TWI774679B - Curable composition, cured film, color filter, light-shielding film, solid-state imaging element, image display device, manufacturing method of cured film, and polyfunctional thiol compound - Google Patents

Abstract

The present invention provides 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 capable of obtaining a cured film having excellent exposure sensitivity and excellent adhesion to a support. A method for producing a film and a polyfunctional thiol compound. The curable composition contains a polyfunctional thiol compound, a polymerizable compound, and a photopolymerization initiator, and the polyfunctional thiol compound contains two or more thiol groups and interactive groups different from the thiol groups.

Description

Curable composition, cured film, color filter, light-shielding film, solid-state imaging element, image display device, manufacturing method of cured film, and polyfunctional thiol compound

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

A color filter used in an image display device is provided with a light-shielding film called a black matrix for the purpose of shielding light between colored pixels, improving contrast, and the like. In addition, in the solid-state imaging element, a light shielding film is provided in order to prevent noise generation, improve image quality, and the like. Currently, small and thin imaging units are mounted on portable terminals of electronic devices such as cellular phones and PDAs (Personal Digital Assistants). These imaging units usually include solid-state imaging elements such as CCD (Charge Coupled Device) image sensors and CMOS (Complementary Metal-Oxide Semiconductor) image sensors, and are used for solid-state imaging. A lens for forming a subject image on the imaging element.

Patent Document 1 describes: "A photosensitive resin composition for forming partition walls separating pixels in an image display device, the photosensitive resin composition containing: (A) as a component, a carboxyl group in the molecule. (B) a photopolymerizable compound as an ingredient; (C) a photopolymerization initiator as an ingredient; (D) a compound having a mercapto group as an ingredient; and (E) a black pigment as an ingredient. ". [Prior Art Literature] [Patent Literature]

[Patent Document 1]: Japanese Patent Laid-Open No. 2014-41188

The inventors of the present invention applied the photosensitive resin composition described in Patent Document 1 on a support, and exposed the obtained photosensitive resin composition layer to produce a cured film. As a result, they found that there is room for further improvement in exposure sensitivity. . Specifically, in the photosensitive resin composition described in Patent Document 1, it has been found that if a finer pattern shape is to be obtained, the energy required for exposure becomes large. And as a result of examining the cured film obtained by the said method, this inventor discovered that there exists room for further improvement of the adhesiveness with a support body (henceforth a "substrate").

The subject of this invention is to provide the curable composition which can obtain the cured film which has the outstanding exposure sensitivity and the outstanding adhesiveness with a support. Moreover, the subject of this invention is to provide the manufacturing method of a cured film, a color filter, a light-shielding film, a solid-state imaging element, an image display device, a cured film, and a polyfunctional thiol compound.

As a result of earnestly examining in order to achieve the above-mentioned problem, the present inventors found that a curable composition containing a predetermined polyfunctional thiol compound can solve the above-mentioned problem, and completed the present invention. That is, it was found that the above-mentioned subject can be achieved by the following configuration.

