TW201827401A - Curable composition, cured film, color filter, light-blocking film, solid-state imaging element, image display device, and method for manufacturing cured film - Google Patents

Abstract

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

Description

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

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

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

As a curable composition, for example, Patent Document 1 describes a colored composition characterized by containing (A) a colorant, (B) a binder resin, and (C) a photopolymerization initiator having a predetermined structure, (D) A compound having two or more polymerizable unsaturated bonds and (E) a polyfunctional thiol. [Prior Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Unexamined Patent Publication No. 2013-83932

As a result of research on the coloring composition described in Patent Document 1, the present inventors have clarified that there is a problem that the pattern shape of the obtained cured film does not reach the level required recently. In addition, in this specification, the pattern shape refers to the pattern shape of the cured film measured by the method described in the examples.

An object of the present invention is to provide a curable composition capable of obtaining a cured film having an excellent pattern shape (hereinafter also referred to as "having the effect of the present invention."). Moreover, the subject of this invention is providing a cured film, a color filter, a light-shielding film, a solid-state imaging element, an image display device, and the manufacturing method of a cured film.

The inventors have conducted intensive studies to achieve the above-mentioned problems and found that the above-mentioned problems can be achieved by the following configuration.

[1] A hardening composition containing a photopolymerization initiator, a polyfunctional thiol compound, a polymerizable compound, and a coloring agent, the aforementioned hardening composition is characterized in that the photopolymerization initiator is represented by formula (1) The oxime compound represented. [2] The curable composition according to [1], wherein the carbon number of R ¹ in formula (1) is 13 or more. [3] The curable composition according to [1] or [2], wherein the content mass ratio of the content of the oxime compound to the content of the polyfunctional thiol compound in the curable composition is 1 to 10. [4] The curable composition according to any one of [1] to [3], wherein the content mass ratio of the content of the oxime compound to the content of the polyfunctional thiol compound in the curable composition is 4 ~ 10. [5] The curable composition according to any one of [1] to [4], wherein the polyfunctional thiol compound is a compound represented by formula (2). [6] The hardenable composition as described in [5], wherein in formula (2), R ²⁴ and R ²⁵ are each independently an alkyl group or -C (= O) -OR ²³ , and M ²¹ is -C (= O) -O-, n is an integer of 3 ~ 10. [7] The hardenable composition according to any one of [1] to [6], wherein the colorant includes an organic pigment. [8] The hardenable composition according to any one of [1] to [6], wherein the colorant includes an inorganic pigment. [9] A cured film obtained by curing the curable composition according to any one of [1] to [8]. [10] A color filter including the cured film described in [9]. [11] A light-shielding film containing the cured film described in [9]. [12] A solid-state imaging element including the cured film described in [9]. [13] An image display device comprising the cured film described in [9]. [14] A method for producing a cured film, comprising: a step of forming a curable composition layer, using the curable composition described in any one of [1] to [8] to form a curable composition on a support Layer; and an exposure step to expose the hardenable composition layer. [15] The method for producing a cured film according to [14], wherein the step of forming the curable composition layer is a step of applying the curable composition on the support and forming the curable composition layer on the support . [16] The method for producing a cured film according to [14] or [15], which further includes a developing step to develop the exposed curable composition layer. [Effect of invention]

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

Hereinafter, the present invention will be described in detail. The description of the constituent elements described below may be completed based on the representative embodiments of the present invention, but the present invention is not limited to these embodiments. In this specification, the numerical range represented by "~" means the range which includes the numerical value described before and after "~" as a lower limit and an upper limit. In the labeling of the group (atomic group) in this specification, the labeling system which is not marked with substituted or unsubstituted includes those having no substituent and those having a substituent. For example, "alkyl" means not only an unsubstituted alkyl group (unsubstituted alkyl group), but also an substituted alkyl group (substituted alkyl group). The "actinic rays" or "radiation" in this specification means, for example, extreme ultraviolet rays, extreme ultraviolet rays (EUV: Extreme ultraviolet lithography light), X-rays, and electron beams. In this specification, "light" refers to actinic rays and radiation. "Exposure" in this specification refers to, unless otherwise specified, not only includes exposure to extreme ultraviolet rays, X-rays, and EUV light, but also includes drawing by particle beams such as electron beams and ion beams. In this specification, "(meth) acrylate" means acrylate and methacrylate. In this specification, "(meth) acrylic acid" means acrylic acid and methacrylic acid. In this specification, "(meth) acryloyl" means acryloyl and methacryloyl. In this specification, "(meth) acrylamide" means acrylamide and methacrylamide. In this specification, "monomer" has the same meaning as "monomer". Single system refers to a compound that is different from oligomers and polymers and has a weight average molecular weight of 2,000 or less. In this specification, a polymerizable compound refers to a compound containing a polymerizable group, and may be a monomer or a polymer. The polymerizable group refers to a group that participates in a polymerization reaction.

[Curable composition] One of the characteristics of the curable composition of the embodiment of the present invention is that it contains a photopolymerization initiator, a polyfunctional thiol compound, a polymerizable compound and a coloring agent, and the photopolymerization initiator is This is the oxime compound (hereinafter, also referred to as "specific oxime compound") represented by formula (1) described later.

According to the curable composition of the present invention having such a structure, a cured film having an excellent pattern shape is obtained. The detailed reason is not clear, but the inventors speculate as follows. In addition, the scope of the present invention is not limited by the following assumptions. In other words, when an effect other than the following estimated mechanism is obtained, it is also included in the scope of the present invention.

A typical method for producing a cured film is a method of applying a curable composition to a support to obtain a curable composition layer, and exposing it to a pattern shape and developing it. However, the optical density (also referred to as optical density (OD)) of the curable composition layer increases in order from the long-wavelength side to the short-wavelength side, and becomes particularly high on the short-wavelength side. For this reason, for example, when the light in the ultraviolet region such as g-rays, h-rays, and i-rays (in other words, short-wavelength light) is used to expose the curable composition layer into a pattern shape, the light does not reach the inside of the curable composition layer As a result, the exposure becomes insufficient, and as a result, the curable composition is not cured as expected, resulting in deterioration of the pattern shape of the cured film. The mechanism by which the shape of the pattern is deteriorated by the above will be described using FIGS. 1 to 6 schematically showing the steps of manufacturing the cured film for each step. First, FIGS. 1 to 3 are cross-sectional views schematically showing the steps of manufacturing a cured film using a curable composition containing no polyfunctional thiol compound for each step. First, as shown in FIG. 1, a curable composition layer 102 is formed on the support 101 using a curable composition. Next, the curable composition layer 102 is exposed through the opening of the mask 103 (in FIG. 1, the arrow indicates the irradiation direction of light, and line A-B is an extension line of the opening end of the mask. The same applies hereinafter.). Then, the curable composition layer 102 after the above exposure is developed to form a pattern-shaped cured film 201. When performing the exposure in the above steps, since the optical concentration of the curable composition layer 102 is high, it is difficult for light to reach the inside of the curable composition layer 102 during exposure, resulting in the exposure change under the curable composition layer 102 Not enough. In this way, by developing, the insufficiently exposed portion of the hardenable composition layer 102 causes the hardenable composition to elute (FIG. 2). Under these conditions, if the cured film 201 is heated and then baked, the thickness of the cured film 301 at the end after the baking is reduced compared to the central portion, and it is presumed that the pattern shape becomes Those who are prone to deterioration (Figure 3).

In contrast, FIGS. 4 to 6 are cross-sectional views schematically showing the steps of manufacturing a cured film using a curable composition containing a polyfunctional thiol compound and not containing a specific oxime compound described below for each step. First, as shown in FIG. 4, a curable composition layer 401 is formed on the support 101 using a curable composition containing a polyfunctional thiol compound. Then, the curable composition layer 401 is exposed through the opening of the photomask 103. At this time, inside the exposed curable composition layer 401, a polymerization reaction is started by the radical generated from the photopolymerization initiator. The multifunctional thiol compound functions as a chain transfer agent. Therefore, for example, even if the peroxy radicals that interfere with the polymerization reaction are generated by the reaction of radicals and oxygen, it is considered that the hydrogen is supplied to the peroxy radicals through the thiol group in the multifunctional thiol compound The polymerization of oxygen deactivates the insensitive sulfonyl radicals and proceeds the polymerization reaction. Therefore, it is presumed that the curable composition containing the polyfunctional thiol compound is easily cured to the inside of the curable composition layer 401. On the other hand, since the polyfunctional thiol compound has high reactivity and easily causes chain transfer, the radical polymerization reaction is chained to the unexposed portion depending on the conditions such as the composition of the curable composition, the amount of exposure, and the shape of the pattern. In particular, In some cases, the unexposed portion of the curable composition layer on the light irradiation surface side may be accidentally cured. In this case, if the curable composition layer after exposure is developed, there may be a problem that the cured film 501 expands unexpectedly to an unexposed portion (FIG. 5). When such a problem occurs, the end portion of the cured film 601 after post-baking unexpectedly expands, sometimes causing the pattern shape to deteriorate (FIG. 6).

The inventors who first discovered the above phenomenon have repeatedly conducted in-depth studies to complete the present invention. The curable composition of the present invention contains an oxime compound (specific oxime compound) as a photopolymerization initiator. The oxime compound contains a hydrocarbon group having 8 or more carbon atoms in which R ¹ of formula (1) described later may contain a hetero atom. The specific oxime compound becomes bulky under the influence of the group represented by R ¹ described above. Since the specific oxime compound has a bulky structure as described above, it is presumed to be difficult to diffuse in the curable composition layer. Therefore, even when a highly reactive polyfunctional thiol compound is used as the chain transfer agent, the free radical species is difficult to diffuse to the unexposed portion, and as a result, it is difficult to generate a hardening reaction in the unexposed portion. Pattern-shaped hardened film. Hereinafter, each component contained in the curable composition of the embodiment of the present invention will be described in detail.

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

[Specific oxime compound] The curable composition of the embodiment of the present invention contains a specific oxime compound described later. The specific oxime compound has a function as a photopolymerization initiator. The content of the specific oxime compound in the curable composition is not particularly limited, but it is usually preferably 1 to 8% by mass relative to the total solid content of the curable composition. The specific oxime compound may be used alone or in combination of two or more. When two or more specific oxime compounds are used at the same time, the total content is preferably within the above range. In addition, as a specific oxime compound, the N—O bond may be (E) or (Z). As a specific oxime compound, the (E) form and the (Z) form can also be used simultaneously.

[Chemical Formula 1]

In formula (1), R ¹ represents a hydrocarbon group having 8 or more carbon atoms which may contain a hetero atom. The hydrocarbon group may be linear, branched, cyclic, or a combination of these. Among them, a linear, branched, or cyclic hydrocarbon group having 13 or more carbon atoms which may contain a hetero atom is preferred from the viewpoint of obtaining a curable composition having more excellent effects of the present invention. The hetero atom contained in R ¹ is not particularly limited, and examples thereof include a nitrogen atom, a sulfur atom, and an oxygen atom. Examples of R ¹ include linear alkyl groups having 8 or more carbon atoms, branched alkyl groups having 8 or more carbon atoms, cycloalkyl groups having 8 or more carbon atoms, and cycloalkyl groups containing 8 or more carbon atoms. Hydrocarbon groups and groups represented by * -L ¹¹ -R ¹¹ . In addition, L ¹¹ represents a divalent linking group, R ¹¹ represents an alkyl group, and * represents a bonding position with a carbon atom. Here, the divalent linking group of L ¹¹ is not particularly limited. For example, alkylene group, carbonyl group, -O-, -S-, -NR ^12- , and combinations thereof, etc. are preferred. A combination of two or more groups of alkyl, -O-, -S-, and -NR ¹² -is more preferable. Here, R ¹² represents a hydrogen atom or an alkyl group.

As R ¹ , from the viewpoint of obtaining a curable composition having more excellent effects of the present invention, a linear alkyl group having 13 or more carbon atoms or a group represented by * -L ¹¹ -R ¹¹ is preferred Preferably, the group represented by * -L ¹¹ -R ¹¹ is more preferred, and the group represented by the following formula (1-1) is further preferred. [Chemical Formula 2]

In formula (1-1), R ¹³ represents an alkylene group having 1 to 3 carbon atoms, Z ¹ represents at least ^one selected from the group consisting of -O-, -S-, and -NR ^12- , and R ¹⁴ represents Alkyl, n ¹¹ represents an integer of 1 or more. R ¹² represents a hydrogen atom or an alkyl group. In addition, when there are a plurality of R ¹³ and Z ¹ in formula (1-1), each R ¹³ and Z ¹ may be the same or different, and * represents a bonding position.

In formula (1), X ² represents a single bond or a divalent linking group. Examples of the divalent linking group include alkylene groups (preferably having 1 to 12 carbon atoms), cycloalkylene groups, and alkenyl groups. , Alkynyl group, carbonyl group, -S-, -O-, -NR ¹⁵ -and groups combining them, etc., from the viewpoint of obtaining a curable composition having more excellent effects of the present invention, X ² is preferably a single bond or an alkylene group or a group formed by combining an alkylene group with -S-. In addition, R ¹⁵ represents a hydrogen atom or an alkyl group.

In formula (1), R ² represents an alkyl group or an aryl group. Among them, from the viewpoint of obtaining a curable composition having more excellent effects of the present invention, R ² may each contain a substituent, a linear alkyl group having 1 to 25 carbon atoms, and a carbon atom having 1 to 25 carbon atoms. A branched alkyl group, or an alicyclic alkyl group having 4 to 25 carbon atoms or an aryl group containing a substituent is preferred. In addition, examples of the substituent include a halogen atom (of which, a fluorine atom is preferred.), Aryloxy, alkoxycarbonyl, aryloxycarbonyl, acetyloxy, acetyl, alkyl, aryl and The groups represented by * -X ⁶ -R ⁶ are not limited to these. In addition, * represents a bonding position, and the form of X ⁶ and R ⁶ will be described later.

In formula (1), X ³ represents a single bond or a carbonyl group. In addition, R ³ represents an aryl group and may contain a substituent. Among them, from the viewpoint of obtaining a curable composition having more excellent effects of the present invention, R ³ is represented by the following formula (1-2) The group is preferred. *-[Ar] -X ⁶ -R ⁶ formula (1-2) In addition, in formula (1-2), * represents a bonding position with X ³ , [Ar] represents an arylene group, which may be a single ring, It can also be a fused ring. X ⁶ represents a single bond or a divalent linking group. Examples of the divalent linking group of X ⁶ include alkylene, aryl, cycloalkyl, alkenyl, alkynyl, carbonyl, -S-, -O-, and -NR ⁶¹ -and They are grouped together. Here, R ⁶¹ represents a hydrogen atom or an alkyl group. Among them, X ⁶ series single bond, -S- or carbonyl group is preferable from the viewpoint of obtaining a curable composition having more excellent effects of the present invention. In the above formula, R ⁶ represents a hydrogen atom or a substituent. The substituent is not particularly limited, and examples thereof include an alkyl group, -NO ₂ , aryl group, and heterocyclic group. In addition, the substituent may be a substituent that the aryl group of R ² may contain.

Examples of the specific oxime compound include compounds represented by the following formula (1-A) to formula (1-D). [Chemical Formula 3]

More specifically, the compound represented by following formula (1-a)-(1-d) is mentioned. [Chemical Formula 4]

In formula (1-A) ~ formula (1-D) and formula (1-a) ~ formula (1-d), the definitions of R ¹ , R ² , X ² and X ³ are the same as those in formula (1) R ¹ , R ² , X ² and X ^{3 are the} same, and the preferred forms are also the same. Formula (1-A) ~ formula (1-D) and formula (1-a) - in the formula (1-d), R ¹⁰ represents a hydrogen atom or a monovalent substituent group. The monovalent substituent is not particularly limited, for example, -NO ₂ (hereinafter, also referred to as nitro.), A group represented by * -X ⁶ -R ⁶ , an aryl group which may contain a substituent, and Aryl heterocyclic groups which may contain substituents and the like.

In formula (1-A) ~ formula (1-D) and formula (1-a) ~ formula (1-d) (except for formula (1-B) and formula (1-b)), R ⁷ represents -O-, -S- or -NR ^71- . R ⁷¹ represents a substituent, and the substituent is not particularly limited, and examples thereof include an alkyl group having 1 to 20 carbon atoms (which may be linear, branched, or cyclic.), And a carbon number of 4 ~ 20 alicyclic hydrocarbon group, aryl group with 6-30 carbon atoms, arylalkyl group with 7-30 carbon atoms, etc. The above-mentioned substituent may contain a hetero atom. Among them, a nitrogen atom, an oxygen atom, a halogen atom, etc. are preferred as a hetero atom from the viewpoint of obtaining a curable composition having more excellent effects of the present invention. The nitrogen atom , An oxygen atom or a fluorine atom is more preferable.

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

Specific examples of the specific oxime compound are shown in Tables 1-1 to 1-4 below, but the specific oxime compound is not limited thereto. In addition, in Table 1, the wavy line indicates the bonding position, and "↑" indicates the same as the column directly above. In addition, the structure described in the "-X ² -R ² " column represents a state in which the linking group X ² is bonded to the group represented by R ² . In addition, the contents of the "formula" column correspond to the above formulas (1-a) to (1-d), and the symbols (R ¹ , -X ² -R ² , X ³ , R ⁷ , R ⁸ and R ¹⁰ ) Corresponds to each symbol in each formula. In addition, "none" in the columns of R ⁷ and R ⁸ means that the compound represented by the corresponding formula does not contain the group represented by R ⁷ and the group represented by R ⁸ , respectively. In addition, the number of each specific oxime compound (“INT-1” to “INT-50”) corresponds to the number of each specific oxime compound in the examples.

[Table 1-1]

[Table 1-2]

[Table 1-3]

[Table 1-4]

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

The specific oxime compound can be synthesized by a known method. Typically, it can be synthesized by the reaction between the corresponding oxime and acetyl chloride in an inert solvent or alkaline solvent in the presence of alkali. Examples of the base include triethylamine and pyridine. Examples of the inert solvent include tertiary butyl methyl ether, tetrahydrofuran (THF), and dimethylformamide. Examples of the alkaline solvent include pyridine.

[Polyfunctional thiol compound] The curable composition of the embodiment of the present invention contains a polyfunctional thiol compound. In this specification, a multifunctional thiol compound refers to a group containing two or more thiol groups (that is, a group represented by -SH) in the same molecule. The content of the polyfunctional thiol compound is not particularly limited, and it is often 0.1 to 10% by mass relative to the content of the colorant. Among them, from the viewpoint of having more excellent effects of the present invention, the content of the curable composition relative to the colorant is preferably 0.5 to 8.0% by mass. In addition, the content of the polyfunctional thiol compound is preferably 0.1 to 8.0% by mass, and more preferably 0.3 to 6.0% by mass relative to the total solid content of the curable composition. In addition, the polyfunctional thiol compound may be used alone, or two or more kinds may be used simultaneously. When two or more kinds are used at the same time, the total amount is preferably within the above range.

The relationship between the content of the polyfunctional thiol compound and the specific oxime compound is not particularly limited, and a cured film having a more excellent pattern shape is obtained from the curable composition (having more excellent effects of the present invention) From this point of view, as the content mass ratio of the content of the specific oxime compound to the content of the polyfunctional thiol compound in the curable composition (content of the specific oxime compound / content of the polyfunctional thiol compound), 0.1 to 15 is Preferably, 0.5 to 12 is more preferred, 1 to 10 is further preferred, and 4 to 10 is particularly preferred.

The polyfunctional thiol compound is preferably represented by the following formula (2) from the viewpoint that the curable composition has more excellent effects of the present invention. [Chemical Formula 5]

In formula (2), R ²⁴ and R ²⁵ represent a hydrogen atom, an alkyl group, an aryl group, -C (= O) -R ²³ , -C (= O) -OR ^23, or -C (= O) -NH- R ²³ , alkyl or -C (= O) -OR ²³ is preferred. In addition, R ²³ represents an alkyl group or an aryl group. A plurality of R ²⁴ , R ^25, and M ²¹ (to be described later) may be the same or different. When there are a plurality of R ²³ , they may be the same or different. .

