ability is a one-valent group derived from a phenol-based compound (preferably 3,5-di- The effect of the present invention is more excellent when the third butyl-4-hydroxyphenyl group is used.

Further, from the comparison of Examples 24 to 26 and Examples 29 to 33, it was confirmed that the content of the compound containing a group having a polymerization inhibiting ability and a thiol group is 0.01 to 3% by mass based on the total solid content ( When the content is preferably 0.2 to 2.5% by mass, more preferably 0.6 to 1.3% by mass, the effects of the present invention are more excellent.

From the comparison of Examples 22 to 33, it was confirmed that the content of the photopolymerization initiator was from 1 to 100 times by mass based on the content of the compound having a group having a polymerization inhibiting ability and a thiol group. The effect of the present invention is more excellent. In particular, when the content of the photopolymerization initiator is from 2.5 to 35 times by mass based on the content of the compound having a group having a polymerization inhibiting ability and a thiol group, the ability to suppress broadening and the ability to suppress undercut are confirmed. Further, it is further confirmed that the content of the photopolymerization initiator is excellent in storage stability when the content of the compound having a group having a polymerization inhibiting ability and a thiol group is 2.5 to 25 times by mass. The development residue suppressing ability is also more excellent. In particular, when the content of the photopolymerization initiator is 5 to 10 times by mass based on the content of the compound having a group having a polymerization inhibiting ability and a thiol group, the undercut can be remarkably suppressed.

On the other hand, it was confirmed that the curable composition of the comparative example did not exhibit the desired effect.

[Example 39] A curable composition of Example 39 was prepared in the same manner as in Example 1 except that the components and the blending amounts described in Table 12 were used. Further, the curable composition of Example 39 obtained was evaluated in the same manner as in Example 1. The results are shown in Table 12. In addition, the various components used in Table 12 are the same as the various components used in Tables 9 to 11.

From the results of Table 12, it was confirmed that the sclerosing property of the compound containing a group having a polymerization inhibiting ability and a thiol group and a polyfunctional thiol compound not containing a group having a polymerization inhibiting ability was used. In the case of the composition, it is also possible to obtain a cured film which is excellent in storage stability, suppresses generation of residue in the unexposed portion, and has an excellent pattern shape.

[Table 12]

[The curable composition containing the coloring agent] The curable composition of Examples 40 to 42 was prepared in the same manner as in Example 1 except that the components and the blending amounts described in Table 13 were used. Further, the curable compositions of Comparative Examples 7 to 9 were prepared in the same manner as in Comparative Example 1, except that the components and the blending amounts described in Table 14 were used. Further, the curable compositions of Examples 40 to 42 and Comparative Examples 7 to 9 obtained were evaluated in the same manner as in Example 1. The results are shown in Table 13 and Table 14. Further, the components other than the colorant dispersion liquids used in Tables 13 and 14 were the same as those of the users in Tables 9 to 11.

Hereinafter, various coloring dispersions used in Tables 13 and 14 will be described. [Preparation of Blue Pigment Dispersion] Pigment blue 15:6 (9.5 parts by mass), Pigment Violet 23 (2.4 parts by mass), and BYK-161 (manufactured by BYK Co., Ltd.) as a coloring agent (5.6 parts by mass) A mixture of propylene glycol monomethyl ether acetate (PGMEA) (82.5 parts by mass) as a solvent was mixed by a bead mill for 15 hours to prepare a blue pigment dispersion.

[Preparation of Green Pigment Dispersion] (Synthesis Example 4) Synthesis of a zinc halide phthalocyanine pigment Zinc phthalocyanine was produced using phthalonitrile, ammonia, and zinc chloride as raw materials. The 1-chloronaphthalene solution has a light absorption at 750 to 850 nm. The halogenation of zinc phthalocyanine is as follows. First, thioindole chloride (45.5 parts by mass), anhydrous aluminum chloride (54.5 parts by mass), and sodium chloride (7 parts by mass) were mixed at 40 ° C, and a zinc phthalocyanine pigment (15 parts by mass) was added. Bromine (35 parts by mass) was added dropwise thereto, and the temperature was raised to 130 ° C for 19.5 hours and maintained for 1 hour. The reaction mixture was then extracted into water to precipitate a crude zinc halide phthalocyanine pigment. The aqueous slurry was filtered, washed with hot water at 60° C., washed with 1% sodium hydrogensulfate water, washed with hot water at 60° C., and dried at 90° C. to obtain 2.7 parts by mass of purified halogenated product. Zinc phthalocyanine crude pigment A. The purified crude zinc halide phthalocyanine pigment A (1 part by mass), sodium chloride (10 parts by mass) obtained by pulverization, and diethylene glycol (1 part by mass) are added to a double-arm type kneader at 100 The mixture was kneaded at ° C for 8 hours. After kneading, the mixture was taken out to water (100 parts by mass) at 80 ° C, and after stirring for 1 hour, it was filtered, washed with hot water, dried, and pulverized to obtain a zinc halide phthalocyanine pigment. The average composition of the obtained zinc halide phthalocyanine pigment was ZnPcBr _9.8 Cl _3.1 H _3.1 based on mass analysis and halogen content analysis using a flask combustion ion chromatograph. In addition, Pc is an abbreviation for phthalocyanine.