[1] A curable composition containing a polyfunctional thiol compound, a polymerizable compound, and a photopolymerization initiator, wherein the polyfunctional thiol compound contains two or more thiol groups and different interactions with the thiol groups sex group. [2] The curable composition according to [1], wherein the polyfunctional thiol compound is a compound represented by formula (1). [3] The curable composition according to [1] or [2], wherein the polyfunctional thiol compound is a compound represented by formula (2). [4] The curable composition according to [2] or [3], wherein m is an integer of 3-14. [5] The curable composition according to any one of [1] to [4], wherein the interactive group different from the thiol group is selected from the group consisting of a hydroxyl group, an amino group, a pyridyl group, and a pyridinium group , ammonium group, phosphonium group, carboxylic acid group or its salt, phosphoric acid group or its salt, sulfonic acid group or its salt, aryl group, -Si(R ^X ) _p (R ^Y ) _3-p and -(OR ^A ) At least one of the group _q - ^RZ . In addition, p represents an integer of 1 to 3, R ^X represents a hydrolyzable group, and R ^Y represents a monovalent organic group other than a hydrolyzable group. The p pieces of R ^X and the 3-p pieces of R ^Y may be respectively the same or may be the same. different. In addition, R ^Z represents a hydrogen atom, an alkyl group or an alkoxy group, q represents an integer of 1 to 4, and R ^A represents an alkylene group having 1 to 15 carbon atoms. [6] The curable composition according to any one of [1] to [5], wherein the interactive group different from the thiol group is selected from the group consisting of a hydroxyl group, an amino group, a pyridyl group, and a pyridinium group , at least one of the group of ammonium group, phosphonium group, carboxylic acid group or its salt, phosphoric acid group or its salt, and sulfonic acid group or its salt. [7] The curable composition according to any one of [1] to [6], wherein the interactive group different from the thiol group is selected from the group consisting of a hydroxyl group, an amino group, a pyridyl group, and a carboxylic acid group or at least one of the group of a salt thereof, a phosphoric acid group or a salt thereof, and a sulfonic acid group or a salt thereof. [8] The curable composition according to any one of [1] to [7], which further contains a colorant. [9] The curable composition according to [8], wherein the colorant contains a black pigment. [10] The curable composition according to any one of [1] to [9], wherein the photopolymerization initiator is an oxime compound. [11] A cured film obtained by curing the curable composition according to any one of [1] to [10]. [12] A color filter comprising the cured film described in [11]. [13] A light-shielding film comprising the cured film described in [11]. [14] A solid-state imaging element comprising the cured film described in [11]. [15] An image display device comprising the cured film described in [11]. [16] A method for producing a cured film, comprising: a process for forming a curable composition layer, wherein the curable composition is formed on a support using the curable composition according to any one of [1] to [10] layer; and an exposure process for exposing the curable composition layer. [17] The method for producing a cured film as described in [16], wherein the process of forming the curable composition layer comprises the process of directly coating the curable composition on the support, thereby forming the curable composition layer on the support . [18] The method for producing a cured film according to [16] or [17], further comprising: a developing process for developing the exposed curable composition layer; and a cleaning process for developing the developed curable composition The material layer is cleaned. [19] A polyfunctional thiol compound containing two or more thiol groups and an interactive group different from the thiol group. [20] The polyfunctional thiol compound according to [19], which is a compound represented by formula (1). [21] The polyfunctional thiol compound according to [19] or [20], which is a compound represented by formula (2). [22] The polyfunctional thiol compound according to [20] or [21], wherein m is an integer of 3-14. [23] The polyfunctional thiol compound according to any one of [19] to [22], wherein the interactive group different from the thiol group is selected from the group consisting of hydroxyl group, amino group, pyridyl group, pyridinium group group, ammonium group, phosphonium group, carboxylic acid group or its salt, phosphoric acid group or its salt, sulfonic acid group or its salt, aryl group, -Si(R ^X ) _p (R ^Y ) _3-p and -(OR ^A ) at least one of the group _q - ^RZ . In addition, p represents an integer of 1 to 3, R ^X represents a hydrolyzable group, and R ^Y represents a monovalent organic group other than a hydrolyzable group. The p pieces of R ^X and the 3-p pieces of R ^Y may be respectively the same or may be the same. different. In addition, R ^Z represents a hydrogen atom, an alkyl group or an alkoxy group, q represents an integer of 1 to 4, and R ^A represents an alkylene group having 1 to 15 carbon atoms. [24] The polyfunctional thiol compound according to any one of [19] to [23], wherein the interactive group different from the thiol group is selected from the group consisting of hydroxyl group, amino group, pyridyl group, pyridinium group at least one of the group consisting of a group, an ammonium group, a phosphonium group, a carboxylic acid group or a salt thereof, a phosphoric acid group or a salt thereof, and a sulfonic acid group or a salt thereof. [Inventive effect]

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

Hereinafter, the present invention will be described in detail. The following description may be based on representative embodiments of the present invention, but the present invention is not limited to such embodiments. In this specification, the numerical range represented by "-" shows the range which includes the numerical value described before and after "-" as a lower limit and an upper limit. In the notation of groups (atomic groups) in the present specification, the notation that is not substituted and unsubstituted includes those that do not contain a substituent and those that contain a substituent. For example, "alkyl" includes not only unsubstituted alkyl groups (unsubstituted alkyl groups), but also substituted alkyl groups (substituted alkyl groups). The "actinic ray" or "radiation" in this specification refers to, for example, the bright line spectrum of a mercury lamp, extreme ultraviolet rays represented by excimer lasers, extreme ultraviolet rays (EUV: Extreme ultraviolet lithography light), X-rays, and electron beams. In addition, in this specification, "light" means actinic rays and radiation. Unless otherwise specified, the term "exposure" in this specification includes not only exposure using the apparent spectrum of mercury lamps and far-ultraviolet rays represented by excimer lasers, X-rays, and EUV light, but also exposure using electron beams and ion beams. Depiction by particle beam. 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 group" means an acryl group and a methacryloyl group. In this specification, "(meth)acrylamide" means acrylamide and methacrylamide. In this specification, "monomer" and "monomer" have the same meaning. Monomers are distinguished from oligomers and polymers, and refer to compounds having a weight average molecular weight of 2,000 or less. In this specification, a polymerizable compound means a compound containing a polymerizable group, and may be a monomer or a polymer. A polymerizable group refers to a group that participates in a polymerization reaction. [Curable composition] The curable composition contains a polyfunctional thiol compound, a polymerizable compound and a photopolymerization initiator, wherein the polyfunctional thiol compound contains two or more thiol groups and different interactions with the thiol groups sex group.