L ²¹ represents an n-valent organic linking group. n represents an integer of 2 ~ 10, preferably 3 ~ 10, more preferably 3 ~ 6. When L ²¹ is a divalent organic linking group, for example, a divalent aliphatic hydrocarbon group (preferably C 1-8), a divalent aromatic hydrocarbon group (preferably C 6-12), -O-, -S-, -N (Rx)-(Rx: monovalent organic group), -C (= O)-, -C (= O) -O-, -OC (= O) -O -, -C (= O) -NH-, -OC (= O) -NH-, -S (= O)-, -S (= O) -O-, -S (= O) ₂ -,- S (= O) ₂ -O-, -CH = N- or a group formed by combining them (for example, alkoxy group, alkoxycarbonyl group, alkylene carbonyloxy group, etc.), etc. When L ²¹ is an organic linking group of 3 or more valences, for example, a trimethylolpropane residue, heterotrimerization containing 3-(CH ₂ ) _k- (k represents an integer of 2 to 6 for example). A trivalent linking group such as a cyanic ring, a tetravalent linking group such as a pentaerythritol residue or a 5-valent linking group, a 6-valent linking group such as a dipentaerythritol residue, and combinations thereof. Examples of the n-valent organic linking group of L ²¹ include groups represented by any of the following formulas (A) to (D) or groups obtained by combining them. [Chemical Formula 6]

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

The n-valent linking group of L ²¹ is, for example, a group represented by the following formulae (E) to (J) or a group obtained by combining them. [Chemical Formula 7]

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

L ²¹ may be a group represented by the following formulas (K) to (O) or a group formed by combining them. In the formula, * represents the bonding position. [Chemical Formula 8]

In formula (2), M ²¹ represents a single bond or -O-, -S-, -N (R ²³ )-, -C (= O) -O-, -OC (= O) -O-, -C (= O) -NH-, -C (= O)-, alkylene, or a combination of two or more of them, -C (= O) -O- is preferred. R ²³ represents an alkyl group or an aryl group, and a plurality of M ²¹ may be the same or different.

Among them, from the viewpoint that the curable composition has more excellent development residue suppression performance, as the polyfunctional thiol compound, in formula (2), at least one selected from the group of R ²⁴ and R ²⁵ is other than a hydrogen atom Preferably (the second-grade thiol compound), both R ²⁴ and R ²⁵ are more than hydrogen atoms (the third-grade thiol compound), R ²⁴ and R ²⁵ are independently alkyl or -C (= O) -OR ²³ is further preferred. In addition, the number of carbons when R ²⁴ and R ²⁵ are each other than a hydrogen atom is not particularly limited, and from the viewpoint that the curable composition has more excellent development residue suppression performance, it is preferably independently 1 or more. At least one of R ²⁴ and R ²⁵ is preferably 2 or more. The upper limit of the carbon number is not particularly limited, but usually 5 or less is preferable. Furthermore, M ²¹ series -C (= O) -O- is preferred, and n series integers of 3 to 10 are preferred. In addition, in this specification, the development residue suppression performance refers to the physical properties of the curable composition evaluated by the method described in the examples.

Specific examples of the polyfunctional thiol compound are shown below. The polyfunctional thiol compound contained in the curable composition according to the embodiment of the present invention is not limited thereto. In addition, L ²¹ , M ²¹ , R ²⁴ , R ²⁵ and n in the table respectively correspond to the symbols in the formula (2). In addition, "*" and "●" in Tables 2-1 to 2-3 respectively indicate the bonding positions, "*" indicates the bonding positions of L ²¹ and M ²¹ , and "●" indicates M ²¹ and -C (R ²⁴ ) (R ²⁵ ) -SH bonding position. In addition, the number of each polyfunctional thiol compound (SH-1 to SH-31) corresponds to the number of each polyfunctional thiol compound in the examples.

[table 2-1] In Table 2, * indicates the bonding point between L ²¹ and M ²¹ , ● indicates the bonding point between M ²¹ and -C (R ²⁴ ) (R ²⁵ ) -SH

[Table 2-2] In Table 2, * indicates the bonding point between L ²¹ and M ²¹ , ● indicates the bonding point between M ²¹ and -C (R ²⁴ ) (R ²⁵ ) -SH

[Table 2-3] In Table 2, * indicates the bonding point between L ²¹ and M ²¹ , ● indicates the bonding point between M ²¹ and -C (R ²⁴ ) (R ²⁵ ) -SH

[Colorant] The curable composition of the embodiment of the present invention contains a colorant. The content of the coloring agent in the curable composition is not particularly limited. Generally, it is preferably 30 to 70% by mass relative to the total solid content of the curable composition. One colorant may be used alone, or two or more may be used simultaneously. When two or more coloring agents are used at the same time, the total content is preferably within the above range. In addition, when the cured film is used as a light-shielding film, the content of the coloring agent in the curable composition is not particularly limited. From the viewpoint of obtaining a cured film (light-shielding film) having more excellent light-shielding properties, 40 mass % Or more is better. In addition, the upper limit of the content of the coloring agent is not particularly limited, and generally, it is preferably 70% by mass or less relative to the total solid content of the curable composition. If the content of the colorant is equal to or less than the upper limit, the curable composition has more excellent coatability. Examples of the colorant include pigments and dyes. Hereinafter, the colorant will be described in detail.

(Pigment) The pigment is not particularly limited, and known inorganic pigments and / or organic pigments can be used. It is preferable that the curable composition of this embodiment contains an inorganic pigment as a coloring agent. In addition, the curable composition of this embodiment preferably contains an organic pigment as a colorant.

･ Inorganic pigments As the above-mentioned inorganic pigments, there is no particular limitation, and known inorganic pigments can be used. Examples of inorganic pigments include zinc white, lead white, zinc barium white, titanium oxide, chromium oxide, iron oxide, precipitated barium sulfate, and barite powder, lead red, iron oxide red, chrome yellow, and zinc yellow (zinc 1 species of yellow, 2 species of zinc yellow), ultramarine blue, Prussian blue (potassium 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 and orange red. In addition, examples of black inorganic pigments include metal oxides and metal nitrogens containing at least one metal element selected from the group consisting of Co, Cr, Cu, Mn, Ru, Fe, Ni, Sn, Ti, and Ag. Compounds and metal nitrogen oxides, etc.

As inorganic pigments, carbon black, titanium black, metallic pigments, etc. (hereinafter, also referred to as "black pigments") can be obtained from the viewpoint of obtaining a curable composition capable of forming a cured film having a high optical concentration even if the content is small. .) Is better. Examples of metal pigments include metal oxides and metals containing at least one metal element selected from the group consisting of Nb, V, Co, Cr, Cu, Mn, Ru, Fe, Ni, Sn, Ti, and Ag nitride. As the inorganic pigment, at least one selected from the group consisting of titanium nitride, titanium oxynitride, niobium nitride, vanadium nitride, metal pigments containing silver or tin, and metal pigments containing silver and tin is preferred, At least one selected from the group consisting of titanium nitride, titanium nitride oxide, niobium nitride, and vanadium nitride is more preferable. In addition, the niobium nitride and vanadium nitride may be niobium oxynitride and vanadium oxynitride. In addition, as the inorganic pigment, carbon black can also be used. Specific examples of carbon black include inorganic pigments such as C.I. Pigment Black 7 which are commercially available products, but are not limited thereto.

In addition to the pigment described as a black pigment, the curable composition contains a pigment having infrared absorption. As the pigment having infrared absorption, a tungsten compound, a metal boride, and the like are preferable. Among them, a tungsten compound is preferable from the viewpoint of excellent light-shielding properties in wavelengths in the infrared region.

Two or more of these pigments can be used at the same time, and they can also be used simultaneously with the dyes described later. In order to adjust the color tone and improve the light-shielding property in the desired wavelength region, for example, black pigments or pigments with infrared light-shielding properties may be mixed with color pigments such as red, green, yellow, orange, purple and blue, or dyes described below Appearance. It is more preferable to mix red pigments or red dyes, or purple pigments or purple dyes into black pigments or pigments with infrared shading properties, and it is more preferable to mix red pigments with black pigments or pigments with infrared shading properties. Furthermore, a near-infrared absorber or an infrared absorber described later may be added to the above-mentioned curable composition.

As the black pigment, titanium black or niobium oxynitride is preferred. Titanium black is black particles containing titanium atoms. It is preferably low-order titanium oxide, titanium oxynitride, titanium nitride, or the like. Titanium black can modify the surface as needed for the purpose of improving dispersibility and suppressing cohesiveness. Specifically, titanium black can be coated with silicon oxide, titanium oxide, germanium oxide, aluminum oxide, magnesium oxide, or zirconium oxide. In addition, titanium black can also be processed using a water-repellent substance as shown in Japanese Patent Laid-Open No. 2007-302836. Titanium black is typically titanium black particles, and it is preferable that the primary particle size and average primary particle size of each particle are smaller. Niobium oxynitride is the same. Specifically, it is preferable that the average primary particle diameter is in the range of 10 nm to 45 nm.

In addition, the average primary particle size of the pigment can be measured using a transmission electron microscope (Transmission Electron Microscope, TEM). As a transmission electron microscope, for example, a transmission microscope HT7700 manufactured by Hitachi High-Technologies CORPORATION can be used. In this specification, regarding the average primary particle size of the pigment, the maximum length of the particle image obtained by a transmission electron microscope (Dmax: the maximum length of two points on the outline of the particle image) and the maximum length vertical length (DV -max: When the image is sandwiched between two straight lines parallel to the maximum length, the shortest length between the two straight lines is vertically connected), and the geometric mean value (Dmax × DV-max) 1/2 is taken as the particle size. By this method, the particle size of 100 particles is measured, and the average primary particle size of the pigment represents its arithmetic average value.

The specific surface area of titanium black and niobium oxynitride is not particularly limited. In order to make the water repellent after surface treatment of titanium black and niobium oxynitride with a water repellent agent a prescribed performance, BET (Brunauer, Emmett, Teller ( Bue Te method)) Determination of the value obtained based 5 ~ 150m ² / g is preferred, 20 ~ 120m ² / g is more preferred. Examples of commercially available products of titanium black include titanium black 10S, 12S, 13R, 13M, 13M-C, 13R, 13R-N, 13M-T (trade name, manufactured by Mitsubishi Materials Corporation), and Tilack D (product Name, manufactured by Ako Kasei Co., Ltd.) and titanium nitride 50nm (trade name, manufactured by Wako Pure Chemical Industries, Ltd.), etc.

As the colorant, it is preferable to use titanium oxynitride, titanium nitride, or niobium oxynitride, and from the reason that the resulting cured film has more excellent moisture resistance, titanium nitride or niobium oxynitride is more preferable, and niobium oxynitride is Further preferred. It is considered that these colorants are hydrophobic.

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

In this form, the titanium black system is contained in the curable composition as the dispersion, and the content ratio (Si / Ti) of Si atoms and Ti atoms in the dispersion in terms of mass conversion is preferably 0.05 or more. 0.05 to 0.5 is more preferable, and 0.07 to 0.4 is more preferable. Here, the to-be-dispersed body includes both the state in which titanium black is a primary particle and the state in agglomerates (secondary particles). In order to change the content ratio (Si / Ti) of the material to be dispersed (for example, 0.05 or more), the following method can be used. First, by using a disperser to disperse titanium oxide and silicon oxide particles to obtain a dispersion, by reducing the dispersion at a high temperature (for example, 850 to 1,000 ° C), it is possible to obtain titanium black particles as the main component and The dispersion containing Si and Ti. The above-mentioned reduction treatment can also be performed in an environment of reducing gas such as ammonia. Examples of titanium oxide include TTO-51N (trade name, manufactured by Ishihara Sangyo Kaisha, Ltd.) and the like. As a commercially available product of silicon oxide particles, AEROSIL (registered trademark) 90, 130, 150, 200, 255, 300, 380 (trade name, manufactured by Evonik), etc. may be mentioned. A dispersant can be used to disperse titanium oxide and silicon oxide particles. Examples of the dispersant include those described in the column of dispersant described below. The above dispersion can also be performed in a solvent. Examples of the solvent include water and organic solvents. Examples of the organic solvent include those described in the column of organic solvents described later. Titanium black with an adjusted content ratio (Si / Ti) can be produced, for example, by the methods described in paragraphs [0005] and [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 preferable range (for example, 0.05 or more), the curable composition containing the dispersion is used When a cured film is formed, residues derived from the curable composition outside the formation area of the cured film are reduced. In addition, the residue material contains components derived from curable compositions such as titanium black particles and resin components. Although the reason for the reduction of the residue is not clear, the particle size of the dispersion as described above tends to decrease (for example, the particle size is 30 nm or less), and the component of the dispersion contains Si atoms increases, thereby The adsorption of the entire membrane to the substrate is reduced. It is presumed that this phenomenon contributes to the improvement of the development-removability of the uncured curable composition (particularly titanium black) when the cured film is formed. Titanium black has excellent light-shielding properties over a wide range of wavelengths from ultraviolet light to infrared light. Therefore, the above-mentioned dispersion containing titanium black and Si atoms (preferably the content ratio (Si / Ti) in mass conversion) is used , Which is 0.05 or more) The cured film formed exhibits excellent light-shielding properties. In addition, the content ratio (Si / Ti) of Si atoms to Ti atoms 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 Perform the measurement. For the dispersion to be contained in the cured film obtained by curing the curable composition, if the content ratio of Si atoms to Ti atoms (Si / Ti) in the dispersion is determined to be 0.05 or more, Japanese special The method (2) described in paragraph 0035 of 2013-249417 is disclosed.

In the dispersion including titanium black and Si atoms, the above-mentioned titanium black can be used. In order to adjust the dispersibility, colorability, etc. of this to-be-dispersed body, one or more types of composite oxides including Cu, Fe, Mn, V, Ni, cobalt oxide, iron oxide and carbon Black pigments such as black and aniline black are used. In this case, it is preferable that the dispersion including titanium black accounts for 50% by mass or more of all the dispersion. In order to adjust the light-shielding property of this to-be-dispersed body, other colorants (organic pigments and / or dyes, etc.) may be used together with titanium black as needed within the range not detracting from the effects of the present invention. Hereinafter, materials used when Si atoms are introduced into the dispersion will be described. When introducing Si atoms into the dispersion, a substance containing Si such as silicon oxide may be used. Examples of usable silica include precipitated silica, vapor-phase silica, colloidal silica, and synthetic silica. These can be selected and used as appropriate. In addition, if the particle size of the silicon oxide particles is smaller than the film thickness when forming the cured film, the light-shielding property is more excellent. Therefore, it is preferable to use fine particle type silicon oxide as the silicon oxide particles. In addition, as an example of fine particle type silicon oxide, for example, the silicon oxide described in paragraph 0039 of Japanese Patent Application Laid-Open No. 2013-249417 can be cited. These contents are incorporated in this specification.

In addition, as a pigment, a tungsten compound and a metal boride can also be used. Hereinafter, the tungsten compound and the metal boride will be described in detail. Tungsten compounds and metal borides are infrared shielding materials that have high absorption to infrared rays (light with a wavelength of about 800 to 1,200 nm) (that is, have high light-shielding properties (shielding properties) to infrared rays) and low absorption to visible light. . Therefore, by containing the tungsten compound and / or the metal boride, the curable composition can form a pattern with high light-shielding properties in the infrared region and high transparency in the visible region. For light with a shorter wavelength than the visible region used in the exposure of high-pressure mercury lamps, KrF, ArF, etc. used to form images, tungsten compounds and metal borides also absorb this light less. Therefore, by combining the polymerizable compound and the alkali-soluble resin described later, an excellent pattern can be obtained, and the development residue can be further suppressed when the pattern is formed.

Examples of the tungsten compound include tungsten oxide compounds, tungsten boride compounds, and tungsten sulfide compounds. Tungsten oxide compounds represented by the following formula (composition formula) (I) are preferred. M _x W _y O _z ･ ･ ･ (I) M represents metal, W represents tungsten, and O represents oxygen. 0.001≤x / y≤1.1 2.2≤z / y≤3.0

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

The M-based alkali metal is preferred, Rb or Cs is more preferred, and Cs is further preferred.

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

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 and Ba _0.33 WO ₃ , and Cs _0.33 WO ₃ or Rb _0.33 WO ₃ is preferred, and Cs _0.33 WO ₃ is more preferred.

Tungsten compound-based fine particles are preferred. The average primary particle size of the tungsten fine particles is preferably 800 nm or less, more preferably 400 nm or less, and even more preferably 200 nm or less. From the viewpoint that it is difficult for tungsten fine particles to cut off visible light by light scattering, by having the average primary particle diameter in this range, the light transmittance in the visible light region can be made more reliable. From the viewpoint of avoiding light scattering, the smaller the average primary particle diameter is, the better. However, the average primary particle diameter of the tungsten fine particles is usually 1 nm or more from the viewpoint of ease of manufacture and other reasons.

Two or more kinds of tungsten compounds can be used.

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

As metal borides, lanthanum boride (LaB ₆ ), boride boride (PrB ₆ ), neodymium boride (NdB ₆ ), cerium boride (CeB ₆ ), yttrium boride (YB ₆ ), titanium boride (TiB ₂ ), zirconium boride (ZrB ₂ ), hafnium boride (HfB ₂ ), vanadium boride (VB ₂ ), tantalum boride (TaB ₂ ), chromium boride (CrB, CrB ₂ ), molybdenum boride (MoB ₂ , Mo ₂ B ₅ , MoB) and tungsten boride (W ₂ B ₅ ), or one or more than two kinds, and lanthanum boride (LaB ₆ ) is preferred.

Metal boride-based fine particles are preferred. The average primary particle size of the metal boride fine particles is preferably 800 nm or less, more preferably 300 nm or less, and even more preferably 100 nm or less. From the viewpoint that it is difficult for the metal boride to cut off visible light by light scattering, if the average primary particle size is in this range, the light transmittance in the visible light region can be made more reliable. From the viewpoint of avoiding light scattering, the smaller the average primary particle diameter is, the better. However, the average primary particle diameter of the metal boride fine particles is usually 1 nm or more for reasons such as ease of handling during manufacturing.

Two or more kinds of metal borides can be used.

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

･ ･ Titanium nitride-containing particles As inorganic pigments, titanium nitride-containing particles containing Fe atoms can also be used. When producing titanium nitride-containing particles, a gas-phase reaction method is generally used, and specific examples include an electric furnace method and a thermal plasma method. Among these production methods, the thermoplasma method is preferred from the viewpoints of low mixing of impurities, the viewpoint of easy uniformity of particle diameters, and the viewpoint of high productivity. Examples of the method for generating thermoplasma include direct current arc discharge, multi-phase arc discharge, high-frequency (RF) plasma, and hybrid plasma. A high-frequency plasma with a small amount of impurities mixed from the electrode is preferred. As a specific manufacturing method of the titanium nitride-containing particles based on the thermoplasma method, for example, titanium powder is evaporated by high-frequency thermoplasma, nitrogen is introduced into the device as a carrier gas, and the titanium powder is nitrided by a cooling process. Thus the method of synthesizing titanium nitride-containing particles and so on. In addition, the thermoplasma method is not limited to the above.

The method for producing titanium nitride-containing particles is not particularly limited, and the production methods 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, instead 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 this component is mixed with a titanium powder material (titanium particles) as Raw material to produce titanium nitride-containing particles contained in the curable composition.

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

The titanium powder material (titanium particles) used in the production of titanium nitride-containing particles may contain atoms other than titanium atoms. Examples of other atoms that can be included in the titanium powder material include Fe atoms and Si atoms. When the titanium powder material contains Fe atoms, the content of Fe atoms is preferably more than 0.001% by mass relative to the total mass of the titanium powder material. When the titanium powder material contains Si atoms, the content of Si atoms relative to the total mass of the titanium powder material is more than 0.002 mass% and less than 0.3 mass%, preferably 0.01 to 0.15 mass%, more preferably 0.02 to 0.1 mass%. Better. When the content of Si atoms exceeds 0.002% by mass, the pattern formability of the cured film is further improved. When the content of Si atoms is less than 0.3% by mass, the polarity of the outermost layer of the obtained titanium nitride-containing particles is more stabilized. This optimizes the adsorption of the titanium nitride-containing particle dispersant when the titanium nitride-containing particles are dispersed, thereby reducing the amount of undispersed titanium nitride-containing particles. The moisture in the titanium powder material (titanium particles) used in the production of the titanium nitride-containing particles is preferably less than 1% by mass relative to the total mass of the titanium powder material, less than 0.1% by mass is more preferable, and is not substantially included. Further preferred.