The zinc halide phthalocyanine pigment (pigment 1) (50 parts by mass), pigment yellow 150 (pigment 2) (15 parts by mass), and pigment derivative A (5 parts by mass) obtained in Synthesis Example 4, and dispersion of the resin were contained. A mixture of the agent A (20 parts by mass) and propylene glycol monomethyl ether acetate (PGMEA) (360 parts by mass) as a solvent was mixed by a bead mill for 15 hours to prepare a green pigment dispersion.

・Pigment derivative A: Structure shown below

[Chemical Formula 42]

・Dispersant A: The structure shown below (the numerical value of each structural unit (the numerical value of the main-chain repeating unit together) is shown by the content of each structural unit [mol%]. It is also described in the side chain. The value of the repeated part indicates the number of repetitions of the repeated part.)

[Chemical Formula 43] Acid value = 50 mg KOH / g, Mw = 24000

[Preparation of Red Pigment Dispersion] <Red Pigment Dispersion: Preparation of Dispersion Containing PR254/PY139> Pigment Red 254 (9.6 parts by mass), Pigment Yellow 139 (4.3 parts by mass), and Pigment Dispersant BYK-161 were contained. (Batch of BYK) (6.8 parts by mass) and a mixture of propylene glycol methyl ether acetate (hereinafter referred to as "PGMEA") (79.3 parts by mass) were mixed by a bead mill (zirconia beads diameter: 0.3 mm) for 3 hours. Thereby, a pigment dispersion liquid was prepared. Then, a high-pressure disperser NANO-3000-10 (manufactured by Nippon BEE Chemical Co., Ltd.) equipped with a pressure reducing mechanism was used, and a flow rate under a pressure of 2000 kg/cm ³ was set to 500 g/min, and dispersion treatment was performed. This dispersion treatment was repeated 10 times to obtain a red pigment dispersion.

Hereinafter, the results are shown in Table 13 and Table 14.

[Table 13]

[Table 14]

From the above results, it was confirmed that the desired effect of the present invention is exhibited even in the case of using a smear coloring agent as a coloring agent.

[Infrared absorbing pigment and curable composition containing color pigment] The curable composition of Example 43 was prepared in the same manner as in Example 1 except that the components and the blending amounts described in Table 16 were used. Further, the curable composition of Comparative Example 10 was prepared in the same manner as in Comparative Example 1, except that the components and the blending amounts described in Table 17 were used. Further, the curable compositions of Example 43 and Comparative Example 10 obtained were evaluated in the same manner as in Example 1. The results are shown in Tables 16 and 17. In addition, various components other than the coloring agent dispersion liquid (IR (infrared rays) pigment dispersion liquid and colored pigment dispersion liquid) and alkali-soluble resin used in Table 16 and Table 17 are shown in Table 9 - Table 11. The user is the same. The coloring agent dispersion liquid (IR pigment dispersion liquid and colored pigment dispersion liquid) and the alkali-soluble resin are respectively used later.

[Colorant dispersion liquid] <Dispersion liquid containing infrared absorbing pigment (IR dispersion)> (Preparation of dispersion containing infrared absorbing pigment) Pyrrolopyrrole pigment 1 (13.5 parts by mass), dispersion resin 1 (4.0 parts by mass) ), a mixture of PGMEA (82.5 parts by mass) using zirconia beads having a diameter of 0.3 mm, and a bead mill (NANO-3000-10 (manufactured by Nippon BEE Co., Ltd.) equipped with a high-pressure dispersing machine with a pressure reducing mechanism) The mixture was mixed and dispersed to prepare an IR pigment dispersion. Further, the dispersion resin 1 is the same as those of the color pigment dispersion liquids 2-1 to 2-4 described later.