The inventors of the present invention found that, by forming a curable composition layer on a support using the curable composition containing a thiol compound described in Patent Document 1, and exposing the curable composition layer to light, a fine In the cured film of the pattern shape, there is a problem that the exposure amount has to be increased. This is presumably because, if the pattern shape is to be made finer, the opening of the mask becomes narrow, and as a result, the amount of light irradiated to the curable composition layer is further reduced. That is, since the amount of light reaching the bottom of the curable composition decreases, it is presumed that the bottom of the curable composition layer is less likely to be cured. In this case, by increasing the exposure amount, the amount of light reaching the bottom of the curable composition layer can be increased. On the other hand, when the exposure amount is increased, the light diffracted at the opening of the mask, that is, so-called "leakage" tends to increase. part), the part that should be masked is exposed, resulting in the deterioration of the pattern shape.

Generally, when a curable composition layer is formed on a support using a curable composition containing a photopolymerization initiator, and the curable composition layer is exposed to light, a radical reaction is initiated by the photopolymerization initiator . In this case, radicals generated by the photopolymerization initiator may react with oxygen in the curable composition layer, thereby generating peroxy radicals. Since the peroxy radical does not have the effect of advancing the reaction, the polymerization reaction may be stopped in some cases.

In one aspect of the present invention, the curable composition contains a polyfunctional thiol compound containing two or more thiol groups. Since the thiol group generates sulfur radicals that are not easily deactivated by polymerization by supplying hydrogen to the peroxy radicals, the polymerization reaction continues. Furthermore, the polyfunctional thiol compound contains an interactive group different from the thiol group. The interactive group interacts with the support (or, when the support is provided with an overcoat, with the molecules that make up the overcoat). Therefore, it is presumed that the polyfunctional thiol compound tends to be concentrated in the portion (ie, the bottom) closer to the support in the curable composition layer formed using the above curable composition. It is presumed that if the polyfunctional thiol compound is concentrated on the bottom of the curable composition layer with a relatively small amount of light reaching the curable composition layer on the curable composition layer, the function of the thiol group is more effectively exerted. That is, it is presumed that with a smaller exposure amount, the amount of light reaching the bottom of the curable composition layer is small, but since the polyfunctional thiol compound tends to be concentrated at the bottom, it is easy to reach the bottom of the curable composition layer. Sulfur radicals are generated, so that even if the amount of light is low, hardening is sufficiently advanced to the bottom. Furthermore, it is presumed that in the cured film, the interaction with the support becomes stronger because the interactive group is concentrated in the part (that is, the bottom) closer to the support, and thus it has excellent performance with the support. The adhesive ones. Hereinafter, components contained in the curable composition of the present invention will be described.

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

The number of thiol groups contained in the polyfunctional thiol compound is 2 or more, preferably 3 or more, and more preferably 4 or more. The upper limit of the number of thiol groups contained in the polyfunctional thiol compound is not particularly limited, but is generally preferably 30 or less, more preferably 20 or less, and further preferably 14 or less.

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

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

As content of a polyfunctional thiol compound, 0.5-10 mass % is preferable with respect to the total solid content of a curable composition. When the content of the polyfunctional thiol compound is 0.5 to 10% by mass, the exposure sensitivity is further excellent. A polyfunctional thiol compound may be used individually by 1 type, and may use 2 or more types together. When two or more types of polyfunctional thiol compounds are used at the same time, the total amount thereof is preferably within the above-mentioned range.

<Preferable state 1 of the polyfunctional thiol compound> As the polyfunctional thiol compound, a compound represented by the following formula (1) is preferable. [Chemical formula 1]

In formula (1), L ¹ and L ² each independently represent a divalent linking group. m represents an integer of 2 to 14, preferably an integer of 3 to 14, more preferably 3 to 6. When m is an integer of 3 or more, the curable composition has more excellent exposure sensitivity. n represents an integer of 1-15. L ³ represents an m+n-valent linking group, and R ¹ represents an interactive group different from a thiol group. In addition, L ¹ and L ² may be the same or different from each other, and the m pieces of L ¹ , the n pieces of L ² , and the n pieces of R ¹ may be respectively the same or different.