By using the thermal plasma method to obtain titanium nitride-containing particles, it becomes easy to adjust the diffraction angle 2θ (peak will be described later) of the peak derived from the (200) plane when CuKα rays are used as the X-ray source to exceed 42.6 ° and below 43.5 °.

The method of containing Fe atoms in the titanium nitride-containing particles is not particularly limited. For example, a method of introducing Fe atoms at the stage of obtaining titanium particles (titanium powder) used as a raw material for the titanium nitride-containing particles can be mentioned. In more detail, when titanium is manufactured by the Kroll method or the like, a material composed of a material containing Fe atoms such as stainless steel is used as a reaction vessel, or used as a material for a punch and pulverizer when crushing titanium Those containing Fe atoms can thereby attach Fe atoms to the surface of the titanium particles. When the thermoplasma method is used in the production of titanium nitride-containing particles, in addition to the titanium particles as raw materials, components such as Fe particles and Fe oxides are added, and these are nitrided by the thermoplasma method. The titanium nitride-containing particles contain Fe atoms. The Fe atoms contained in the titanium nitride-containing particles can be oxidized by ions, metal compounds (including complex compounds), intermetallic compounds, alloys, oxides, composite oxides, nitrides, nitrogen oxides, sulfides, and sulfur Include arbitrary forms such as things. The Fe atoms contained in the titanium nitride-containing particles may exist as impurities at positions between crystal lattices, or may exist as impurities in an amorphous state at the grain boundaries.

The content of Fe atoms in the titanium nitride-containing particles is preferably more than 0.001 mass% and less than 0.4 mass% with respect to the total mass of the titanium nitride-containing particles. Among them, 0.01 to 0.2% by mass is more preferable, and 0.02 to 0.1% by mass is even more preferable. The content of Fe atoms in the titanium nitride-containing particles can be measured by ICP (Inductively Coupled Plasma; high frequency inductively coupled plasma) luminescence spectrometry.

It is preferable that the titanium nitride-containing particles also contain Si atoms (silicon atoms). With this, the pattern formability of the cured film is further improved. It is considered that the reason for improving the pattern formability by containing Si atoms is the same as the Fe atoms described above. The content of Si atoms in the titanium nitride-containing particles is preferably more than 0.002 mass% and less than 0.3 mass% relative to the total mass of the titanium nitride-containing particles, more preferably 0.01 to 0.15 mass%, and further 0.02 to 0.1 mass% Better. The content of Si atoms in the titanium nitride-containing particles can be measured by the same method as the Fe atoms described above.

The method of containing Si atoms in the titanium nitride-containing particles is not particularly limited. For example, a method of introducing Si atoms at the stage of obtaining the titanium particles (titanium powder) used as the raw material for the titanium nitride-containing particles can be mentioned. In more detail, when titanium is produced by the Kroll method, etc., those composed of materials containing Si atoms are used as reaction vessels, or those containing Si atoms are used as materials for punches and pulverizers when titanium is broken, This allows Si atoms to adhere to the surface of the titanium particles. When the thermoplasma method is used in the production of titanium nitride-containing particles, in addition to the titanium particles as raw materials, components such as Si particles and Si oxides are added, and these are nitrided by the thermoplasma method. The titanium nitride-containing particles contain Si atoms. The Si atoms contained in the titanium nitride-containing particles can be oxidized by ions, metal compounds (including complex compounds), intermetallic compounds, alloys, oxides, composite oxides, nitrides, nitrogen oxides, sulfides, and sulfur Include arbitrary forms such as things. The Si atoms contained in the titanium nitride-containing particles may exist as impurities at positions between crystal lattices, or may exist as impurities in an amorphous state at the grain boundaries.

The content of titanium atoms (Ti atoms) in the titanium nitride-containing particles is preferably 10 to 85% by mass, more preferably 15 to 75% by mass, and 20 to 70% by mass relative to 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 nitrogen atoms (N atoms) in the titanium nitride-containing particles relative to the total mass of the titanium nitride-containing particles is preferably 3 to 60% by mass, more preferably 5 to 50% by mass, and 10 to 40% by mass Further preferred. The content of nitrogen atoms can be analyzed by the inert gas fusion thermal conductivity method. Titanium nitride-containing particles contain titanium nitride (TiN) as a main component, and are usually noticeable when oxygen is mixed during synthesis and when the particle size is small, but may also be included by oxidation of the particle surface, etc. Some oxygen atoms. The content of oxygen atoms in the titanium nitride-containing particles relative to the total mass of the titanium nitride-containing particles is preferably 1 to 40% by mass, more preferably 1 to 35% by mass, and even more preferably 5 to 30% by mass. The content of oxygen atoms can be analyzed by inert gas fusion infrared absorption method.

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

The titanium nitride-containing particles may be composite particles including titanium nitride particles and metal particles. Composite fine particles refer to particles in which titanium nitride particles are combined with metal fine particles or in a highly dispersed state. Here, "combined" means that the particles are composed of two components, titanium nitride and metal, and "highly dispersed state" means that the titanium nitride particles and the metal particles are separately present, and the particles of a small amount of components are not agglomerated and uniform. Disperse in the same way. The metal fine particles are not particularly limited, and examples thereof include copper, silver, gold, platinum, palladium, nickel, tin, cobalt, rhodium, iridium, ruthenium, osmium, manganese, molybdenum, tungsten, niobium, tantalum, and calcium. , Titanium, bismuth, antimony and lead, and at least one of their alloys. Among them, at least one selected from copper, silver, gold, platinum, palladium, nickel, tin, cobalt, rhodium, and iridium, and alloys thereof is preferably selected from copper, silver, gold, platinum, and tin, and these At least one of the alloys is more preferred. From the viewpoint of more excellent moisture resistance, silver is preferred. The content of the metal fine particles in the titanium nitride-containing particles is preferably 5-50% by mass relative to the total mass of the titanium nitride-containing particles, and more preferably 10-30% by mass.

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

When measuring the X-ray diffraction spectrum of a titanium compound using CuKα rays as an X-ray source, the peak with the strongest intensity is TiN, the peak originating from the (200) plane appears near 2θ = 42.5 °, and TiO is originating from (200 ) The surface peak appears near 2θ = 43.4 °. On the other hand, although not the intensity of the strongest peak, but on anatase type TiO _2, in the vicinity of 2θ = 48.1 ° derived from the observed (200) plane of the peak on the rutile type TiO _2, in the vicinity of 2θ = 39.2 ° A peak originating from the (200) plane was observed. Therefore, as the crystal state contains a large amount of oxygen atoms, the peak position shifts toward the higher angle side with respect to 42.5 °.

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

The size of the crystallites constituting the titanium nitride-containing particles can be obtained from the half-width of the X-ray diffraction peak and calculated using the Scherrer formula.

A crystallite size of 20 nm or more is preferable, and 20-50 nm is more preferable. By using titanium nitride-containing particles with a crystallite size of 20 nm or more to form a black matrix, the transmitted light of the cured film exhibits a blue to blue-violet color with a peak wavelength of 475 nm or less, and black with high light-shielding properties and ultraviolet sensitivity can be obtained 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 nitride-containing particles containing atom A Also, as inorganic pigments, metal nitride-containing particles containing predetermined atoms A can be used as metal nitride-containing particles. Examples of the metal in the metal-containing nitride particles include Nb, V, Cr, Y, Zr, Nb, Hf, Ta, W, and Re. The curable composition has more excellent effects of the present invention. From a viewpoint, 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 aforementioned atom A, the content 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 metal-containing nitride particles containing the atom A is not particularly limited, and a known method can be used. When producing metal-containing nitride particles, a gas-phase reaction method is generally used, and specifically, an electric furnace method, a thermal plasma method, etc. may be mentioned. Among these production methods, the thermoplasma method is preferred from the viewpoints of low mixing of impurities, the viewpoint of easy uniformity of particle diameters, and the viewpoint of high productivity. As a specific manufacturing method of metal nitride-containing particles based on the thermoplasma method, for example, those using a metal fine particle manufacturing apparatus (the same apparatus as the "black composite fine particle manufacturing apparatus" described later) can be cited. Metal particle manufacturing equipment includes, for example, a plasma torch that generates thermal plasma, a material supply device that supplies metal raw material powder into the plasma torch, a chamber with a cooling function, a cyclone separator that classifies the generated metal particles, and metal recovery The recovery part of the particles constitutes. In addition, in this specification, the metal fine particles refer to particles containing a metal element and having a primary particle diameter of 20 nm to 40 μm.

･ Organic pigments As organic pigments, for example, Color Index (CI) Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 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, etc .; 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. In addition, one kind of pigment may be used alone, or two or more kinds may be used simultaneously.

(Dye) As the dye, for example, Japanese Patent Laid-Open No. 64-90403, Japanese Patent Laid-Open No. 64-91102, Japanese Patent Laid-Open No. 1-94301, Japanese Patent Laid-Open No. 6-11614, Japanese Patent No. No. 2592207, U.S. Patent No. 4808501, U.S. Patent No. 5667920, U.S. Patent No. 505950, Japanese Unexamined Patent Publication No. 5-333207, Japanese Unexamined Patent Publication No. 6-35183, Japanese Unexamined Patent Publication No. 6-51115 , Japanese Unexamined Patent Publication No. 6-194828 and the like. If distinguished as a chemical structure, pyrazole azo compounds, pyrrole methylene compounds, anilino azo compounds, triphenylmethane compounds, anthraquinone compounds, benzylidene compounds, oxacyanine compounds, pyrazolo Triazole azo compounds, pyridone azo compounds, cyanine compounds, phenothiazine compounds and pyrrolopyrazole azomethine compounds. As the dye, a pigment polymer can also be used. Examples of the dye polymer include compounds described in Japanese Patent Application Laid-Open No. 2011-213925 and Japanese Patent Application Laid-Open No. 2013-041097. A polymerizable dye having polymerizability in the molecule can be used, and as a commercially available product, for example, RDW series manufactured by Wako Pure Chemical Industries, Ltd. can be cited.

(Infrared absorber) The colorant may further contain an infrared absorber. The infrared absorber means a compound having absorption in the infrared region (preferably wavelength 650 to 1,300 nm). The infrared absorber is preferably a compound having a maximum absorption wavelength in the wavelength range of 675 to 900 nm. Examples of the coloring agent having such a spectroscopic property include pyrrole-pyrrole compounds, copper compounds, cyanine compounds, phthalocyanine compounds, iminium compounds, thiol complex compounds, and transition metal oxide compounds. Compounds, squarylium compounds, naphthalocyanine compounds, quartrenene compounds, dithiol metal complex compounds, ketonium compounds, etc. Phthalocyanine compounds, naphthalocyanine compounds, ammonium compounds, cyanine compounds, squarylium compounds, and ketonium compounds can be used as disclosed in paragraphs 0010 to 0081 of Japanese Patent Application Laid-Open No. 2010-111750, the contents of which are incorporated herein. In the manual. The cyanine compound can be referred to, for example, "Functional Pigments, Ogawara Nobuyuki / Song Gangxian / Kitao Tiejiro / Hirashima Hiroshi, Kodansha Scientific Ltd.", and this content is incorporated in this specification.

As the coloring agent having the above-mentioned spectral characteristics, compounds disclosed in paragraphs 0004 to 0016 of JP-A-07-164729 and / or compounds disclosed in paragraphs 0027-0062 of JP-A 2002-146254 can also be used. Japanese Patent Laid-Open No. 2011-164583, paragraphs 0034 to 0067, disclose near-infrared absorbing particles that include crystallites containing oxides of Cu and / or P and have an average number aggregated particle diameter of 5 to 200 nm.

As the compound having a maximum absorption wavelength in the wavelength range of 675-900 nm, at least one selected from the group consisting of cyanine compounds, pyrrolopyrrole compounds, squarylium compounds, phthalocyanine compounds, and naphthalocyanine compounds is more suitable good. The infrared absorber is preferably a compound that dissolves 1% by mass or more in water at 25 ° C, and more preferably a compound that dissolves 10% by mass or more in water at 25 ° C. By using this compound, the solvent resistance is optimized. The pyrrolopyrrole compound can refer to paragraphs 0049 to 0062 of Japanese Patent Application Laid-Open No. 2010-222557, and the contents are incorporated in this specification. The cyanine compound and the squaraine compound can refer to paragraphs 0022 to 0063 of International Publication No. 2014/088063, paragraphs 0005 to 0118 of International Publication No. 2014/030628, and paragraphs 0028 to 0074 of Japanese Patent Laid-Open No. 2014-59550. International Publication No. 2012/169447, paragraphs 0013 to 0091, Japanese Patent Laid-Open No. 2015-176046, paragraphs 0019 to 0033, Japanese Patent Laid-Open No. 2014-63144, paragraphs 0503 to 0099, Japanese Patent Laid-Open No. 2014-52431 Paragraphs 0085 to 0150, paragraphs 0076 to 0124 of Japanese Patent Laid-Open No. 2014-44301, paragraphs 0045 to 0078 of Japanese Patent Laid-Open No. 2012-8532, paragraphs 0027 to 0067 of Japanese Patent Laid-Open No. 2015-172102, Japanese Patent Laid-Open Paragraphs 0029 to 0067 of 2015-172004, Paragraphs 0029 to 085 of Japanese Patent Laid-Open No. 2015-40895, Paragraphs 0022 to 0036 of Japanese Patent Laid-Open No. 2014-126642, and 0011 to Japanese Patent Laid-Open No. 2014-148567 Paragraph 0017, paragraphs 0010 to 0025 of Japanese Patent Laid-Open No. 2015-157893, paragraphs 0013 to 0026 of Japanese Patent Laid-Open No. 2014-095007, paragraphs 0013 to 0047 of Japanese Patent Laid-Open No. 2014-80487 and Japanese Patent Laid-Open 2013- Paragraphs 0007 to 0028 of 227403, etc., the contents are incorporated into this text In the book.

The infrared absorber is preferably at least one selected from the group consisting of compounds represented by the following formulas 1 to 3. Formula 1 [Chemical Formula 9] In Formula 1, A ¹ and A ² each independently represent an aryl group, a heteroaryl group, or a group represented by the following Formula 1-A. Formula 1-A [Chemical Formula 10] In Formula 1-A, Z ^1A represents a non-metallic atomic group forming a nitrogen-containing heterocycle, R ^2A represents an alkyl group, alkenyl group, or aralkyl group, d represents 0 or 1, and a wavy line represents a bond. Formula 2 [Chemical Formula 11] In Formula 2, R ^1a and R ^1b each independently represent an alkyl group, an aryl group or a heteroaryl group, R ² ~ R ⁵ each independently represent a hydrogen atom or a substituent, and R ² and R ³ , R ⁴ and R ⁵ also Can be bonded to form a ring, R ⁶ and R ⁷ independently represent a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group, -BR ^A R ^B or a metal atom, R ^A and R ^B independently represent a hydrogen atom Or a substituent, R ⁶ may be covalently bonded or coordinated to R ^1a or R ³ , and R ⁷ may be covalently bonded or coordinated to R ^1b or R ⁵ . Formula 3 [Chemical Formula 12] In Formula 3, Z ¹ and Z ² are each independently a non-metallic atomic group that can be fused to form a 5-membered or 6-membered nitrogen-containing heterocyclic ring, and R ¹⁰¹ and R ¹⁰² independently represent an alkyl group, an alkenyl group, and an alkyne Group, aralkyl group or aryl group, L ¹ represents a methine chain including an odd number of methine groups, a and b are independently 0 or 1, when a is 0, the carbon atom and the nitrogen atom through a double bond For bonding, when b is 0, the carbon atom and the nitrogen atom are bonded by a single bond. When the part represented by Cy in the formula is a cation part, X ¹ represents an anion, and c represents a balance of charge The required quantity, when the part represented by Cy in the formula is an anion part, X ¹ represents a cation, c represents the quantity required to achieve a charge balance, when the charge represented by Cy in the formula is When the molecule is neutralized, c is 0.

(Pigment derivative) The hardenable 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 acid group, a base group, or phthalimide methyl group. As the pigment derivative, a pigment derivative having an acid group or a base group is preferred from the viewpoint of the dispersibility and dispersion stability of the colorant A. Particularly preferred are pigment derivatives having base groups. The combination of the above resin (dispersant) and pigment derivative-based dispersant is an acidic dispersant and the combination in which the pigment derivative has a base group is preferred.

Examples of the organic pigment used to constitute the pigment derivative include diketopyrrolopyrrole-based pigments, azo-based pigments, phthalocyanine-based pigments, anthraquinone-based pigments, quinacridone-based pigments, di 㗁 -based pigments, and purple rings Ketone pigments, perylene pigments, Thioindigo pigments, isoindoline pigments, isoindolinone pigments, quinoline yellow pigments, reduction pigments and metal complex pigments Wait. As the acid group possessed by the pigment derivative, a sulfonic acid group or its salt or a carboxylic acid group or its salt is preferred, a carboxylic acid group or a sulfonic acid group is more preferred, and a sulfonic acid group is further preferred. As the base group of the pigment derivative, an amine group is preferable, and a tertiary amine group is more preferable.

When the curable composition contains a pigment derivative, the content of the pigment derivative relative to the mass of the pigment is preferably 1 to 30% by mass, and more preferably 3 to 20% by mass. Only one type of pigment derivative may be used, or two or more types may be used simultaneously.

[Polymerizable Compound] The curable composition contains a polymerizable compound. In this specification, a polymerizable compound refers to a compound containing a polymerizable group, and refers to a component different from a resin (dispersant and binder resin).

The content of the polymerizable compound in the curable composition is not particularly limited, but it is usually preferably 5 to 30% by mass relative to the total solid content of the curable composition. One type of polymerizable compound may be used alone, or two or more types may be used simultaneously. When two or more polymerizable compounds are used at the same time, the total content is preferably within the above range.

The polymerizable compound is preferably a compound containing one or more ethylenically unsaturated bond-containing groups, a compound containing two or more such groups is more preferable, and a compound containing three or more groups is still more preferable, containing More than 5 of these groups are particularly preferred. The upper limit is, for example, 15 or less. Examples of the group containing an ethylenically unsaturated bond include vinyl, (meth) allyl, and (meth) acryloyl.

As the polymerizable compound, for example, the compounds described in paragraph 0050 of Japanese Patent Laid-Open No. 2008-260927 and paragraph 0040 of Japanese Patent Laid-Open No. 2015-68893 can be used, and the above contents are incorporated in this specification.

The polymerizable compound may be, for example, any one of chemical forms such as monomers, prepolymers, oligomers, and mixtures thereof, and polymers thereof. The polymerizable compound is preferably a 3 to 15-functional (meth) acrylate compound, and more preferably a 3 to 6-functional (meth) acrylate compound.

As the polymerizable compound, a compound containing one or more ethylenically unsaturated bond-containing groups and having a boiling point of 100 ° C. or higher under normal pressure is preferred. For example, the compounds described in paragraph 2227 of Japanese Patent Application Laid-Open No. 2013-29760 and paragraphs 0254 to 0257 of Japanese Patent Application Laid-Open No. 2008-292970 can be used, and the contents are incorporated in this specification.

As the polymerizable compound, for example, dipentaerythritol triacrylate (as a commercial product, KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (as a commercial product) , KAYARAD D-320; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol penta (meth) acrylate (as a commercially available product, KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.) , Dipentaerythritol hexa (meth) acrylate (as a commercial product, KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., A-DPH-12E; manufactured by Shin-Nakamura Chemical Co., Ltd.) and The structure of their (meth) acryloyl group via ethylene glycol residues or propylene glycol residues (for example, SR454, SR499 commercially available from Sartomer Company, Inc.) is preferred. Their oligomer type can also be used. In addition, NK Ester A-TMMT (neopentaerythritol tetraacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.) and KAYARAD RP-1040 (manufactured by Nippon Kayaku Co., Ltd.) and the like can also be used.

The polymerizable compound may have an acid group such as a carboxylic acid group, a sulfonic acid group, or a phosphoric acid group. As the polymerizable compound containing an acid group, an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid is preferred, and the unreacted hydroxyl group of the aliphatic polyhydroxy compound reacts with a non-aromatic carboxylic acid anhydride to have a polymerizable acid group The compound is more preferable, and in this ester, the compound in which the aliphatic polyhydroxy compound is neopentaerythritol and / or dipentaerythritol is still more preferable. Examples of commercially available products of the polymerizable compounds include ARONIX TO-2349, M-305, M-510, and M-520 manufactured by TOAGOSEI CO., LTD.