Pyrrolopyrrole pigment 1: The following structure (synthesized by the method described in JP-A-2009-263614) (having an infrared absorbing agent having a large absorption in the range of 800 to 900 nm)

[Chemical Formula 44]

<Preparation of Colored Pigment Dispersions 2-1 to 2-4> A mixture of the compositions shown in Table 15 below was used with zirconia beads having a diameter of 0.3 mm, and was subjected to a bead mill (high pressure with a pressure reducing mechanism) The disperser NANO-3000-10 (manufactured by Nippon BEE Co., Ltd.) was mixed and dispersed for 3 hours to prepare a chromatic pigment dispersion 2-1 to 2-4. The amounts of the respective components used (unit: parts by mass) are shown in Table 15 below.

[Table 15]

Hereinafter, the components used in Table 15 are shown. Further, the alkali-soluble resin 2 is also separately used in the preparation of the curable composition.

(Dispersant) ・Dispersion resin 1: Disperbyk-111 (manufactured by BYK Chemie Co., Ltd.)

- Dispersion Resin 2: The following structure (Mw: 7950) (the numerical value of each structural unit (the numerical value of the main-chain repeating unit) is shown together, and the content of each structural unit [% by mole] is shown together. The value of the repeating part of the side chain indicates the number of repetitions of the repeating part.)

[Chemical Formula 45]

- Dispersion Resin 3: The following structure (Mw: 30000) (the numerical value of each structural unit (the numerical value of the main-chain repeating unit) is shown together, and the content of each structural unit [% by mole] is shown together. The value of the repeating part of the side chain indicates the number of repetitions of the repeating part.)

[Chemical Formula 46]

(Alkali-soluble resin) - Alkali-soluble resin 2: The following structure (Mw: 12000) (the numerical value of each structural unit is shown together with the content of each structural unit [% by mole].)

[Chemical Formula 47]

Hereinafter, the results are shown in Tables 16 and 17.

[Table 16]

[Table 17]

From the above results, it was confirmed that the desired effect of the present invention is exhibited even in the case of using a curable composition using an infrared ray absorbing agent and a colored pigment as a coloring agent.

[The curable composition containing a white coloring agent] The curable composition of Example 44 was prepared in the same manner as in Example 1 except that the components and the blending amounts described in Table 18 were used. Further, the curable composition of Comparative Example 11 was prepared in the same manner as in Comparative Example 1, except that the components and the blending amounts described in Table 19 were used. Further, the curable compositions of Example 44 and Comparative Example 11 obtained were evaluated in the same manner as in Example 1. The results are shown in Table 18 and Table 19. In addition, the components other than the coloring agent dispersion liquid and the alkali-soluble resin used for the curable composition of Table 18 and Table 19 are the same as those of the user of Table 9 - Table 11. The coloring agent dispersion liquid and the alkali-soluble resin are each used later.

[Colorant Dispersion Liquid] <Preparation of White Pigment Dispersion> In the dispersion liquid containing titanium black A-1 (colorant dispersion liquid 1), a colorant dispersion liquid was prepared by using a titanium oxide pigment instead of titanium black A-1 ( The composition of the colorant dispersion was as follows. Titanium oxide: 38.5 parts by mass, manufactured by Solsperse 36000 Lubrizol Japan Ltd.: 11.5 parts by mass, PGMEA: 50 parts).

[Alkali-Soluble Resin 3] Further, the weight-average molecular weight Mw of the alkali-soluble resin 3 described below was 12,000. (The numerical values stated in each structural unit indicate the content of each structural unit [% by mole].)

[Chemical Formula 48]

Hereinafter, the results are shown in Table 18 and Table 19.

[Table 18]

[Table 19]

From the above results, it was confirmed that the desired effect of the present invention was exhibited even in the case of using a white coloring agent as a curable composition of a coloring agent.

[Example 45] A curable composition was produced and evaluated in the same manner as in Example 3 except that the surfactant was not used. As a result, the same results as in Example 3 were obtained.

[Example 46] A curable composition was produced in the same manner as in Example 3 except that the dispersion resin was changed from the dispersion resin 1A to the dispersion resin 1B shown below, in the color dispersion liquid used in Example 3, The evaluation was carried out, and as a result, the same results as in Example 3 were obtained. - Dispersing Resin 1B: The dispersing agent represented by the following formula (the numerical value of each structural unit (the numerical value of the main-chain repeating unit together) is shown by the content of each structural unit [mol%]. The value of the repeating part of the side chain indicates the number of repetitions of the repeating part.)