The acid value of the polymerizable compound containing an acid group is preferably 0.1 to 40 mgKOH / g, and more preferably 5 to 30 mgKOH / g. If the acid value of the polymerizable compound is 0.1 mgKOH / g or more, the curable composition has more excellent developability (the characteristic of being easily dissolved by an alkaline developer), and if it is 40 mgKOH / g or less, the It is advantageous in manufacturing and / or operation, and has more excellent photopolymerization. As a result, the curable composition has more excellent curability.

As the polymerizable compound, a compound containing a caprolactone structure is preferred. The compound containing a caprolactone structure is not particularly limited as long as it contains a caprolactone structure in the molecule, and known compounds can be used. As the compound containing a caprolactone structure, for example, ε-caprolactone modified polyfunctional (meth) acrylate is obtained by combining trimethylolethane, ditrimethylolethane, trihydroxy Polyhydric alcohols such as methylpropane, ditrimethylolpropane, neopentaerythritol, dipentaerythritol, tripentaerythritol, glycerol, diglycerol, and trimethylolmelamine (methyl) Acrylic acid and ε-caprolactone are obtained by esterification. Among them, compounds containing a caprolactone structure represented by the following formula (Z-1) are preferred.

[Chemical Formula 13]

In formula (Z-1), 6 Rs are all groups represented by the following formula (Z-2) or 1 to 5 of the 6 Rs are groups represented by the following formula (Z-2), The remainder is a group represented by the following formula (Z-3).

[Chemical Formula 14]

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

[Chemical Formula 15]

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

The polymerizable compound containing a caprolactone structure is commercially available as KAYARAD DPCA series from Nippon Kayaku Co., Ltd., for example, DPCA-20 (in the above formulas (Z-1) to (Z-3), m is 1. The number of groups represented by formula (Z-2) is 2, and R ¹ is a compound of hydrogen atom), DPCA-30 (in the above formulas (Z-1) to (Z-3), m is 1. The number of groups represented by formula (Z-2) is 3, and R ¹ is a compound of hydrogen atom), DPCA-60 (in the above formulas (Z-1) to (Z-3), m is 1. The number of groups represented by formula (Z-2) is 6, and R ¹ is a compound of hydrogen atom) and DPCA-120 (in the above formulas (Z-1) to (Z-3), m is 2. The number of groups represented by formula (Z-2) is 6, and R ¹ is a compound of hydrogen atoms), etc.

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

[Chemical Formula 16]

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

In formula (Z-4), an integer of 0 to 6 of m is more preferable, and an integer of 0 to 4 is more preferable. The total of each m is preferably an integer of 2 to 40, an integer of 2 to 16 is more preferable, and an integer of 4 to 8 is even more preferable. In formula (Z-5), an integer of 0 to 6 of n series is more preferable, and an integer of 0 to 4 is more preferable. The total of each n is preferably an integer of 3 to 60, an integer of 3 to 24 is more preferable, and an integer of 6 to 12 is even more preferable. In the formula (Z-4) or formula (Z-5),-((CH ₂ ) _y CH ₂ O)-or ((CH ₂ ) _y CH (CH ₃ ) O)-is the end of the oxygen atom side and X The form of bonding is better.

The compound represented by formula (Z-4) or formula (Z-5) may be used alone or in combination of two or more. In particular, a compound in which 6 X in formula (Z-5) are all acryloyl groups, and a compound in which 6 X in formula (Z-5) are all acryloyl groups and at least one of 6 X is hydrogen Atomic compounds are preferred. The curable composition containing the above compound has more excellent developability.

The total content of the polymerizable compound of the compound represented by formula (Z-4) or formula (Z-5) is preferably 20% by mass or more, and more preferably 50% by mass or more. Among the compounds represented by formula (Z-4) or formula (Z-5), neopentaerythritol derivatives and / or dipentaerythritol derivatives are more preferred.

The polymerizable compound may contain a cardo skeleton. As the polymerizable compound containing a cardo skeleton, a polymerizable compound containing a 9,9-bisaryl stilbene skeleton is preferred. The polymerizable compound containing a cardo skeleton is not particularly limited, and examples thereof include Oncoat EX series (manufactured by NAGASE & CO., LTD) and Ogsol (manufactured by Osaka Gas Chemicals Co., Ltd.).

[Arbitrary component] The curable composition may contain other components within the range of exerting the effects of the present invention. Examples of other components include resins, polymerization inhibitors, solvents, surfactants, ultraviolet absorbers, and silane coupling agents. Hereinafter, arbitrary components contained in the curable composition will be described in detail.

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

Examples of thermal polymerization initiators include 2,2'-azobisisobutyronitrile (AIBN), 3-carboxypropionitrile, azobismalononitrile, and dimethyl- (2,2 ')- Azo compounds such as azobis (2-methylpropionate) [V-601], and organic peroxides such as benzoyl peroxide, lauryl peroxide and potassium persulfate. Examples of the thermal polymerization initiator include compounds described on pages 65 to 148 of Kato Kiyoshi's "Ultraviolet Curing System" (published by the Comprehensive Technology Center Co., Ltd .: 1989).

Examples of the photopolymerization initiator include halogenated hydrocarbon derivatives (for example, those containing a tri-skeleton and those containing an oxadiazole skeleton), acylphosphine compounds such as acylphosphine oxide, and hexaarylbisimidazole (Hexaarylbiimidazole), oxime derivatives and other oxime compounds (except for specific oxime compounds), organic peroxides, sulfur compounds, ketone compounds, aromatic onium salts, aminoacetophenone compounds and hydroxyacetophenone, etc. As the photopolymerization initiator, for example, paragraphs 0265 to 0268 of JP-A-2013-29760 can be referred to, and this content is incorporated in this specification.

As the photopolymerization initiator, more specifically, for example, an acetophenone-based initiator described in Japanese Patent Application Laid-Open No. 10-291969 or an acetylphosphine-based initiator described in Japanese Patent No. 4225898 can be used. Starting agent, the above content is incorporated into this specification. As the hydroxyacetophenone compound, for example, IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, or IRGACURE-127 (trade name: all manufactured by BASF) can be used, but it is not limited thereto. As the aminoacetophenone compound, for example, IRGACURE-907, IRGACURE-369, or IRGACURE-379EG (trade names: all manufactured by BASF) can be used as a commercially available product, but it is not limited thereto. As the aminoacetophenone compound, the compound described in Japanese Patent Laid-Open No. 2009-191179 whose absorption wavelength matches a long-wavelength light source such as 365 nm or 405 nm can also be used. The above content is incorporated in this specification. As the acetylphosphine compound, IRGACURE-819 or IRGACURE-TPO (trade name: all manufactured by BASF) can be used.

<Resin> The curable composition preferably contains resin. Examples of the resin include dispersant and binder resin. The content of the resin in the curable composition is not particularly limited, but it is usually preferably 5 to 40% by mass relative to the total solid content of the curable composition. One type of resin may be used alone, or two or more types may be used simultaneously. When two or more resins are used at the same time, the total content is preferably within the above range.

(Dispersant) The curable composition preferably contains a dispersant (equivalent to resin). In addition, in this specification, the dispersant refers to a compound different from the alkali-soluble resin described later. The content of the dispersant in the curable composition is not particularly limited, but it is usually preferably 5 to 40% by mass relative to the total solid content of the curable composition. One type of dispersant may be used alone, or two or more types may be used simultaneously. When two or more dispersants are used at the same time, the total content is preferably within the above range.

The dispersant is not particularly limited, and a well-known dispersant can be used. Examples of the dispersant include polymer dispersants. Examples of the polymer dispersant include polyamidoamine and its salts, polycarboxylic acid and its salts, high molecular weight unsaturated acid ester, modified polyurethane, modified polyester, and modified poly (meth) acrylate , (Meth) acrylic copolymer and formalin naphthalenesulfonate condensate, etc. In addition, as the dispersant, polyoxyethylidene alkyl phosphate, polyoxyethylidene alkylamine, pigment derivative and the like can be used. Among them, a polymer compound is preferred as a dispersant. According to its structure, polymer compounds can be further classified into linear polymers, terminal modified polymers, graft polymers, and block polymers.

･ High molecular compound The high molecular compound acts to adsorb on the surface of the colorant (hereinafter sometimes referred to as "pigment") and prevent re-agglomeration of the dispersion. Therefore, a terminal-modified polymer, a graft-type polymer (containing a polymer chain) polymer, and a block-type polymer containing an anchoring portion on the surface of the pigment are preferred.

The above polymer compound may contain a curable group. Examples of the curable group include ethylenically unsaturated groups (for example, (meth) acryl, vinyl, and styryl groups) and cyclic ether groups (for example, epoxy groups and oxetanyl groups). Etc.) but not limited to such. Among them, the ethylenically unsaturated group is preferred as the curable group from the viewpoint that polymerization can be inhibited by radical reaction. As the ethylenically unsaturated group, (meth) acryloyl group is more preferable.

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

It is preferable that the polymer compound has a structural unit containing a graft chain. In addition, in this specification, the definition of "structural unit" is the same as "repeating unit". The polymer compound having structural units containing such grafted chains has more excellent affinity with solvents. Since the polymer compound having a structural unit containing a graft chain has more excellent affinity with the solvent, it is easier to disperse the pigment and the like, and even after a certain period of time has elapsed after the pigment and the like are dispersed, the initial dispersion state is not easy Further changes (with more excellent stability over time). In addition, since the polymer compound having a structural unit containing a graft chain contains a graft chain, it has a more excellent affinity with a polymerizable compound and / or with other components described below. As a result, when a polymer compound having a structural unit containing a graft chain is subjected to alkali development described later, it is difficult to generate residues caused by unreacted polymerizable compounds and the like. If the graft chain becomes longer (the amount of formula increases), the space repulsion effect increases, and the dispersibility of the pigment and the like improves. On the other hand, if the graft chain becomes too long, the adsorption force to the pigment and the like will decrease, and the dispersibility of the pigment and the like will tend to decrease. Therefore, as the number of atoms of the graft chain (excluding hydrogen atoms), 40 to 10,000 is more preferable, 50 to 2,000 is more preferable, and 60 to 500 is even more preferable. Here, the graft chain refers to from the base of the main chain of the polymer compound (the atom bonded to the main chain among the groups branching from the main chain) to the end of the group branching from the main chain.

The graft chain is preferably a polymer chain containing a polymer structure. The polymer structure included in the polymer chain is not particularly limited, and examples thereof include a poly (meth) acrylate structure (for example, a poly (meth) acrylic structure), a polyester structure, a polyurethane structure, and a polyurea structure. , Polyamide structure and polyether structure, etc. From the viewpoint that the polymer chain and the solvent have more excellent affinity and the polymer compound easily disperses the pigment and the like, the polymer chain contains a structure selected from the group consisting of a polyester structure, a polyether structure, and a poly (meth) acrylate structure. At least one kind of the group is preferable, and at least one kind selected from the group including a polyester structure and a polyether structure is more preferable.

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

Examples of commercially available macromonomers corresponding to the structural unit containing the polymer chain contained in the polymer compound and usable in the synthesis of the polymer compound include, for example, AA-6, AA-10, and AB- 6. AS-6, AN-6, AW-6, AA-714, AY-707, AY-714, AK-5, AK-30 and AK-32 (the above are the trade names, which are produced by TOAGOSEI CO., LTD.); BLEMMER PP-100, BLEMMER PP-500, BLEMMER PP-800, BLEMMER PP-1000, BLEMMER 55-PET-800, BLEMMER PME-4000, BLEMMER PSE-400, BLEMMER PSE-1300 and BLEMMER 43PAPE- 600B (the above are trade names, manufactured by NOF CORPORATION); etc.

The dispersant preferably contains at least one structure selected from the group consisting of polymethyl acrylate, polymethyl methacrylate, and cyclic or chain polyester, and contains at least one structure selected from the group consisting of polymethyl acrylate, polymethyl At least one structure of the group of methyl acrylate and chain polyester is more preferable, and contains at least one structure selected from the group consisting of polymethyl acrylate structure, polymethyl methacrylate structure, polycaprolactone structure and polyvalerolactone structure At least one structure of the group is further preferred. Regarding the dispersant, one of the above-mentioned structures may be contained alone in the molecule, or a plurality of such structures may be contained in the molecule. Here, the polycaprolactone structure refers to 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 delta-valerolactone as a repeating unit. Examples of the dispersant containing a polycaprolactone structure include those in which j or k in formula (1) or formula (2) is 5 respectively. In addition, examples of the dispersant containing a polyvalerolactone structure include those in which j or k in the following formula (1) or the following formula (2) is 4, respectively. Examples of the dispersant containing a polymethyl acrylate structure include those in which X ⁵ is a hydrogen atom and R ⁴ is a methyl group in the following formula (4). Examples of the dispersant containing a polymethyl methacrylate structure include those in which X ⁵ is methyl and R ⁴ is methyl in the following formula (4).

･ Structure unit containing graft chain For a polymer compound, as a structure unit containing a graft chain, it contains at least one kind selected from the group including the following formula (1) to formula (4) and has a polymer chain Preferably, the structural unit contains at least one selected from the group consisting of the following formula (1A), the following formula (2A), the following formula (3A), the following formula (3B), and the following (4) And the structural unit with polymer chain is better.

[Chemical Formula 17]

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

In Formula (1) to Formula (4), Y ¹ , Y ² , Y ³ and Y ⁴ each independently represent a divalent linking group. The structure of the linking group is not particularly limited. Examples of the divalent linking groups represented by Y ¹ , Y ² , Y ³ and Y ⁴ include linking groups represented by the following formulae (Y-1) to (Y-21). In the following formulas (Y-1) to (Y-21), A and B each represent a bonding site. In the structure shown below, from the viewpoint of convenience of synthesis, (Y-2) or (Y-13) is more preferable.

[Chemical Formula 18]

In Formula (1) to Formula (4), Z ¹ , Z ² , Z ³ and Z ⁴ each independently represent a monovalent organic group. The structure of the organic group is not particularly limited. Examples of organic groups include alkyl groups, hydroxyl groups, alkoxy groups, aryloxy groups, heteroaryloxy groups, alkyl sulfide groups, aryl sulfide groups, heteroaryl sulfide groups, and amine groups. Among them, from the viewpoint of further dispersing the pigment and the like, as the organic groups represented by Z ¹ , Z ² , Z ³ and Z ⁴ , it is preferable to have a steric repulsion effect, and each of them independently has 5 to 24 carbon Alkyl groups or alkoxy groups are more preferable, and are independently branched alkyl groups having 5 to 24 carbon atoms, cyclic alkyl groups having 5 to 24 carbon atoms or alkoxy groups having 5 to 24 carbon atoms. In addition, the alkyl group contained in the alkoxy group may be any of linear, branched, and cyclic.

In formula (1) to formula (4), n, m, p, and q each independently represent an integer of 1 to 500. In formula (1) and formula (2), j and k independently represent integers of 2 to 8, respectively. In formula (1) and formula (2), from the viewpoint that the curable composition has more excellent stability over time and more excellent developability, j and k are preferably integers of 4 to 6, and 5 is more good. In formula (1) and formula (2), n and m are preferably integers of 10 or more, and integers of 20 or more are more preferable. In addition, when the dispersant contains a polycaprolactone structure and a polyvalerolactone structure, as the sum of the repeating number of the polycaprolactone structure and the repeating number of the polyvalerolactone, an integer of 10 or more is preferable, and 20 or more Integer is better.

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

The polymer compound may have a structural unit containing two or more types of graft chains with different structures. That is, the molecules of the polymer compound may contain structural units represented by formulas (1) to (4) whose structures are different from each other. When formulas (1) to (4), n, m, p, and q are When representing an integer of 2 or more, in formula (1) and formula (2), j and k in the side chain may contain different structures from each other, and in formula (3) and formula (4), there are a plurality of R ³ , R ⁴ and X ⁵ may be the same as or different from each other.

From the viewpoint that the curable composition has more excellent stability over time and more excellent developability, the structural unit represented by the following formula (1A) is more preferable as the structural unit represented by the formula (1). From the viewpoint that the curable composition has more excellent stability over time and developability, as the structural unit represented by the formula (2), the structural unit represented by the following formula (2A) is more preferable.

[Chemical Formula 19]

In the formula (1A), described X ^1, Y ^1, Z ¹ and n are as in system ^1, Y ^1, Z ¹ and n are as formula X (1) is only performed. In formula ^{(2A), X 2, Y} 2, Z ² and m are described as based only formula X ^2, Y ^2, Z ² and m (2) is performed.

From the viewpoint that the curable composition has more excellent stability over time and more excellent developability, as the structural unit represented by formula (3), the structure represented by the following formula (3A) or formula (3B) The unit is better.

[Chemical Formula 20]

Formula (3A) or (3B) in, X ^3, description Y ^3, Z ³ and p are as based formula X (3) is ^3, Y ^3, Z ³ and p only performed.

As a structural unit containing a graft chain, especially a polymer chain, it is more preferable that the polymer compound contains a structural unit represented by formula (1A).

The content of the structural unit containing the graft chain in the polymer compound (for example, the structural unit represented by the above formula (1) to formula (4)) is calculated in terms of mass, relative to the total mass of the polymer compound, 2 ~ 90% by mass is better, and the range of 5-30% is even better. If the content of the structural unit containing the graft chain in the polymer compound is within the above range, the dispersant can more easily disperse the pigment and the like, and the curable composition has more excellent developability.

･ Hydrophobic structural unit The polymer compound has a hydrophobic structural unit that is different from the structural unit containing the graft chain (that is, not equivalent to the structural unit containing the graft chain). In this specification, the hydrophobic structural unit is a structural unit that does not contain an acid group (for example, carboxylic acid group, sulfonic acid group, phosphoric acid group, phenolic hydroxyl group, etc.).

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

The ClogP value is a value calculated using the program "CLOGP" available from Daylight Chemical Information System, Inc. This program provides the value of "calculated logP" calculated by Hansch, Leo's Fragment Approach (see the following literature). The fragment method divides the chemical structure into partial structures (fragments) based on the chemical structure of the compound, and sums up the logP contribution allocated to the fragment to calculate the logP value of the compound. The details are described in the following documents. In this manual, the ClogP value represents 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 value indicating the physical property value of how an organic compound is distributed in the equilibrium of the 2-phase system of oil (usually 1-octanol) and water. Representation. logP = log (Coil / Cwater) where Coil represents the molar concentration of the compound in the oil phase and Cwater represents the molar concentration of the compound in the water phase. If the value of logP is between 0 and the plus (plus) increases, it means that the oil solubility increases. If the absolute value minus increases (minus), it means that the water solubility increases, which has a negative correlation with the water solubility of the organic compound. It is widely used to estimate the hydrophilicity and hydrophobicity of organic compounds.

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

[Chemical Formula 21]

In the above formulas (i) to (iii), R ¹ , R ² and R ³ each independently represent a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom and a bromine atom) or a C 1-6 alkyl group (For example, methyl, ethyl, propyl, etc.). R ¹ , R ² and R ³ are preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom or a methyl group. R ² and R ³ are more preferably hydrogen atoms. X represents an oxygen atom (-O-) or an imino 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, alkylene group, substituted alkylene group, alkenyl group, substituted alkenyl group, alkynyl group, substituted alkynyl group, etc.), divalent Aromatic group (for example, arylene group and substituted arylene group), divalent heterocyclic group, oxygen atom (-O-), sulfur atom (-S-), imino group (-NH-), Substituted imino groups (-NR ^31- , where R ³¹ represents an aliphatic group, an aromatic group or a heterocyclic group), a carbonyl group (-CO-), and combinations thereof, etc.

The divalent aliphatic group may contain a cyclic structure or a branched structure. The carbon number system of the aliphatic group is preferably 1-20, more preferably 1-15, and further preferably 1-10. The aliphatic group may be an unsaturated aliphatic group or a saturated aliphatic group, and a saturated aliphatic group is preferred. The aliphatic group may contain a substituent. The substituent is not particularly limited, and examples thereof include halogen atoms, aromatic groups, and heterocyclic groups.