[Chemical Formula 49] Further, "Mw" represents a weight average molecular weight.

[Example 47] In Example 3, except that 15 parts by mass of M-1 as a polymerizable compound was replaced by M-1 10 parts by mass and PET-30 (neopentitol triacrylate, Nippon Kayaku Co., Ltd.) The evaluation was carried out in the same manner except for 5 parts by mass. As a result, the same results as in Example 3 were obtained.

[Example 48] In Example 3, instead of TiN-1, TiN-1 and carbon black (trade name "Color Black S170", manufactured by Degussa Co., Ltd., average primary particle diameter: 17 nm, BET specific surface area: 200 m ² /g, were used. The carbon black produced by the gas black method was evaluated in the same manner as in Example 3 except that the solid content ratio was 7:3, and the results were obtained except that the evaluation of the undercut was changed from AA to A. The same effects as in the first embodiment are obtained.

[Example 49] A curable composition was prepared in the same manner as in Example 40 except that the green pigment dispersion liquid of Example 41 was replaced with the following green pigment dispersion liquid 2, and the same procedure as in Example 41 was carried out. As a result of evaluation, the same effect as that of Example 41 was obtained. <Green Pigment Dispersion 2> In the preparation of the green pigment dispersion of Example 41, the green pigment dispersion 2 was prepared in the same manner except that the dispersant A was replaced by the following Dispersant B.

・Dispersant B: The structure shown below (the numerical value of each structural unit is shown together with the number of repetitions of the repeating part.) a=3.5, b=2.5, acid value=30 mgKOH/g, Mw=20000 [Chemical Formula 50]

100‧‧‧ Solid-state camera

101‧‧‧ Solid-state photographic components

102‧‧‧Photography Department

103‧‧‧ Cover glass

104‧‧‧ spacers

105‧‧‧Laminated substrate

106‧‧‧ wafer substrate

107‧‧‧ circuit board

108‧‧‧electrode pads

109‧‧‧External connection terminal

110‧‧‧through electrode

111‧‧‧ lens layer

112‧‧‧Lens material

113‧‧‧Support

114, 115‧‧‧Shade film

201‧‧‧Light-receiving components

202‧‧‧ color filter

203‧‧‧Microlens

204‧‧‧Substrate

205b‧‧‧Blue pixels

205r‧‧‧Red Pixels

205g‧‧‧ green pixels

205bm‧‧‧Black matrix

206‧‧‧p hole layer

207‧‧‧Reading the gate

208‧‧‧ vertical transfer path

209‧‧‧Component separation area

210‧‧‧Gate insulation film

211‧‧‧Vertical transfer electrode

212‧‧‧Shade film

213, 214‧‧ ‧ insulating film

215‧‧‧flat film

300‧‧‧Infrared sensor

310‧‧‧Solid camera components

311‧‧‧Infrared absorption filter

312‧‧‧ color filter

313‧‧‧Infrared transmission filter

314‧‧‧ resin film

315‧‧‧Microlens

316‧‧‧Flat film

4‧‧‧ wafer

2, 6‧‧‧ pattern edge

Hν‧‧‧ incident light

T‧‧‧ slit length

P‧‧‧檐 Length

L ₁ ‧‧‧Exposure area

L ₂ ‧‧‧Unexposed areas

Fig. 1 is a schematic cross-sectional view showing a configuration example of a solid-state image pickup device. Fig. 2 is a schematic cross-sectional view showing the image pickup unit of Fig. 1 in an enlarged manner. Fig. 3 is a schematic cross-sectional view showing a configuration example of an infrared sensor. Fig. 4 is a schematic cross-sectional view showing the measurement evaluation of the undercut width (μm). Fig. 5 is a schematic cross-sectional view showing the measurement evaluation of the width increase (μm).

Claims (17)