The carbon number system of the divalent aromatic group is preferably 6-20, more preferably 6-15, and even more preferably 6-10. The aromatic group may contain a substituent. The substituent is not particularly limited, and examples thereof include halogen atoms, aliphatic groups, aromatic groups, and heterocyclic groups.

The bivalent heterocyclic group preferably contains a 5-membered ring or a 6-membered ring as a heterocyclic ring. Other heterocycles, aliphatic rings or aromatic rings may be fused to the heterocycle. The heterocyclic group may contain a substituent. The substituent is not particularly limited, and examples thereof include a halogen atom, a hydroxyl group, an oxo group (= O), a thio group (= S), an imino group (= NH), and a substituted imino group (= NR ³² , Where R ³² is an aliphatic group, an aromatic group or a heterocyclic group), an aliphatic group, an aromatic group, a heterocyclic group and the like.

As L, a single bond, an alkylene group or a divalent linking group containing an oxyalkylene structure is preferred. The oxyalkylene structure is preferably an oxyethylated structure or an oxypropylated structure. L may contain an oxyalkylene structure which repeatedly contains two or more polyoxyalkylene structures. As the polyoxyalkylene structure, a polyoxyethylene structure or a polyoxypropylene structure is preferred. The polyoxyethylene group structure is represented by-(OCH ₂ CH ₂ ) _n- , where n is an integer of 2 or more, and an integer of 2 to 10 is more preferable.

Examples of Z include aliphatic groups (for example, alkyl groups, substituted alkyl groups, unsaturated alkyl groups and substituted unsaturated alkyl groups, etc.), and aromatic groups (for example, aryl groups, substituted aryl groups, arylene groups and substitutions) Aryl groups, etc.), heterocyclic groups or combinations thereof. Such groups may contain an oxygen atom (-O-), a sulfur atom (-S-), an imino group (-NH-), a substituted imino group (-NR ^31- , where R ³¹ is an aliphatic group, Aromatic or heterocyclic) or carbonyl (-CO-).

The aliphatic group may contain a cyclic structure or a branched structure. The carbon number system of the aliphatic group is preferably 1-20, more preferably 1-15, and further preferably 1-10. The aliphatic group further contains a ring-assembled hydrocarbon group or a cross-linked cyclic hydrocarbon group. Examples of the ring-assembled hydrocarbon group include dicyclohexyl, perfluoronaphthyl, biphenyl, 4-cyclohexylphenyl, and the like. Examples of the cross-linked cyclic hydrocarbon ring include pinane, bornane, norpinane, norbornane, and bicyclooctane ring (bicyclo [2.2.2] octane Alkane ring and bicyclic [3.2.1] octane ring, etc.) and other 2-ring hydrocarbon rings; adamantane, tricyclic [5.2.1.0 ^2,6 ] decane and tricyclic [4.3.1.1 ^2,5 ] undecane 3 cyclic hydrocarbon ring and the like; tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] dodecane, perhydro-1,4 (methylene) methylene-5,8-naphthalene ring or the like 4-ring hydrocarbon ring; etc. The cross-linked cyclic hydrocarbon ring also contains a fused cyclic hydrocarbon ring, for example, a plurality of perhydronaphthalene (decalin), perhydroanthracene, perhydrophenanthrene, perhydroacenaphthene, perhydrofluorene, perhydroindene A condensed ring derived from a 5- to 8-membered cycloalkane ring such as a full hydrogen ring. As the aliphatic group, a saturated aliphatic group is preferable to an unsaturated aliphatic group. The aliphatic group may contain a substituent. Examples of the substituent include halogen atoms, aromatic groups, and heterocyclic groups. Among them, the aliphatic group does not contain an acid group as a substituent.

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

The heterocyclic group preferably contains a 5-membered ring or a 6-membered ring as a heterocyclic ring. Other heterocycles, aliphatic rings or aromatic rings may be fused to the heterocycle. . The heterocyclic group may contain a substituent. Examples of the substituents include halogen atoms, hydroxyl groups, oxo groups (= O), thio groups (= S), imino groups (= NH), and substituted imino groups (= NR ³² , where R ³² For aliphatic groups, aromatic groups or heterocyclic groups), aliphatic groups, aromatic groups and heterocyclic groups. Among them, the heterocyclic group does not contain 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 and a bromine atom), and an alkyl group having 1 to 6 carbon atoms (for example, Methyl, ethyl and propyl, etc.), Z or LZ. Among them, the definitions of L and Z are the same as those described 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 the monomer represented by the above formula (i), the following compounds are preferred. In this compound, R ¹ , R ² and R ³ are a hydrogen atom or a methyl group, L is a single bond or an alkylene group, or contains oxygen The divalent linking group of the alkylene structure, X is an oxygen atom or an imine group, and Z is an aliphatic group, a heterocyclic group or an aromatic group. As the monomer represented by the above formula (ii), the following compounds are preferred. In this compound, 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. base. As the monomer represented by the above formula (iii), the following compounds are preferred, in which R ⁴ , R ⁵ and R ⁶ are hydrogen atoms or methyl groups, and Z is an aliphatic group, a heterocyclic group or an aromatic group base.

Examples of the representative compounds represented by formulae (i) to (iii) include radical polymerizable compounds such as acrylates, methacrylates, and styrenes. In addition, as examples of the representative compounds represented by the formulas (i) to (iii), the compounds described in paragraphs 0089 to 0093 of JP-A-2013-249417 can be referred to, and these contents are incorporated in this specification.

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

･ Structural units containing functional groups that can interact with pigments etc. Polymer compounds can incorporate functional groups that can interact with pigments etc. Here, it is preferable that the polymer compound further has a structural unit containing a functional group that can interact with a pigment or the like. Examples of functional groups that can interact with the pigment and the like include acid groups, base groups, coordination groups, and reactive functional groups. When the polymer compound contains an acid group, a base group, a coordination group or a reactive functional group, it has a structural unit containing an acid group, a structural unit containing a base group, a structural unit containing a coordination group or having Reactive structural units are 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. That is, by introducing an alkali-soluble group into the polymer compound, the polymer compound as a dispersant that contributes to the dispersion of the pigment and the like of the curable composition also has alkali solubility. The curable composition containing such a polymer compound has more excellent alkali developability (the unexposed portion is more easily dissolved by alkali development), and the resulting cured film has more excellent light-shielding properties.

The polymer compound containing an acid group has a higher affinity with a solvent described later. Therefore, the curable composition having a polymer compound containing an acid group has more excellent coatability. This is presumably because the acid group in the structural unit containing an acid group easily interacts with the pigment and the like, and the polymer compound stably disperses the pigment and the like, and further reduces the viscosity of the polymer compound dispersed with the pigment and the like, so that the polymer compound It is also easy to disperse itself stably.

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

Among the functional groups that can interact with the pigment and the like, examples of the acid group include a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, and a phenolic hydroxyl group. At least one of the groups is preferable, and from the viewpoint of more excellent adsorption to pigments and more excellent dispersibility, the carboxylic acid group is more preferable. That is, it is preferable that the polymer compound further has at least one structural unit selected from the group including carboxylic acid group, sulfonic acid group and phosphoric acid group.

The polymer compound may have one kind or two or more kinds of structural units containing acid groups. The polymer compound may not have a structural unit containing an acid group. The content of the polymer compound containing the structural unit of the acid group is preferably 5 to 80% by mass relative to the total mass of the polymer compound. From the viewpoint of further suppressing damage to the image strength caused by alkali development, 10 to 60% by mass is better.

Among the functional groups that can interact with the pigment and the like, examples of the base group include a primary amine group, a secondary amine group, a tertiary amine group, a heterocyclic group containing an N atom, and an amide group. Among them, a tertiary amine group is preferable from the viewpoint of more excellent adsorption to pigments and more excellent dispersibility. The polymer compound may contain one kind of base alone or two or more kinds. The polymer compound may not have a structural unit containing a base. The content of the base group-containing structural unit in the polymer compound is preferably 0.01 to 50% by mass relative to the total mass of the polymer compound, and from the viewpoint of the curable composition showing more excellent developability, 0.01 to 30 mass % Is better.

Among the functional groups that can interact with pigments and the like, the coordination group and the reactive functional group include, for example, acetyl acetyl oxy group, trialkoxy silyl group, isocyanate group, acid anhydride group And acetyl chloride and so on. Among them, acetoacetoxy is preferred from the viewpoint of having more excellent adsorption power for pigments and making the pigments and the like more easily dispersed. The polymer compound may contain one kind of coordination group and reactive functional group alone, or may contain two or more kinds. The polymer compound may not have any one of the structural unit containing a coordination group and the structural unit containing a reactive functional group. The content of the structural unit containing a coordination group and the reactive functional group in the polymer compound is preferably 10 to 80% by mass relative to the total mass of the polymer compound, and is more excellent from the curable composition From the viewpoint of developability, 20 to 60% by mass is better.

When the polymer compound contains functional groups that can interact with the pigment and the like in addition to the graft chain, it is sufficient to contain functional groups that can interact with the pigment and the like. How to introduce these functional groups is not particularly limited. High The molecular compound preferably contains one or more structural units selected from structural units derived from monomers represented by the following formulas (iv) to (vi).

[Chemical Formula 22]

In formula (iv) to formula (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, a bromine atom, etc.) or an alkane having 1 to 6 carbon atoms Group (for example, methyl, ethyl, propyl, etc.). In formula (iv) to formula (vi), R ¹¹ , R ¹² and R ¹³ are preferably independently hydrogen atoms or alkyl groups having 1 to 3 carbon atoms, respectively independently hydrogen atoms or methyl groups For better. In formula (iv), it is further preferred that R ¹² and R ¹³ are each a hydrogen atom.

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

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

As L ₁ , a single bond, an alkylene group, or a divalent linking group containing an oxyalkylene structure is preferred. The oxyalkylene structure is preferably an oxyethylated structure or an oxypropylated structure. L ₁ may contain a polyoxyalkylene structure which repeatedly contains two or more oxyalkylene structures. As the polyoxyalkylene structure, a polyoxyethylene structure or a polyoxypropylene structure is preferred. The polyoxyethylene group structure is represented by-(OCH ₂ CH ₂ ) n-, where n is an integer of 2 or more, and an integer of 2 to 10 is more preferable.

In the formula (iv) to the formula (vi), in addition to the graft chain, Z ₁ represents a functional group that can form an interaction with a pigment, etc. A carboxylic acid group or a tertiary amine group is preferable, and a carboxylic acid group is more preferable.

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

As the monomer represented by formula (iv), the following compounds are preferred. In this compound, R ¹¹ , R ^12, and R ¹³ are each independently a hydrogen atom or a methyl group, and L ₁ is an alkylene group or contains an oxygen group. The divalent linking group of the alkyl structure, X ₁ is an oxygen atom or an imino group, and Z ₁ is a carboxylic acid group. As the monomer represented by the formula (v), the following compounds are preferred. In this compound, 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 . As the monomer represented by formula (vi), the following compounds are preferred. In this compound, R ¹⁴ , R ¹⁵ and R ¹⁶ are each independently a hydrogen atom or a methyl group, L ₁ is a single bond or an alkylene group, Z ₁ is a carboxylic acid group.

Hereinafter, representative examples of monomers (compounds) represented by formula (iv) to formula (vi) are shown. Examples of the monomer include a reaction product of methacrylic acid, crotonic acid, isocrotonic acid, a compound containing an addition-polymerizable double bond and a hydroxyl group in the molecule (for example, 2-hydroxyethyl methacrylate), and succinic anhydride , Reactant of compound containing addition polymerizable double bond and hydroxy group and phthalic anhydride, reactant and molecule of compound containing addition polymerizable double bond and hydroxy group and tetrahydroxyphthalic anhydride Reaction product of compound containing addition polymerizable double bond and hydroxyl group and trimellitic anhydride, reaction product of compound containing addition polymerizable double bond and hydroxyl group and pyromellitic anhydride, acrylic acid, acrylic acid dimer, low acrylic acid Polymer, maleic acid, itaconic acid, fumaric acid, 4-vinyl benzoic acid, vinyl phenol, 4-hydroxyphenylmethacrylamide, etc.

From the viewpoints of interaction with pigments, stability over time, and permeability to developer, the content of structural units containing functional groups that can interact with pigments, etc. in the polymer compound relative to that of the polymer compound The total mass is preferably 0.05 to 90% by mass, more preferably 1.0 to 80% by mass, and further preferably 10 to 70% by mass.

･ Other structural units In addition, in order to improve various properties such as image strength, the polymer compound may also have a structural unit containing a graft chain, a hydrophobic structural unit, and a pigment which may be combined with Other structural units that are different from the structural units that form the functional groups that interact with each other (for example, structural units that contain functional groups that have affinity with the solvent used in the dispersion composition, etc.). Examples of other structural units include structural units derived from radically polymerizable compounds selected from the group consisting of acrylonitriles and methacrylonitriles. The polymer compound may contain one kind of other structural unit alone, or may contain two or more kinds. The content of other structural units in the polymer compound relative to the total mass of the polymer compound is preferably 0% to 80% by mass, and more preferably 10% to 60% by mass. If the content of other structural units is 0 to 80% by mass, the curable composition has more excellent pattern formability.

･ Physical properties of the polymer compound The acid value of the polymer compound is not particularly limited, preferably 0 to 250 mgKOH / g, more preferably 10 to 200 mgKOH / g, and even more preferably 20 to 120 mgKOH / g. If the acid value of the polymer compound is 250 mgKOH / g or less, the peeling of the cured film from the support is further suppressed in the development step described later. If the acid value of the polymer compound is 10 mgKOH / g or more, the curable composition has more excellent alkali developability. If the acid value of the polymer compound is 20 mgKOH / g or more, the precipitation of the pigment and the like in the curable composition is further suppressed, and the number of coarse particles is smaller. As a result, the curable composition has more excellent stability over time. Sex.

The acid value of the polymer compound can be calculated based on the average content of acid groups in the polymer compound, for example. Furthermore, by changing the content of the structural unit containing the acid group in the polymer compound, a polymer compound having a desired acid value can be obtained.

From the viewpoint that the curable composition has more excellent developability and the resulting cured film is more difficult to peel off during the development step, as a polystyrene conversion value by GPC (Gel Permeation Chromatography) method, The weight average molecular weight of the polymer compound is preferably 4,000 to 300,000, more preferably 5,000 to 200,000, further preferably 6,000 to 100,000, and particularly preferably 10,000 to 50,000. The GPC method is based on the following method, that is, using HLC-8020GPC (manufactured by TOSOH CORPORATION), using TSKgel SuperHZM-H, TSKgel SuperHZ4000, TSKgel SuperHZ2000 (manufactured by TOSOH CORPORATION, 4.6mmID × 15cm) as the column, and THF as the eluent (Tetrahydrofuran). In addition, the polymer compound can be synthesized based on a known method.

Specific examples of the polymer compound include "DA-7301" manufactured by Kusumoto Chemicals, Ltd., and "Disperbyk-101 (polyamide amine phosphate), 107 (carboxylate), and 110 manufactured by BYK Chemie". (Copolymer containing acid groups), 111 (phosphoric acid dispersant), 130 (polyamide), 161, 162, 163, 164, 165, 166, 170, 190 (polymer copolymer) "," BYK- P104, P105 (high molecular weight unsaturated polycarboxylic acid) "," EFKA4047, 4050-4010-4165 (polyurethane system), EFKA4330-4340 (block copolymer), 4400-4402 (modified polyacrylate) manufactured by EFKA Corporation ), 5010 (polyesteramide), 5765 (high molecular weight polycarboxylate), 6220 (fatty acid polyester), 6745 (phthalocyanine derivative), 6750 (azo pigment derivative) ", Ajinomoto Fine-Techno Co ., Inc. "AJISPER PB821, PB822, PB880, PB881", "Flowlen TG-710 (urethane oligomer)" manufactured by Kyoeisha Chemical Co., Ltd., "polyflow No. 50E, No. .300 (acrylic copolymer) "," disparon KS- "manufactured by Kusumoto Chemicals, Ltd. 860, 873SN, 874, # 2150 (aliphatic polyvalent carboxylic acid), # 7004 (polyether ester), DA-703-50, DA-705, DA-725 "," DEMOL RN, N (" Naphthalenesulfonate formalin polycondensate), MS, C, SN-B (aromatic sulfonate formalin polycondensate) "," HOMOGENOL L-18 (polymer polycarboxylic acid) "," EMULGEN 920, 930, 935, 985 (polyoxyethenylnonylphenyl ether) "," ACETAMIN 86 (stearylamine acetate) "," Solsperse 5000 (phthalocyanine derivatives), 22000 (azo pigment derivatives) manufactured by Lubrizol Japan Limited ), 13240 (polyesteramine), 3000, 12000, 17000, 20000, 27000 (polymer containing functional part at the end), 24000, 28000, 32000, 38500 (graft copolymer) ", Nikko Chemicals Co. , Ltd. "NIKKOL T106 (polyoxyethylidene sorbitan monooleate), MYS-IEX (polyoxyethylidene monostearate)", manufactured by Kawaken Fine Chemicals Co., Ltd. HINOACT T-8000E, etc., organic silicone polymer KP341 manufactured by Shin-Etsu Chemical Co., Ltd., "W001: Yang, manufactured by Yusho Co., Ltd. "Ionic surfactant", polyoxyethyl lauryl ether, polyoxyethyl stearyl ether, polyoxyethyl oleyl ether, polyoxyethyl octyl phenyl ether, polyoxyethyl ethyl ether Nonionic surfactants such as nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid esters, and anionic systems such as "W004, W005, W017" Surfactant, "EFKA-46, EFKA-47, EFKA-47EA, EFKA Polymer 100, EFKA Polymer 400, EFKA Polymer 401, EFKA Polymer 450" manufactured by Morishita Sangyo Co., Ltd., and "Disperse" manufactured by SAN NOPCO LIMITED Aid 6, Disperse Aid 8, Disperse Aid 15, Disperse Aid 9100 and other polymer dispersants, "ADEKA Pluronic L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, ADEKA CORPORATION F87, P94, L101, P103, F108, L121, P-123 ", and" Ionet (trade name) S-20 "manufactured by Sanyo Chemical Industries, Ltd., etc. In addition, Acrylic base FFS-6752, Acrylic base FFS-187, Acrycure-RD-F8, and Cyclomer P can also be used. In addition, DISPERBYK-130, DISPERBYK-140, DISPERBYK-142, DISPERBYK-145, DISPERBYK-180, DISPERBYK-187, DISPERBYK-191, DISPERBYK-2001, DISPERBYK-2010, DISPERBYK-2012, DISPERBYK -2025, BYK-9076, AJISPER PB821, AJISPER PB822 and AJISPER PB881 manufactured by Ajinomoto Fine-Techno Co., Inc. One type of these polymer compounds may be used alone, or two or more types may be used simultaneously.

In addition, as the polymer compound, the compounds described in paragraphs 0127 to 0129 of Japanese Patent Laid-Open No. 2013-249417 can also be used, and such contents are incorporated in this specification.

As the dispersant, a graft copolymer of paragraphs 0037 to 0115 (corresponding to paragraphs 0075 to 0133 of US2011 / 0124824) of Japanese Patent Laid-Open No. 2010-106268 can also be used, and these contents are incorporated in this specification. As a dispersant, it is also possible to use a side chain structure containing an acidic group having paragraphs 0028 to 0084 of Japanese Patent Laid-Open No. 2011-153283 (corresponding paragraphs 0075 to 0133 of the corresponding US2011 / 0279759) via a linking group The polymer compounds constituting the components are incorporated in this specification. As the dispersant, the resin described in paragraphs 0033 to 0049 of Japanese Patent Laid-Open No. 2016-109763 can also be used, and this content is incorporated in this specification.

(Binder resin) It is preferable that the curable composition contains a binder resin. The content of the binder resin is preferably 0.1 to 30% by mass relative to the total solid content of the curable composition. One type of binder resin can be used alone, or two or more types can be used simultaneously. When two or more binder resins are used at the same time, the total amount 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. Preferably, in order to realize water development or weak alkali water development, a linear organic polymer that is soluble or swellable to water or weak alkali water is selected. Among them, as the binder resin, alkali-soluble resins (resins containing groups that promote alkali-solubility) are particularly preferred.

Alkali-soluble resin refers to a resin containing a group that promotes alkali solubility (alkali-soluble group), and refers to a resin that is different from the dispersant described. Examples of the alkali-soluble resin include resins containing at least one alkali-soluble group in the molecule, for example, polyhydroxystyrene resin, polysiloxane resin, (meth) acrylic resin, (meth) acrylamide Resin, (meth) acrylic acid / (meth) acrylamide copolymer, epoxy resin and polyimide resin, etc.

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

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

In addition, it is also possible to use a combination of ethylenically unsaturated compounds capable of copolymerization and compounds containing an ethylenically unsaturated group in the side chain. As the ethylenically unsaturated group, a (meth) acrylic group is preferred. Acrylic resins containing ethylenically unsaturated groups in the side chain can be obtained, for example, by the addition reaction of the carboxylic acid groups of acrylic resins containing carboxylic acid groups with ethylenically unsaturated compounds containing epoxypropyl or alicyclic epoxy groups .

As the alkali-soluble resin, for example, Japanese Patent Publication No. 59-44615, Japanese Patent Publication No. 54-34327, Japanese Patent Publication No. 58-12577, Japanese Patent Publication No. 54-25957, Japanese Patent Publication No. 54-92723, Japanese Patent Laid-Open No. 59-53836 and Japanese Patent Laid-Open No. 59-71048 describe a radical polymer containing a carboxylic acid group in the side chain; European Patent No. 993966, European Patent No. 1204000 and Japanese Patent Laid-Open 2001- Acetal-modified polyvinyl alcohol-based binder resins containing alkali-soluble groups described in various publications such as 318463; polyvinylpyrrolidone; polyethylene oxide; alcohol-soluble nylon and 2,2-bis- ( 4-Hydroxyphenyl) -Propane and epichlorohydrin reactant polyether, etc .; Polyimide resin described in International Publication No. 2008/123097; etc.

As the alkali-soluble resin, for example, the compounds described in paragraphs 0225 to 0245 of Japanese Patent Laid-Open No. 2016-75845 can also be used, and the above contents are incorporated in this specification.

As the alkali-soluble resin, a polyimide precursor can also be used. Polyimide precursor refers to a resin obtained by addition polymerization of a compound containing an acid anhydride group and a diamine compound at 40 to 100 ° C. Examples of the polyimide precursor include resins containing repeating units represented by formula (1). The structure of the polyimide precursor includes, for example, the following structure including an amic acid structure represented by the following formula (2), and ring closure of the amide imide structure with an amide acid structure. Formula (3) and / or the amide imide structure represented by the following formula (4) formed by ring-closing amide imide with all amide acid structures. In addition, in this specification, a polyimide precursor having an amide acid structure may be referred to as a polyamic acid.

[Chemical Formula 23]

[Chemical Formula 24]

[Chemical Formula 25]

[Chemical Formula 26]

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

Examples of the above-mentioned polyimide precursor include compounds described in paragraphs 0011 to 0031 of Japanese Patent Laid-Open No. 2008-106250, compounds described in paragraphs 0022 to 0039 of Japanese Patent Laid-Open No. 2016-122101, and Japan The compounds described in paragraphs 0061 to 0092 of JP-A-2016-68401 are incorporated in this specification.

From the viewpoint that the pattern shape of the cured film obtained from the curable composition is more excellent, it is preferable that the alkali-soluble resin contains at least one selected from the group consisting of polyimide resins and polyimide precursors. The alkali-soluble group-containing polyimide resin is not particularly limited, and a known alkali-soluble group-containing polyimide resin can be used. Examples of the above-mentioned polyimide resin include the resin described in paragraph 0050 of Japanese Patent Application Laid-Open No. 2014-137523, the resin described in paragraph 0058 of Japanese Patent Application Laid-Open No. 2015-187676, and Japanese Patent Application No. 2014-106326 The resins described in paragraphs 0012 to 0013 of the Gazette are incorporated in this specification.

<Polymerization inhibitor> The curable composition preferably contains a polymerization inhibitor. The polymerization inhibitor is not particularly limited, and known polymerization inhibitors can be used. Examples of polymerization inhibitors include phenol-based polymerization inhibitors (for example, p-methoxyphenol, 2,5-di-tert-butyl-4-methylphenol, 2,6-di-tert-butyl -4-methylphenol, 4,4'-thiobis (3-methyl-6-third butylphenol), 2,2'-methylenebis (4-methyl-6-third butyl Phenol) and 4-methoxynaphthol, etc.); hydroquinone-based polymerization inhibitors (for example, hydroquinone and 2,6-di-tert-butyl hydroquinone, etc.); quinone-based polymerization Inhibitors (eg, benzoquinone, etc.); free radical polymerization inhibitors (eg, 2,2,6,6-tetramethylpiperidine 1-oxyl radical and 4-hydroxy-2,2,6,6- Tetramethylpiperidine 1-oxyl radical, etc.); nitrobenzene-based polymerization inhibitors (eg, nitrobenzene and 4-nitrotoluene, etc.); phenothiazine-based polymerization inhibitors (eg, phenothiazine and 2-methyl Oxyphenithiol, etc.); etc. Among them, a phenol-based polymerization inhibitor or a radical-based polymerization inhibitor is preferred from the viewpoint that the curable composition has more excellent effects of the present invention. In addition, when preparing the curable composition, the above-mentioned polymerization initiator may be mixed together with other components. For example, when synthesizing the above-mentioned resin, the user may mix other components together with the above-mentioned resin.

The content of the polymerization inhibitor in the curable composition is not particularly limited. From the viewpoint that the curable composition has more excellent stability over time and more excellent curability, relative to the total solids of the curable composition The content is preferably 0.0001 to 1% by mass. One type of polymerization inhibitor may be used alone, or two or more types may be used simultaneously. When two or more kinds of polymerization inhibitors are used at the same time, the total content is preferably within the above range. When the polymerization inhibitor is used together with a resin containing a curable group, its effect is remarkable. For example, when making a dispersion composition, after making a dispersion composition, when making a curable composition, after making a curable composition, etc., even when the dispersion composition and / or curable composition becomes high temperature or is stored for a long time If the resin containing a curable group is polymerized, the polymerization inhibitor can be used without any problem.

<Solvent> The curable composition may contain a solvent. The solvent is not particularly limited, and known solvents can be used. The content of the solvent in the curable composition is not particularly limited. Generally, the solid content of the curable composition is adjusted to 20 to 90% by mass, preferably 30 to 90% by mass. One type of solvent may be used alone, or two or more types may be used simultaneously. When two or more solvents are used simultaneously, it is preferable to adjust the total solid content of the curable composition within the above range.

Examples of the solvent include water and organic solvents. Examples of organic solvents include acetone, methyl ethyl ketone, cyclohexane, ethyl acetate, dichloroethane, tetrahydrofuran, toluene, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and ethylene glycol diethyl ether. Methyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, acetone acetone, cyclohexanone, cyclopentanone, diacetone alcohol, ethylene glycol monomethyl ether acetate, ethylene glycol ethyl ether acetate, ethylene glycol mono Isopropyl ether, ethylene glycol monobutyl ether acetate, 3-methoxypropanol, methoxymethoxyethanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol di Methyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxypropyl acetate, N, N-dimethylformamide, dimethyl sulfoxide , Γ-butyrolactone, ethyl acetate, butyl acetate, methyl lactate, N-methyl-2-pyrrolidone, ethyl lactate, etc., but not limited to these.

<Surfactant> The curable composition preferably contains a surfactant. The curable composition containing a surfactant has more excellent coatability. The content of the surfactant in the curable composition is not particularly limited, and it is preferably 0.001 to 2.0% by mass relative to the total solid content of the curable composition. One type of surfactant may be used alone, or two or more types may be used simultaneously. When two or more surfactants are used simultaneously, the total amount is preferably within the above range.

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

For example, if the curable composition contains a fluorine-based surfactant, the liquid characteristics (especially fluidity) of the curable composition are further improved. That is, when a curable composition containing a fluorine-based surfactant is used to form a curable composition layer on a support, the curable composition is improved by reducing the interfacial tension between the support and the curable composition The wettability of the support improves the coatability of the curable composition. Therefore, even when a curable composition layer of about several μm is formed with a small amount of liquid, it is possible to form a curable composition layer with less uneven thickness and a more uniform thickness.

The fluorine content in the fluorine-based surfactant is not particularly limited, and 3 to 40% by mass is more preferable, 5 to 30% by mass is more preferable, and 7 to 25% by mass is further preferable. According to a curable composition containing a fluorine-based surfactant having a fluorine content of 3 to 40% by mass, a curable composition layer having a more uniform thickness can be formed, and as a result, the curable composition has more excellent liquidity saving . In addition, within the above range, the fluorine-based surfactant is more easily dissolved in the curable composition.

Examples of fluorine-based surfactants 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 and PF7002 (manufactured by OMNOVA), etc. As the fluorine-based surfactant, a block polymer can also be used. For example, the compound described in Japanese Patent Application Laid-Open No. 2011-89090 can also be used, and the above content is incorporated in this specification.

<Ultraviolet absorbent> The curable composition may contain an ultraviolet absorbent. The cured film obtained by the curable composition containing an ultraviolet absorber has a more excellent pattern shape (finer pattern shape). As the ultraviolet absorber, a salicylic acid-based, benzophenone-based, benzotriazole-based, substituted acrylonitrile-based, and tertiary-based ultraviolet absorbers can be used. As the ultraviolet absorber, for example, the compounds described in paragraphs 0137 to 0142 of Japanese Patent Laid-Open No. 2012-068418 (corresponding paragraphs 0251 to 0254 of the corresponding US2012 / 0068292) can be used, and the above contents are incorporated in this specification. As the ultraviolet absorber, a diethylamino-benzenesulfonyl-based ultraviolet absorber (manufactured by DAITO CHEMICAL CO., LTD., Trade name: UV-503) and the like can also be used. As the ultraviolet absorber, the compounds described in paragraphs 0134 to 0148 of Japanese Patent Laid-Open No. 2012-32556 can also be used, and the above contents are incorporated in this specification. The content of the ultraviolet absorber in the curable composition is not particularly limited, and relative to the total solid content of the curable composition, 0.001 to 15% by mass is preferable, 0.01 to 10% by mass is more preferable, and 0.1 to 5 The mass% is more preferably.

<Silane coupling agent> The hardening composition may contain a silane coupling agent. In this specification, the silane coupling agent refers to a compound containing the following hydrolyzable group and other functional groups in the molecule. The above-mentioned hydrolyzable group refers to a substituent directly bonded to a silicon atom and capable of generating a siloxane bond through a hydrolysis reaction and / or a condensation reaction. Examples of the hydrolyzable group include a halogen atom directly bonded to a silicon atom, an alkoxy group, an alkoxy group, an alkenyloxy group, and the like. When the hydrolyzable group contains carbon atoms, its carbon number is preferably 6 or less, and more preferably 4 or less. In particular, an alkoxy group having 4 or less carbon atoms or an alkoxy group having 4 or less carbon atoms is preferred.

It is preferable that the silane coupling agent does not contain silicon atoms and fluorine atoms other than the silicon atoms bonded by any hydrolyzable group. If a curable composition containing the above-mentioned silane coupling agent is used to form a cured film on the support, the cured film has more excellent adhesion to the support.

The content of the silane coupling agent in the curable composition relative to the total solid content in the curable composition is preferably 0.1 to 10% by mass, more preferably 0.5 to 8% by mass, and further preferably 1.0 to 6% by mass. . The silane coupling agent can be used alone or in combination of two or more. When two or more silane coupling agents are used at the same time, the total content is preferably within the above range.

[Manufacturing method of curable composition] The curable composition can use a known mixing method (for example, a mixing method using a stirrer, a homogenizer, a high-pressure emulsifier, a wet pulverizer, a wet disperser, etc.) The ingredients are mixed and prepared. When preparing a hardenable composition, each component may be blended together, or each component may be separately dissolved or dispersed in a solvent and then blended sequentially. In addition, there is no particular restriction on the order of input and operating conditions during blending.

It is preferable to use a filter to filter the curable composition for the purpose of removing foreign substances, reducing defects, and the like. The filter is not particularly limited, and a known filter can be used. The material of the filter is not particularly limited, and examples thereof include fluorine resins such as PTFE (polytetrafluoroethylene), polyamide resins such as nylon, and polyolefin resins such as polyethylene and polypropylene (PP). Including high density, ultra high molecular weight) and other filters formed. Among them, filters formed from polypropylene (including high-density polypropylene) or nylon are preferred. The pore size of the filter is not particularly limited. Usually, 0.1 to 7.0 μm is preferred, 0.2 to 2.5 μm is more preferred, 0.2 to 1.5 μm is further preferred, and 0.3 to 0.7 μm is particularly preferred. By setting it in this range, it is possible to suppress the filtration clogging of the pigment, and it is possible to reliably remove fine foreign substances such as impurities and aggregates contained in the pigment. When using filters, different filters can be combined. In this case, the filtering by the first filter may be performed only once, or may be performed twice or more. When combining different filters for more than two filtrations, the pore size of the filter used in the second filtration is the same or larger than the pore size of the filter used in the first filtration. Also, filters of the same material but different pore sizes can be combined. The pore size here can refer to the nominal value of the filter manufacturer. Examples of commercially available filters include those manufactured by NIHON PALL LTD., Advantec Toyo Kaisha, Ltd., Nihon Entegris K.K. (old Nippon Mykrolis Corporation), and KITZ MICRO FILTER CORPORATION.

The second filter can be formed of the same material as the first filter described above. The pore size of the second filter is not particularly limited, but usually 0.2 to 10.0 μm is preferred, 0.2 to 7.0 μm is more preferred, and 0.3 to 6.0 μm is further preferred. It is preferable that the curable composition contains substantially no impurities such as metals (particles and ions), metal salts containing halogen, acids and alkalis. In addition, in this specification, substantially not containing means that it cannot be detected by the following measurement method. The content of impurities contained in the curable composition, the above-mentioned components, the above-mentioned filter, etc. is not particularly limited, and it is preferably 1 mass ppm or less relative to the total mass, preferably 1 mass ppb or less, 100 The mass ppt or less is more preferably, and the mass ppt or less is particularly good, and it is most preferably not substantially contained. In addition, the content of the above impurities can be measured with an inductively coupled plasma mass analyzer (manufactured by Yokogawa Analytical Systems, Inc., Agilent 7500cs type). In addition, ppm means parts per million (parts per million), ppb means parts per billion (parts per billion), ppt means parts per trillion (parts per trillion).

[Container] The curable composition can be temporarily stored in a container before use. The container for storing the curable composition is not particularly limited, and a known container can be used. As a container for storing the curable composition, a container with high cleanliness and low elution of impurities is preferred. For example, those that are commercially available for semiconductor applications can be used. Specific examples of usable containers include the "clean bottle" series manufactured by AICELLO CHEMICAL CO., LTD. And the "pure bottle" manufactured by KODAMA PLASTICS Co., Ltd., but they are not limited thereto. For example, it is also preferable to use a multilayer bottle in which the inner wall of the container is composed of 6 kinds of resins and has a 6-layer structure, or a multilayer bottle in which the inner wall of the container is composed of 6 kinds of resins and has a 7-layer structure. Examples of such containers include those described in Japanese Patent Laid-Open No. 2015-123351.

[Cured film and method for producing cured film] The cured film according to the embodiment of the present invention is a cured film obtained by curing the curable composition. The thickness of the cured film is not particularly limited, but usually 0.2 to 7 μm is preferable, and 0.4 to 5 μm is more preferable. The above thickness is an average thickness, which is a value obtained by measuring the thickness of any 5 points or more of the light-shielding film and arithmetically averaging these.

The production method of the cured film is not particularly limited, and a method of applying a curable composition to a support to form a coating film and subjecting the coating film to curing treatment to produce a cured film. The method of curing treatment is not particularly limited, and examples thereof include photo-curing treatment or thermal-curing treatment. From the viewpoint of easy pattern formation, photo-curing treatment (particularly, curing treatment by irradiation with actinic rays or radiation) is Better.

The cured film of the embodiment of the present invention is a cured film obtained by curing a curable composition layer formed using a curable composition. The method for producing the cured film is not particularly limited, and the following steps are preferably included. ･ Step of forming a curable composition layer ･ Exposure step ･ Development step The following describes each step.

<Step of forming curable composition layer> The step of forming a curable composition layer is a step of forming a curable composition layer using the curable composition. As a step of forming the curable composition layer using the curable composition, for example, a step of applying the curable composition on the support to form the curable composition layer (coating step) can be mentioned. The type of the support is not particularly limited. When the cured film is applied to a solid-state imaging element, for example, a silicon substrate can be used, and when a color filter (including color filters for solid-state imaging elements) is used as the cured film, an example can be given. A glass substrate (glass wafer), etc. Examples of the method for applying the curable composition to the support include spin coating, slit coating, inkjet method, spray coating, spin coating, cast coating, roll coating, and screen printing method. Various coating methods. The curable composition coated on the support is usually dried at 70 to 150 ° C. for about 1 to 4 minutes to form a curable composition layer.

<Exposure step> In the exposure step, the curable composition layer formed in the curable composition layer formation step is exposed to actinic rays or radiation through a photomask having a pattern-shaped opening, and only the The hardening composition layer subjected to light irradiation is hardened. The exposure is preferably performed by irradiating radiation, and it is preferable to use ultraviolet rays such as g-rays, h-rays, and i-rays. As a light source, a high-pressure mercury lamp is preferred. The irradiation intensity is not particularly limited, but usually 5 to 1500 mJ / cm ² is preferable.

<Development step> The development process (development step) is carried out after the exposure step, so that the unexposed part in the exposure step is eluted from the developing solution. In this way, only the portion that has been photohardened remains on the support. The developer is not particularly limited, and examples thereof include alkali developer, and among them, organic alkali developer is preferred. The development conditions are not particularly limited. The development temperature is usually 20 to 40 ° C, and the development time is usually 20 to 180 seconds. The alkaline aqueous solution (alkaline developer) is not particularly limited, and examples of the alkaline compound contained in the inorganic alkaline developer include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, sodium silicate and Sodium metasilicate, etc. The content of the above compound in the alkaline aqueous solution is not particularly limited, but it is usually preferably 0.001 to 10% by mass relative to the total mass of the alkaline aqueous solution, and more preferably 0.005 to 0.5% by mass. Examples of the alkaline compound contained in the organic alkali developer include ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, and tetrapropylammonium hydroxide. , Tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo- [5,4,0] -7-undecene, etc. The content of the above compound in the alkaline aqueous solution is not particularly limited, but it is usually preferably 0.001 to 10% by mass relative to the total mass of the alkaline aqueous solution, and more preferably 0.005 to 0.5% by mass.

The aqueous alkali solution may contain, for example, water-soluble organic solvents such as methanol and ethanol. In addition, the alkaline aqueous solution may contain a surfactant. In addition, when using these alkaline aqueous solutions as a developing solution, it is preferable to wash the curable composition layer that has been developed with pure water or the like. In this specification, this step is referred to as a cleaning step, and it is preferable that the method for producing a cured film includes a cleaning step.

In addition, the manufacturing method of the cured film may include other steps. The other steps are not particularly limited, and can be appropriately selected according to the purpose. Examples of other steps include a surface treatment step of the base material, a pre-heating step (pre-baking step), and a post-heating step (post-baking step). The heating temperature in the pre-heating step and the post-heating step is not particularly limited, but it is generally preferably 80 to 300 ° C. The heating time in the pre-heating step and the post-heating step is not particularly limited, and 30 to 500 seconds is preferable.

It is preferable that the cured film has a surface uneven structure. This can reduce the light reflectance of the cured film. The cured film may have an uneven structure on its surface, or a coating film may be arranged on the cured film to give the uneven structure. The shape of the surface uneven structure is not particularly limited, and the surface roughness is preferably in the range of 0.55 to 1.5 μm or less. The light reflectance of the cured film is preferably 5% or less, more preferably 3% or less, and further preferably 2% or less. The method for producing the surface uneven structure is not particularly limited, and examples include a method of roughening the surface of the cured film and / or the coating film by the following methods: the cured film or the coating film contains an organic filler and / or Inorganic filler method; photolithography method, etching method, sputtering method and nano-imprint method, etc. In addition, as a method of reducing the light reflectance of the cured film, for example, a method of arranging a low refractive index film on the cured film; arranging a film with a different refractive index (for example, a high refractive index film) on the low refractive film Method; for example, the method for forming a low optical density layer and a high optical density layer described in Japanese Patent Laid-Open No. 2015-1654.