A curable composition comprising: a compound containing a group having a polymerization inhibiting ability and a thiol group; a polymerizable compound; a photopolymerization initiator; and a colorant. The curable composition according to claim 1, wherein the compound having a group having the polymerization inhibiting ability and a thiol group has a value R1 of from 1 to 50% represented by the following formula (1). Formula (1): R1 = [Number of groups having polymerization inhibition ability / (Number of thiol groups + Number of groups having polymerization inhibition ability)] × 100. The curable composition according to claim 2, wherein the compound having the group having the polymerization inhibiting ability and the thiol group has a value R1 represented by the formula (1) of from 3 to 30%. The curable composition according to claim 2, wherein the compound having the group having the polymerization inhibiting ability and the thiol group has a value R1 represented by the formula (1) of 8 to 15%. The curable composition according to any one of claims 1 to 4, wherein the photopolymerization initiator is present in an amount relative to a compound having a group having a polymerization inhibiting ability and a thiol group. The content is 1 to 100 times in mass ratio. The curable composition according to any one of the items 1 to 4, wherein the content of the compound having a group having the polymerization inhibiting ability and the thiol group is 0.01 to 3 with respect to the total solid content. quality%. The curable composition according to any one of claims 1 to 4, wherein the group having the polymerization inhibiting ability is selected from the group consisting of a phenol-based compound and represented by the formula (IH-2) a compound of any one of the group of compounds derived from a valence group, In the formula (IH-2), W represents an alkylene group. The curable composition according to any one of claims 1 to 4, wherein the compound having a group having the polymerization inhibiting ability and a thiol group is a compound represented by the formula (1). In the formula (1), m represents 0, 1 or 2, and L ₁ independently represents a member selected from the group consisting of an alkylene group, an extended aryl group, an ether group, an ester group, a thioester group, a decyl group, and an amine group. any of a group of the ester group, and a urea group or a combination of two or more coupling group, Q ₁ each independently represents a hydrogen atom or a group represented by the general formula (2), In the formula (2), L ₂ represents a group selected from the group consisting of an alkylene group, an extended aryl group, an ether group, an ester group, a thioester group, a decylamino group, a urethane group, and a ureido group. One or a combination of two or more kinds, and Q ₂ is a monovalent group derived from a compound selected from the group consisting of a phenolic compound and a compound represented by the general formula (IH-2), and * represents When a plurality of L ₂ and Q ₂ are present in the formula (1), the plurality of L ₂ and the plurality of Q ₂ may be the same or different, wherein the formula is In the compound represented by the formula (1), the value R3 represented by the following formula (3) and the value R4 represented by the following formula (4) are both more than 0%, and the formula (3): R3 = [number of Q ₂ / (number of thiol groups + number of Q ₂ )] × 100 Formula (4): R4 = [number of thiol groups / (number of thiol groups + number of Q ₂ )] × 100 In the formula (IH-2), W represents an alkylene group. The curable composition according to any one of claims 1 to 4, further comprising a thiol compound which does not contain a group having a polymerization inhibiting ability. A compound containing a group having a polymerization inhibiting ability and a thiol group. The compound according to claim 10, wherein the group having the polymerization inhibiting ability is derived from any one selected from the group consisting of a phenolic compound and a compound represented by the formula (IH-2). Monovalent group, In the formula (IH-2), W represents an alkylene group. A compound according to claim 10 or 11, which is represented by the formula (1), In the formula (1), m represents 0, 1 or 2, and L ₁ independently represents a member selected from the group consisting of an alkylene group, an extended aryl group, an ether group, an ester group, a thioester group, a decyl group, and an amine group. Any one or a combination of two or more of a group of an acid ester group and a urea group, and Q ₁ each independently represents a hydrogen atom or a group represented by the formula (2). In the formula (2), L ₂ represents a group selected from the group consisting of an alkylene group, an extended aryl group, an ether group, an ester group, a thioester group, a decylamino group, a urethane group, and a ureido group. Any one or a combination of two or more, Q ₂ is a monovalent group derived from a compound selected from the group consisting of a phenolic compound and a compound represented by the general formula (IH-2), * In the case of a plurality of L ₂ and Q ₂ in the formula (1), the plurality of L ₂ and the plurality of Q ₂ may be the same or different, wherein the In the compound represented by the formula (1), the numerical value R3 represented by the following formula (3) and the numerical value R4 represented by the following formula (4) are both numbers exceeding 0%, and the formula (3): R3 = [number of Q ₂ / (number of thiol group number + Q _2)] × 100 (4): number R4 = [thiol groups / (the number of thiol group number + Q _2)] × 100 In the formula (IH-2), W represents an alkylene group. A cured film obtained by hardening the curable composition according to any one of claims 1 to 9. A method for producing a cured film, comprising: a step of forming a curable composition layer, wherein the curable composition layer is formed using the curable composition according to any one of claims 1 to 9; The curable composition layer is exposed to a pattern; and a developing step is performed to remove the unexposed portion to form a cured film. A method of producing a color filter comprising the method for producing a cured film according to item 14 of the patent application. A solid-state photographic element comprising the cured film described in claim 13 as a color filter. An infrared sensor comprising the cured film described in claim 13 as a color filter.