The above-mentioned cured film can be used in the light-shielding member and the light-shielding film of the optical filter and the module, and the anti-reflection member and the anti-reflection film used in the following equipment, such as personal computers, digital tablets, mobile phones, smart phones, etc. Portable devices such as mobile phones and digital cameras; OA (Office Automation) devices such as multifunction devices and scanners; port area monitors, bar code readers, automated teller machines (ATM: automated teller machine), high-speed cameras Industrial equipment such as face authentication personal authentication function equipment; vehicle-mounted camera equipment; medical camera equipment such as endoscopes, capsule endoscopes and catheters; biosensors, biosensors (biosensor ), Military reconnaissance cameras, three-dimensional map cameras, meteorological and marine observation cameras, land resource exploration cameras, and space astronomy and deep space target exploration cameras and other space equipment.

The cured film can also be used for micro LEDs (Light Emitting Diode) and micro OLEDs (Organic Light Emitting Diode). In addition to optical filters and optical films used in micro LEDs and micro OLEDs, the above-mentioned cured film is also suitable for members that impart a light-shielding function or an anti-reflection function. Examples of micro LEDs and micro OLEDs include those described in Japanese Special Table No. 2015-500562 and Japanese Special Table 2014-533890.

The above hardened film is suitable for optical filters and optical films used in quantum dot displays. Moreover, it is suitable for the member which gives a light-shielding function and an anti-reflection function. Examples of quantum dot displays include US Patent Application Publication No. 2013/0335677, US Patent Application Publication No. 2014/0036536, US Patent Application Publication No. 2014/0036203, and US Patent Application Publication No. 2014/0035960 Writer.

[Solid-state imaging device and solid-state imaging element] The solid-state imaging device and the solid-state imaging element according to an embodiment of the present invention include the above-mentioned cured film. The form in which the solid-state imaging element contains a cured film is not particularly limited. For example, a plurality of photoelectric cells including a light-receiving area constituting the solid-state imaging element (CCD image sensor, CMOS image sensor, etc.) on the support may be mentioned. A light-receiving element such as a diode and polysilicon, and having the above-mentioned hardened film on the side of the light-receiving element forming surface of the support (for example, a portion other than the light-receiving portion and / or pixels for color adjustment) or the side opposite to the forming surface By. The solid-state imaging device includes the above-mentioned solid-state imaging element.

7 to 8, a configuration example of the solid-state imaging device and solid-state imaging element will be described. In addition, in FIGS. 7 to 8, in order to make each part clearer, the ratio of the thickness and / or width of each structure is partially exaggerated regardless of the actual situation. As shown in FIG. 7, the solid-state imaging device 700 includes a rectangular solid-state imaging element 701 and a transparent cover glass 703 that is held above the solid-state imaging element 701 and seals the solid-state imaging element 701. Furthermore, a lens layer 711 is superposed on the cover glass 703 via a spacer 704. The lens layer 711 is composed of a support 713 and a lens material 712. The lens layer 711 can be formed by integrally forming the support 713 and the lens material 712. When stray light enters the peripheral region of the lens layer 711, the light-gathering effect in the lens material 712 due to light diffusion is reduced, and the light reaching the imaging unit 702 is reduced. In addition, interference caused by stray light may also occur. Therefore, a light shielding film 714 is provided in the peripheral area of the lens layer 711 to shield the light. The cured film of the embodiment of the present invention (especially when a black pigment is contained as a colorant) can also be used as the light-shielding film 714.

The solid-state imaging element 701 photoelectrically converts the optical image formed by the imaging unit 702 which becomes the light-receiving surface, and outputs it as an image signal. The solid-state imaging element 701 includes a laminated substrate 705 in which two substrates (equivalent to supports) are laminated. The build-up substrate 705 includes a rectangular-shaped wafer substrate 706 and a circuit substrate 707 of the same size, and a circuit substrate 707 is layered on the back area of the wafer substrate 706.

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

An imaging unit 702 is provided at the center of the surface of the wafer substrate 706. In addition, when stray light enters the peripheral area of the imaging unit 702, dark current (interference) is generated from the circuit in the peripheral area. Therefore, a light shielding film 715 is provided in the peripheral area to shield the light. The cured film of the embodiment of the present invention (especially when a black pigment is contained as a colorant) can also be used as the light-shielding film 715.

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

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

As shown in FIG. 8, the imaging unit 702 is composed of various parts provided on the substrate 804 such as a light receiving element 801, a color filter 802, and a microlens 803. The color filter 802 has a blue pixel 805b, a red pixel 805r, a green pixel 805g, and a black matrix 805bm. The cured film of the embodiment of the present invention (particularly, when a black pigment is contained as a colorant) can also be used as the black matrix 805bm.

As the material of the substrate 804, the same material as the aforementioned wafer substrate 706 can be used. A p-hole layer 806 is formed on the surface layer of the substrate 804. A light-receiving element 801 is formed in the p-hole layer 806 in a square network arrangement. The light-receiving element 801 is formed of an n-type layer, and accumulates signal charges generated by photoelectric conversion.

A vertical transmission path 808 formed of an n-type layer is formed on one side of the light receiving element 801 via the read gate portion 807 of the surface layer of the p-hole layer 806. In addition, on the other side of the light receiving element 801, a vertical transmission path 808 belonging to an adjacent pixel is formed through an element separation region 809 formed of a p-type layer. The read gate portion 807 is a channel area for the vertical transmission path 808 to read the signal charge accumulated in the light receiving element 801.

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

A light-shielding film 812 is formed on the vertical transfer electrode 811 so as to cover its surface. The light-shielding film 812 has an opening at a position directly above the light-receiving element 801, and shields light from other areas. The cured film of the embodiment of the present invention (in particular, when a black pigment is contained as a colorant) can also be used as the light-shielding film 812. The light shielding film 812 is provided with a transparent intermediate layer, which includes an insulating film 813 formed of BPSG (borophospho silicate glass), an insulating film (passivation film) 814 formed of P-SiN, and transparent A planarization film 815 formed of resin or the like. The color filter 802 is formed on the intermediate layer.

[Black Matrix] The black matrix contains the cured film of the embodiment of the present invention. The color filter, solid-state imaging element, and liquid crystal display device sometimes include a black matrix. Examples of the black matrix include those described above; black edges provided on the peripheral portion of a display device such as a liquid crystal display device; grid-like and / or striped black between red pixels, blue pixels, and green pixels Part; a black pattern of dots and / or lines for shading TFT (thin film transistor); etc. The definition of the black matrix is described in, for example, Taihe Kanno, "Dictionary of Liquid Crystal Display Manufacturing Devices", 2nd Edition, NIKKAN KOGYO SHINBUN, LTD., 1996, p.64. In order to improve the display contrast, and in order to prevent the deterioration of the image quality caused by the photocurrent leakage in the case of an active matrix driving liquid crystal display device using a thin-film transistor (TFT), it is preferable that the black matrix has a high light-shielding property.

The manufacturing method of the black matrix is not particularly limited, and can be manufactured by the same method as the manufacturing method of the above-mentioned cured film. Specifically, a curable composition layer is coated on a support to form a curable composition layer, and exposure and development are performed, so that a pattern-shaped cured film (black matrix) can be produced. In addition, the thickness of the cured film used as the black matrix is preferably 0.1 to 4.0 μm.

The material of the above-mentioned support is not particularly limited, and preferably has a transmittance of 80% or more with respect to visible light. Specific examples of such materials include soda lime glass, alkali-free glass, quartz glass, and borosilicate glass; plastics such as polyester resins and polyolefin resins; etc., from chemical resistance and From the viewpoint of heat resistance, alkali-free glass, quartz glass, or the like is preferred.

[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 a color filter provided with a support and the above black matrix can be mentioned. That is, a color filter including red colored pixels, green colored pixels, and blue colored pixels formed in the openings of the black matrix formed on the support can be exemplified.

The color filter containing a black matrix (cured film) can be manufactured by the following method, for example. First, a coating film (resin composition layer) containing a resin composition containing a pigment corresponding to each colored pixel of the color filter is formed on the opening of the pattern-shaped black matrix formed on the support. In addition, the resin composition for each color is not particularly limited, and a known resin composition can be used, but it is preferable to use the curable composition of the embodiment of the present invention. Then, the resin composition layer is exposed through a mask having a pattern corresponding to the opening of the black matrix. Next, after removing the unexposed portion by the development process, by performing baking, a colored pixel can be formed on the opening of the black matrix. For example, a color filter having red pixels, green pixels, and blue pixels can be manufactured by performing a series of operations using resin compositions for each color containing red pigment, green pigment, and blue pigment.

[Image display device] The image display device of the embodiment of the present invention contains a cured film. The form in which the image display device contains a cured film is not particularly limited, and the form described above having a color filter containing a black matrix (cured film) can be mentioned.

As a typical example of the image display device of the present embodiment, a liquid crystal display device can be mentioned. For example, a form including a pair of opposed supports and a liquid crystal compound enclosed between the supports can be given. As the above-mentioned support, it has been explained as the support for the black matrix.

Specific examples of the liquid crystal display device include, for example, a polarizer / support / color filter / transparent electrode layer / alignment film / liquid crystal layer / alignment film / transparent electrode layer / TFT (Thin (Thin Film Transistor) laminated body of element / support / polarizer / backlight unit.

The liquid crystal display device is not limited to the above-mentioned device, and examples thereof include "electronic display devices (by Shosaki Sasaki, Kogyo Chosakai Publishing Co., Ltd., published in 1990)", and "display devices (by Ibuki Shunzo, Sangyo Tosho Publishing Co., Ltd. was released in the first year of Heisei) "and other liquid crystal display devices. In addition, for example, a liquid crystal display device described in "Next Generation Liquid Crystal Display Technology (Edited by Uchida Ryuo, Kogyo Chosakai Publishing Co., Ltd., 1994)" can be cited.

[Infrared Sensor] The infrared sensor of the embodiment of the present invention contains the above-mentioned cured film. The infrared sensor of the above-described embodiment will be described using FIG. 9. In the infrared sensor 900 shown in FIG. 9, the element symbol 910 indicates a solid-state imaging element. The imaging area provided on the solid-state imaging element 910 is composed of an infrared absorption filter 911 and a color filter 912 according to an embodiment of the present invention. The infrared absorption filter 911 transmits light in the visible light region (for example, light with a wavelength of 400 to 700 nm) and blocks light in the infrared region (for example, light with a wavelength of 800 to 1,300 nm, preferably light with a wavelength of 900 to 1,200 nm , More preferably a light with a wavelength of 900 to 1,000 nm), as a colorant, a cured film containing an infrared absorber (in the form of an infrared absorber, as already explained.) Can be used. The color filter 912 is a color filter formed with pixels that transmit and absorb light of a specific wavelength in the visible light region. For example, red (R) pixels, green (G) pixels, and blue (B) pixels can be used. The shape of the color filter, etc., is as explained above. A resin film 914 (for example, a transparent resin film or the like) is disposed between the infrared transmission filter 913 and the solid-state imaging element 910, and can transmit light having a wavelength that transmits the infrared transmission filter 913. The infrared transmission filter 913 is a filter that has visible light shielding properties and transmits infrared rays of a specific wavelength, and can use a coloring agent (for example, a perylene compound and / or a bisbenzofuranone compound, etc.) that absorbs light in the visible light region. , And a cured film of an embodiment of the present invention of an infrared absorber (for example, pyrrolopyrrole compound, phthalocyanine compound, naphthalocyanine compound, polymethine compound, etc.). For example, the infrared transmission filter 913 shields light with a wavelength of 400 to 830 nm and transmits light with a wavelength of 900 to 1,300 nm. A microlens 915 is arranged on the incident light hν side of the color filter 912 and the infrared transmission filter 913. A planarizing film 916 is formed to cover the microlens 915. In the embodiment shown in FIG. 9, the resin film 914 is arranged, but an infrared transmission filter 913 may be formed instead of the resin film 914. That is, the infrared transmission filter 913 can be formed on the solid-state imaging element 910. In the embodiment shown in FIG. 9, the film thickness of the color filter 912 and the film thickness of the infrared transmission filter 913 are the same, but the film thickness of the two may be different. In the embodiment shown in FIG. 9, the color filter 912 is disposed closer to the incident light hν side than the infrared absorption filter 911, but in the order of replacing the infrared absorption filter 911 and the color filter 912, The infrared absorption filter 911 is provided on the incident light hν side of the color filter 912. In the embodiment shown in FIG. 9, the infrared absorption filter 911 is stacked adjacent to the color filter 912, but the two filters are not necessarily adjacent, and other layers may be provided between them. The cured film of the embodiment of the present invention can be used as a light-shielding film such as the end or side surface of the surface of the infrared absorption filter 911. In addition, the inner wall of the device used for the infrared sensor can also prevent the inside The reflected or unexpected light enters the light-receiving portion, thereby improving sensitivity. According to the infrared sensor, since the image information can be acquired at the same time, it is possible to realize the motion sensing of the object that detects motion and so on. Moreover, since distance information can be acquired, it is also possible to realize the photography of images including 3D information.

Next, a solid-state imaging device to which the above-mentioned infrared sensor 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, regarding each configuration of the solid-state imaging device, refer to paragraphs 0032 to 0036 of Japanese Patent Laid-Open No. 2011-233983, and the contents are incorporated in this specification. [Example]

Hereinafter, the present invention will be described in more detail based on examples. As long as it does not deviate from the gist of the present invention, the materials, usage amounts, ratios, processing contents, and processing steps shown in the following examples can be appropriately changed. Therefore, the scope of the present invention should not be interpreted restrictively by the embodiments shown below.

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

[Chemical Formula 27]

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

[Synthesis of INT-31] [Chemical Formula 28]

Using the method described in paragraph 0379 of Japanese Patent Application Laid-Open No. 2009-191061, the precursor B in the above formula was synthesized, and then, the precursor B (6.00 g, 11.3 mmol) dissolved in the ice bath was dissolved To a solution of ethylamine (1.62g, 16.0mmol) in THF (tetrahydrofuran, 60g) was added dropwise myristic acid chloride (3.34g, 13.5mmol). After the dropwise addition, the mixture was stirred at the same temperature for 1 hour and then further at 20 ° The mixture was stirred for 3 hours to obtain a reaction solution. Then, 400 mL of ethyl acetate and 200 mL of a 4% by mass sodium bicarbonate aqueous solution were added to the reaction solution, and liquid separation was performed to obtain an organic phase. Then, the obtained organic phase was washed twice with 200 mL of sodium bicarbonate aqueous solution, and then dried with magnesium sulfate. Then, the solvent was distilled off from the dried organic phase to obtain an oily liquid. Then, using a silica gel column chromatography for the oily liquid, the developing solvent was made into a mixture of hexane and ethyl acetate, and its mixing ratio (volume ratio) was changed from hexane / ethyl acetate = 4/1 to hexane / Ethyl acetate = 1/1 for purification to obtain the oxime compound INT-31 (8.51 g, 6.36 mmol). The structure of the resulting product was identified by NMR. ( ¹ H-NMR 300MHz heavy chloroform): 1.20-1.45 (m, 23H), 1.67 (quin., 2H), 2.39 (t, 2H), 3.02 ~ 3.23 (m, 4H), 7.23 ~ 7.30 (m, 4H ), 7.39 (d, 2H), 7.49 ~ 7.55 (m, 4H), 7.60 (t, 1H), 7.75 ~ 7.85 (m, 4H), 8.02 (d, 2H)

[Synthesis of INT-17] [Chemical Formula 29]

The precursor C in the above formula was synthesized by the method described in paragraph 0355 of Japanese Patent Table 2016-531926. Next, the "precursor C (5.01 g, 11.3 mmol)" was used instead of the "precursor B (6.00 g, 11.3 mmol)", and the oxime compound was obtained in the same manner as the synthesis of INT-31 described above. INT-17 (4.94g, 7.56mmol). The structure of the resulting product was identified by NMR. ( ¹ H-NMR 300MHz heavy chloroform): 0.90 (d, 6H), 1.20-1.70 (m, 26H), 2.39 (t, 2H), 2.66-2.89 (m, 2H), 7.30 ~ 8.08 (m, 13H)

[Synthesis of INT-26] [Chemical Formula 30]

The precursor D in the above formula was synthesized by the method described in paragraph 0368 of Japanese Patent Laid-Open No. 2009-191061. Then, the "precursor D (6.27g, 11.3mmol)" was used instead of the "precursor B (6.00g, 11.3mmol)", and the oxime compound was obtained in the same manner as the synthesis of INT-31 described above INT-26 (4.72g, 6.17mmol). The structure of the resulting product was identified by NMR. ( ¹ H-NMR 300MHz heavy chloroform): 1.19-1.44 (m, 23H), 1.49 (t, 3H), 1.70 (quin., 2H), 2.36 (s, 3H), 2.42 (t, 2H), 3.10 ~ 3.25 (m, 4H), 4.43 (q, 2H), 7.22-7.51 (m, 8H), 8.08 (dd, 2H), 8.33 (dd, 2H), 8.56 (d, 1H), 8.87 (d, 1H)

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

[Synthesis of polyfunctional thiol compound] [Synthesis of SH-16] [Chemical Formula 31]

<Synthesis Step of Intermediate 1> Add neopentaerythritol (PE) (13.5g, 99.2mmol) and N, N-dimethylacetamide (DMAc) (200g) to a three-necked flask under a nitrogen atmosphere at The mixture was obtained by stirring in a water bath at 20 ° C. Then, 2-bromoisobutyl amide bromide (100.3 g, 595 mmol) was added dropwise to the mixed liquid so that the temperature of the mixed liquid did not exceed 30 ° C, and the reaction liquid was obtained by stirring at room temperature for 2 hours. Then, the reaction solution was added little by little to 1 mol / L hydrochloric acid (350 g) to stop the reaction, thereby obtaining a solution. Then, ethyl acetate (500 g) was added to the solution, and liquid separation was performed to obtain an organic phase. Then, the organic phase was washed with saturated sodium bicarbonate water (250 g), water (250 g), and saturated brine (150 g), respectively. Then, after adding sodium sulfate to the washed organic phase, it was filtered to obtain a filtrate. Then, the filtrate was concentrated under reduced pressure to obtain Intermediate 1 (70.1 g, 95.7 mmol) in the above formula.

<Synthesis Step of Intermediate 2> Intermediate 1 (70.0g, 95.6mmol), DMAc (210g), and tetrabutylammonium bromide (TEAB) (12.8g, 61.2mmol) were added to a three-necked flask under an air environment. Stir in a water bath to obtain a mixed liquid. Then, potassium thioacetate (51.0 g, 446 mmol) was added to the mixed solution in 4 portions, and reacted at 50 ° C. for 4 hours to obtain a reaction solution. Then, ethyl acetate (310 g) and saturated aqueous sodium bicarbonate solution (380 g) were added to the reaction liquid, and liquid separation was performed to obtain an organic phase. Then, the organic phase was separated once with 1 mol / L hydrochloric acid (350 g) and twice with saturated brine (350 g), and the organic phase was washed. Then, sodium sulfate was added to the washed organic phase and filtered to obtain a filtrate. Then, the filtrate was concentrated under reduced pressure to obtain Intermediate 2 (65.8 g, 92.3 mmol) in the above formula.

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

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

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

In addition, the organic solvent was adjusted so that the final solid content of each curable composition became 28% by mass. In addition, for the organic solvent, the mass ratio in each curable composition was adjusted to be PGMEA (propylene glycol monomethyl ether acetate) / butyl acetate / cyclohexanone = 27/18/27 and used simultaneously.

In addition, the following shows compounds used in place of specific oxime compounds in the curable compositions of Comparative Examples (referred to as Comparative Compound 1 and Comparative Compound 2, in Table 5-2, they are represented as "CINT-1" and "CINT- 2 ".) The structure.

[Chemical Formula 32]

[Preparation of Colorant] In addition, each colorant used for preparing the curable composition was prepared by the following method.

(Titanium nitride-containing particles (TiN-1)) First, Ti particles (TC-200, manufactured by TOHO TECHNICAL SERVICE CO., LTD.) Were plasma-treated in Ar gas to thereby form Ti nanoparticles . After the plasma-treated Ti nanoparticles were allowed to stand in an Ar gas environment under an O ₂ concentration of 50 ppm or less and 30 ° C. for 24 hours, they were introduced into the Ar environment so that the O ₂ concentration became 100 ppm. In the state of O ₂ gas, it was allowed to stand at 30 ° C for 24 hours (pretreatment of Ti particles). Thereafter, using a TTSP separator manufactured by Hosokawa Micron Corporation, the obtained Ti nanoparticles were classified under the condition that the yield became 10%, thereby obtaining Ti particle powder. The primary particle size of the obtained powder was observed by TEM, and the average particle size of 100 particles was obtained by arithmetic average. The result was 120 nm. Titanium nitride-containing particles TiN-1 were manufactured using the apparatus for manufacturing black composite fine particles described in FIG. 1 according to International Publication No. 2010/147098. Specifically, in the black composite particle manufacturing apparatus, a high-frequency voltage of about 4 MHz and about 80 kVA is applied to the high-frequency oscillation coil of the plasma torch, and argon gas is supplied as a plasma gas from the plasma gas supply source at 50 L / min The mixed gas of nitrogen 50L / min produced argon-nitrogen thermal plasma flame in the plasma torch. In addition, a carrier gas of 10 L / min was supplied from the 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) are mixed so that the respective mass ratio becomes Ti / Fe / Si = residual amount / 0.05 /0.05, and together with the argon as the carrier gas is supplied to the hot plasma flame in the plasma torch, so that it evaporates in the hot plasma flame, so as to be highly dispersed in the gas phase state. In addition, nitrogen was used as the gas supplied into the chamber by the gas supply device. The flow velocity in the chamber at this time was set to 5 m / sec, and the supply amount was set to 1,000 L / min. In addition, the pressure in the cyclone was set to 50 kPa, and the supply speed of each raw material from the chamber to the cyclone was set to 10 m / s (average value). In this way, titanium nitride-containing particles TiN-1 are obtained.

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

Regarding X-ray diffraction of titanium nitride-containing particles TiN-1, a powder sample was placed in an aluminum standard sample holder, and was performed by wide-angle X-ray diffraction method (manufactured by Rigaku Corporation, trade name "RU-200R") Measured. As measurement conditions, the X-ray source is CuKα rays, the output is 50kV / 200mA, the slit system is 1 ° -1 ° -0.15mm-0.45mm, and the measurement step (2θ) is 0.02 ° , Set the scanning speed to 2 ° / min. Then, the diffraction angle of the peak derived from the TiN (200) plane observed near the diffraction angle 2θ (42.6 °) was measured. Furthermore, based on the half-width of the peak originating from the (200) plane, the size of the crystallites constituting the particles was obtained using Scherrer's formula. As a result, the diffraction angle of the peak was 42.62 °, and the crystallite size was 10 nm. In addition, no X-ray diffraction peak caused by TiO _{2 was} observed at all.

(TiN-2 particles containing titanium nitride) As Ti particles, instead of "TC-200" manufactured by TOHO TECHNICAL SERVICE CO., LTD., Use "578347" manufactured by Sigma-Aldrich Co. LLC. The TiN-containing particles TiN-2 were obtained in the same manner as TiN-1 except that Fe powder and Si powder were mixed so that Ti / Fe / Si = balance / 0.5 / 1. In addition, the diffraction angle of the peak measured by X-ray diffraction was 42.81 °, and the crystallite size was 12 nm.

(TiN-3 particles containing titanium nitride) Fe powder and Si powder are mixed in such a way that the respective mass ratio becomes Ti / Fe / Si = balance / 1/2, except that it is the same as TiN-1 Titanium nitride-containing particles TiN-3 are obtained. In addition, the diffraction angle of the peak measured by X-ray diffraction was 43.1 °, and the crystallite size was 12 nm.

(Preparation of Fe atom-containing niobium nitride-containing particles (NbN)) The Fe atom-containing niobium nitride-containing particles were produced by the following method. First, niobium (powder) <100-325mesh> manufactured by Mitsuwa Chemicals Co., Ltd. was prepared as a raw material (hereinafter, also referred to as "metal raw material powder"). Next, by subjecting the above-mentioned metal raw material powder to plasma treatment in Ar gas (processing conditions based on the following plasma treatment (1)), Nb nanoparticles were formed.

･ Plasma treatment (1) Plasma treatment (1) was performed by the following method. Plasma treatment (1) was carried out under the following conditions using the device according to the above black composite particle manufacturing device. ･ High-frequency voltage applied to the coil for high-frequency oscillation: frequency of about 4MHz, voltage of about 80kVA ･ plasma gas: argon (supply volume 100L / min) ･ carrier gas: argon (supply volume 10L / min) ･ chamber Environment: Argon gas (supply volume 1,000L / min, flow rate in the chamber 5m / sec) ･ Inner environment of cyclone separator: Argon gas, internal pressure: 50kPa ･ Supply speed of material supplied from the chamber to the cyclone separator: 10m / s (average value)

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

Next, the Nb nanoparticles and Fe nanoparticles obtained as described above were mixed to obtain a raw metal powder. Regarding this raw material metal powder, by performing plasma treatment in nitrogen (processing conditions based on the following plasma treatment (2)), niobium nitride-containing particles are obtained.

･ Plasma treatment (2) Plasma treatment (2) was performed by the following method. In addition, the equipment used is the same as the plasma treatment (1). ･ High-frequency voltage applied to the coil for high-frequency oscillation: frequency of about 4MHz, voltage of about 80kVA ･ plasma gas: argon and nitrogen (supply volume of 50L / min) ･ carrier gas: nitrogen (supply volume of 10L / min) ･ Environment in the chamber: nitrogen (supply volume 1,000L / min, flow rate in the chamber 5m / sec) ･ Inner environment of the cyclone separator: nitrogen, internal pressure 50kPa ･ Supply speed of material supplied from the chamber to the cyclone: 10m / s (average value)

The particles after the plasma treatment (2) were completed, Ar gas was used, and nitrogen gas at 20 ° C was introduced under the condition that the relative humidity in the atmosphere was 95% by using a split-type humidity supply device SRH manufactured by NIHON SHINTECH CO., LTD. , And stood still for 24 hours. Then, using a TTSP separator manufactured by Hosokawa Micron Corporation, the obtained particles were classified under the condition that the yield became 10%, thereby obtaining niobium nitride-containing particles (NbN). In addition, nitrogen gas was supplied to the separator. For the obtained niobium nitride-containing particles, the content of iron (Fe) atoms was measured by ICP emission spectrometry, and it was 50 mass ppm.

(Preparation of vanadium nitride-containing particles (VN) containing Fe atoms) In the production of niobium nitride-containing particles containing Fe atoms, instead of niobium (powder) <100-325mesh> manufactured by Mitsuwa Chemicals Co., Ltd., In addition to the use of metal vanadium powder VHO manufactured by TAIYO KOKO Co., LTD., Vanadium nitride-containing particles (VN) containing Fe atoms were produced in the same manner. For the obtained vanadium nitride-containing particles, the content of iron (Fe) atoms was measured by ICP emission spectrometry, and the result was 50 mass ppm.

In addition, the coloring agents in Table 5 other than the above are coloring agents or mixtures of coloring agents described in Table 4 below. [Table 4]

In addition, the structures of Compound SQ-23 and Compound A-52 in Table 4 are shown below. ･ Compound SQ-23 [Chemical Formula 33]

･ Compound A-52 (In the formula, Ph represents phenyl.) [Chemical Formula 34]

[Dispersant] As the dispersant, Dispersant A of the following structure was used. The numerical value described in each structural unit represents the mass% of each structural unit relative to the total structural unit. [Chemical Formula 35]

[Binder Resin] As the binder resin, resin A of the following structure was used. In addition, in the formula of resin A, each abbreviation represents as follows. The numerical value described in each structural unit represents the mass% of each structural unit relative to the total structural unit. In addition, resin A corresponds to an alkali-soluble resin. ･ BzMA: benzyl methacrylate ･ MMA: methyl methacrylate [Chemical formula 36]

[Polymerizable Compound] As the polymerizable compound, the polymerizable compound M1 and the polymerizable compound M2 were used. ･ The structure of the polymerizable compound M1 (dipentaerythritol hexaacrylate) is as shown in the following formula (manufactured by Nippon Kayaku Co., Ltd., trade name "KAYARAD"). [Chemical Formula 37] ･ Polymer compound M2: PET-30 (neopentaerythritol triacrylate, manufactured by Nippon Kayaku Co., Ltd.)

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

[Evaluation of Curable Composition] [Pattern Shape] Each curable composition was sealed in a 100 mL capacity Bloom bottle and stored in a thermostat at 60 ° C. for 7 days (forced heating time). Then, using various curable compositions after forced heating over time, on a Si substrate (equivalent to a support.) Whose surface was treated with SiO ₂ , the rotation speed was adjusted so that the film thickness after drying became 1.5 μm. A coating film (hardening composition layer) was formed by spin coating. Then, the formed substrate with a coating film was placed on a hot plate, and heat-treated (pre-baked) at 100 ° C for 2 minutes to dry it. Then, for the pre-baked substrate with a coating film (curable composition layer), an i-ray stepper (FPA3000i5 + manufactured by Canon Inc.) was used, and a line pattern with a length of 200 μm × width 20 μm was formed The photomask was exposed (negative) to the coating film. Then, using Coater Developer ACT8 manufactured by Tokyo Electron Limited, and using tetramethylammonium hydroxide as a developing solution, the exposed coating film was subjected to spin immersion development for 30 seconds, and then sprayed with pure water for 20 seconds. A rinse film is obtained by washing to obtain a pattern-shaped cured film. Then, the pattern-shaped cured film was post-baked (temperature: 220 ° C., time: 300 seconds). The pattern shape of the cured film after post-baking was measured using a length measuring SEM (Scanning Electron Microscope). Specifically, the film thickness at the end of the line pattern and the film thickness at the center were measured, the ratio (the film thickness at the end of the pattern / the film thickness at the center) was calculated, and the evaluation was performed based on the following criteria. In addition, evaluation "2" or more is a practical range. The results are shown in Table 5.・ 7: The ratio exceeds 0.98 to 1.00 or less, and there is no difference in film thickness between the center and the end of the pattern observed by SEM.・ 6: The ratio exceeds 0.96 and 0.98 or less, and a slight difference in film thickness between the center and the end of the pattern can be observed.・ 5: The ratio exceeds 0.94 and 0.96 or less, and a difference in film thickness between the center and the end of the pattern can be observed.・ 4: The ratio exceeds 0.92 to 0.94, and the film thickness at the end is thin and slightly deformed, but it is a level that is practically not a problem.・ 3: The ratio exceeds 0.90 and 0.92 or less, and the film thickness at the end is thin and deformed, but it is a level that is practically not a problem.・ 2: The ratio exceeds 0.80 to 0.90 and the film thickness at the end is thin, but it is a practical level.・ 1: The ratio is 0.80 or less, and the film thickness at the end is thin, which is outside the allowable range.

[Development residue suppression performance] Using the same method as above, a substrate with a coating film was produced using each constituent composition. After that, development was performed by the same method as described above, and the number of development residues on the Si substrate was measured. Specifically, when the coating film was exposed to light, the number of residues in the area (unexposed portion) that was not irradiated with light was observed by SEM (magnification: 20,000 times), and the development residue suppression performance was evaluated. The evaluation criteria are as follows. The results are shown in Table 5. A: No residue was observed at all in the unexposed area. B: One or more and three or less residues were observed on the unexposed area of 1.0 μm square. C: 4 or more and 7 or less residues were observed on the unexposed area of 1.0 μm square. D: 8 or more and 10 or less residues were observed on the unexposed part of 1.0 μm square. E: Eleven or more residues were observed on the unexposed area of 1.0 μm square. In practice, "D" or higher is preferable, and "A" and "B" are evaluated as having particularly excellent performance.

･ In Table 5, the "content" of the specific oxime compound (A) and the polyfunctional thiol compound (B) refers to the specific oxime compound (A) and (A) when the total solid content of the curable composition is set to 100% by mass Each content (mass%) of the polyfunctional thiol compound (B). ･ In Table 5, “A / B” refers to the content mass ratio of the content of the specific oxime compound (A) to the content of the polyfunctional thiol compound (B) in the curable composition. ･ In Table 5, CP-1 to CP-8 represent the color pigments 1 to 8 in Table 4, respectively, as the type of colorant. [Table 5-1]

[Table 5-2]

According to the results shown in Table 5, the curable compositions of the examples have the effects of the present invention. On the other hand, the curable composition of the comparative example does not have the effect of the present invention. Compared with the curable composition of Example 8, the curable composition of Example 1 containing the specific oxime compound having R ¹ of formula (1) having a carbon number of 13 or more, the pattern shape of the resulting cured film is more excellent . Compared with the curable composition of Example 4 (both R ²⁴ and R ²⁵ are first-order thiol compounds of a hydrogen atom), R ²⁴ containing the formula (2) is a polyfunctional thiol compound other than a hydrogen atom (The second-grade thiol compound) The curable composition of Example 3 has more excellent development residue suppression performance. In addition, the curable composition of Example 35 containing both R ²⁴ and R ²⁵ as polyfunctional thiol compounds (third-level thiol compounds) other than hydrogen atoms has more excellent development residue suppression performance. In addition, compared to the curable composition of Example 46 (n is 2), for the curable compositions of Example 43 and Example 47 in which n of formula (2) is 3 to 10, the pattern of the resulting cured film The shape is more excellent. Compared with the curable compositions of Example 10 and Example 13, the curable composition of Example 12 with respect to the content of the oxime compound relative to the content of the polyfunctional thiol compound in the mass ratio of 4 to 10 was obtained. The pattern shape of the cured film is more excellent. Compared with the curable composition of Example 20, R ¹⁵ of the formula (1) is a linear alkyl group having 13 or more carbon atoms or a group represented by * -L ¹¹ -R ¹¹ In the curable compositions of 19 and Examples 21 to 22, the resulting cured film has a more excellent pattern shape.

[Example 71] Instead of TiN-1, TiN-1 and carbon black (trade name "COLOR BLACK S170", manufactured by Degussa Corporation, with an average primary particle diameter of 17 nm, a BET specific surface area of 200 m ² / g, and borrowed Carbon black produced by the gas black method) was evaluated in the same manner as in Example 43 except that the solid content mass ratio was 7: 3, and as a result, the same effects as in Example 43 were obtained.

[Example 72] A curable composition was prepared and evaluated in the same manner as in Example 43 except that no surfactant was used. As a result, the same results as in Example 43 were obtained.

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

101‧‧‧Support

102, 401‧‧‧ hardening composition layer

103‧‧‧mask

201, 501‧‧‧ hardened film

301,601‧‧‧hardened film after baking

700‧‧‧Solid camera device

701‧‧‧Solid imaging element

702‧‧‧Camera Department

703‧‧‧ Cover glass

704‧‧‧ spacer

705‧‧‧Multilayer substrate

706‧‧‧ Wafer substrate

707‧‧‧ circuit board

708‧‧‧electrode pad

709‧‧‧External connection terminal

710‧‧‧through electrode

711‧‧‧Lens layer

712‧‧‧Lens material

713‧‧‧Support

714,715‧‧‧hardened film

801‧‧‧Light receiving element

802‧‧‧Color filter

803‧‧‧Microlens

804‧‧‧ substrate

805b‧‧‧blue pixels

805r‧‧‧Red pixel

805g‧‧‧green pixels

805bm‧‧‧Black Matrix

806‧‧‧p hole layer

807‧‧‧Read gate

808‧‧‧Vertical transmission path

809‧‧‧Component separation area

810‧‧‧Gate insulating film

811‧‧‧Vertical transmission electrode

812‧‧‧hardened film

813、814‧‧‧Insulating film

815‧‧‧flat film

900‧‧‧Infrared sensor

910‧‧‧Solid image sensor

911‧‧‧Infrared absorption filter

912‧‧‧Color filter

913‧‧‧Infrared transmission filter

914‧‧‧Resin film

915‧‧‧Microlens

916‧‧‧flat film

hν‧‧‧incident light

FIG. 1 is a cross-sectional view schematically showing a step of manufacturing a cured film using a curable composition containing no polyfunctional thiol compound for each step. FIG. 2 is a cross-sectional view schematically showing a step of manufacturing a cured film using a curable composition containing no polyfunctional thiol compound for each step. FIG. 3 is a cross-sectional view schematically showing a step of manufacturing a cured film using a curable composition containing no polyfunctional thiol compound for each step. Fig. 4 is a cross-sectional view schematically showing a step of manufacturing a cured film using a curable composition containing a polyfunctional thiol compound and not containing a specific oxime compound for each step. FIG. 5 is a cross-sectional view schematically showing a step of manufacturing a cured film using a curable composition containing a polyfunctional thiol compound and not containing a specific oxime compound for each step. FIG. 6 is a cross-sectional view schematically showing a step of manufacturing a cured film using a curable composition containing a polyfunctional thiol compound and not containing a specific oxime compound for each step. 7 is a schematic cross-sectional view showing a solid-state imaging device according to an embodiment of the present invention. FIG. 8 is an enlarged schematic cross-sectional view of the imaging unit of FIG. 7. 9 is a schematic cross-sectional view showing a configuration example of an infrared sensor according to an embodiment of the present invention.

Claims (16)

A curable composition comprising a photopolymerization initiator, a polyfunctional thiol compound, a polymerizable compound, and a coloring agent, the curable composition is characterized in that the photopolymerization initiator is represented by the following formula (1) Represented by the oxime compound, In formula (1), R ¹ represents a hydrocarbon group having 8 or more carbon atoms which may contain hetero atoms, R ² represents an alkyl group or an aryl group, X ² represents a single bond or a divalent linking group, R ³ represents an aryl group, X ³ Represents a single bond or carbonyl. The curable composition as described in item 1 of the patent application, wherein the carbon number of R ¹ in the aforementioned formula (1) is 13 or more. The curable composition according to item 1 or 2 of the patent application range, wherein the content ratio of the content of the oxime compound to the content of the multifunctional thiol compound in the curable composition is 1 to 10 . The curable composition as described in item 1 or 2 of the patent application range, wherein the content ratio of the content of the oxime compound to the content of the polyfunctional thiol compound in the curable composition is 4 to 10 . The curable composition as described in item 1 or 2 of the patent application, wherein the polyfunctional thiol compound is a compound represented by the following formula (2), In formula (2), R ²⁴ and R ²⁵ independently represent a hydrogen atom, an alkyl group, an aryl group, -C (= O) -R ²³ , -C (= O) -OR ²³ or -C (= O) -NH-R ²³ , L ²¹ represents an n-valent organic linking group, n represents an integer from 2 to 10, M ²¹ represents a single bond or -O-, -S-, -N (R ²³ )-, -C (= O) -O-, -OC (= O) -O-, -C (= O) -NH-, -C (= O)-, alkylene, or a combination of two or more of them R ²³ represents an alkyl group or an aryl group, and a plurality of R ²⁴ , R ^25, and M ²¹ may be the same or different, and when there are a plurality of R ²³ , they may be the same or different. The curable composition as described in item 5 of the patent application scope, wherein in the aforementioned formula (2), R ²⁴ and R ²⁵ are each independently an alkyl group or -C (= O) -OR ²³ , and M ²¹ is -C (= O) -O-, n is an integer of 3 ~ 10. The hardenable composition according to item 1 or 2 of the patent application, wherein the colorant includes an organic pigment. The hardenable composition as described in item 1 or 2 of the patent application, wherein the colorant includes an inorganic pigment. A cured film obtained by curing the curable composition described in any one of claims 1 to 8 of the patent application. A color filter containing the cured film described in item 9 of the patent application. A light-shielding film containing the cured film described in item 9 of the patent application. A solid-state imaging element containing the cured film described in item 9 of the patent application. An image display device containing the cured film described in item 9 of the patent application. A method for manufacturing a cured film, comprising: a step of forming a layer of a curable composition, using the curable composition described in any one of claims 1 to 8 to form a curable composition on a support Layer; and an exposure step to expose the aforementioned curable composition layer. The method for manufacturing a cured film as described in item 14 of the patent application range, wherein the step of forming the curable composition layer is to apply the curable composition on the support and form the curable composition on the support Steps of the physical layer. The method for manufacturing a cured film as described in item 14 or item 15 of the scope of the patent application further includes a developing step to develop the exposed curable composition layer.