Examples of the divalent linking group of L ¹ include a divalent aliphatic hydrocarbon group (preferably having 1 to 8 carbon atoms), a divalent aromatic hydrocarbon group (preferably having 6 to 12 carbon atoms), -O -, -S-, -N(R ⁴ )-(R ⁴ : 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-, -N(R)-(R: alkyl) or groups obtained by combining these (for example, alkyleneoxy, alkyleneoxycarbonyl and alkylene carbonyloxy, etc.), etc.

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

Examples of the m+n-valent linking group of L ³ include an isocyanuric ring having three trimethylolpropane residues, -(CH ₂ ) _k - (k represents, for example, an integer of 2 to 6.) Trivalent linking groups such as neopentaerythritol residues; tetravalent linking groups or pentavalent linking groups such as neopentaerythritol residues; m+n is 3 or more, preferably 4 or more. m+n is 29 or less, preferably 10 or less.

Examples of the m+n-valent linking group of L ³ include a group represented by any one of the following formulae (A) to (D) or a group obtained by combining these. [Chemical formula 2]

In formulas (A) to (D), L ⁴ represents a trivalent group. T ³ represents a single bond or a divalent linking group, and three T ^3s may be the same or different from each other. L ⁵ represents a tetravalent group. T ⁴ represents a single bond or a divalent linking group, and four T ^4s may be the same or different from each other. L ⁶ represents a pentavalent group. T ⁵ represents a single bond or a divalent linking group, and five T ^5s may be the same or different from each other. L ⁷ represents a hexavalent group. T ⁶ represents a single bond or a divalent linking group, and six T ^6s may be the same 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 the above-mentioned L ¹ .

As the m+n-valent linking group of L ³ , for example, groups represented by the following formulae (E) to (J) or groups obtained by combining these are preferable. [Chemical formula 3]

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

L ³ may be a group represented by the following formulae (K) to (O) or a group obtained by combining these. In the formula, * represents the bonding position. [Chemical formula 4]

In the formula (1), R ¹ is the same as the state of the interacting group other than the thiol group already explained. Among them, from the viewpoint that the cured film has more excellent adhesion to the support, the interactive group different from the thiol group is selected from the group consisting of a hydroxyl group, an amino group, a pyridyl group, a pyridinium group, an ammonium group , phosphonium group, carboxylic acid group or its salt, phosphoric acid group or its salt, sulfonic acid group or its salt, aryl group, -Si(R ^X ) _p (R ^Y ) _3-p (hereinafter, also referred to as "Si group".) and -(OR ^A ) _q -R ^Z is preferably at least one kind selected from the group consisting of hydroxyl group, amino group, pyridyl group, pyridinium group, ammonium group, phosphonium group, carboxyl group More preferably, at least one of the group of acid group or its salt, phosphoric acid group or its salt, and sulfonic acid group or its salt is selected from the group consisting of hydroxyl group, amine group, pyridyl group, carboxylic acid group or its salt, phosphoric acid group At least one kind selected from the group of a salt thereof and a sulfonic acid group or a salt thereof is further preferable. Although the mechanism by which the interactive group different from the thiol group is the above-mentioned functional group, the cured film has more excellent adhesion to the support is not clear, but the present inventors speculate as follows. That is, it is assumed that interactions (non-bonding intermolecular forces) can be roughly classified into van der Waals interactions, π-π stacking, hydrogen-π bonding, and electrostatic interactions. Or hydrogen bonding, roughly in this order, with "hydrogen bonding" being the strongest, followed by "electrostatic interactions" being stronger. Among them, for example, the hydrogen-π bond, which is the bond between the π electron of the phenyl group and the hydrogen of the OH, is considered to be weaker than the above two, and it is presumed that the above effect can be obtained. In addition, the mechanism for obtaining the effect of the present invention is not limited to the above-mentioned speculation. In addition, the above-mentioned amine group includes a primary amine group (NH ₂ -), a secondary amine group (NR _a H-), and a tertiary amine group (NR _a R _a -). R _a contained in the secondary amino group and the tertiary amino group is not particularly limited as long as it is a monovalent organic group, and examples thereof include hydrocarbon groups (eg, alkyl groups).

In the above -Si(R ^X ) _p (R ^Y ) _3-p , R ^X represents a hydrolyzable group. In this specification, the hydrolyzable group refers to a group which is directly bonded to a silicon atom (Si) and can undergo a hydrolysis reaction.

R ^Y represents a monovalent organic group. However, the above-mentioned hydrolyzable group is removed from the above-mentioned organic group. The monovalent organic group may be any organic group other than a hydrolyzable group, and examples thereof include an alkyl group, an alkenyl group, an aryl group, an alkylcarbonyl group, a cycloalkylcarbonyl group, an arylcarbonyl group, and an alkoxy group. A carbonyl group, a cycloalkoxycarbonyl group, an aryloxycarbonyl group, an alkylaminocarbonyl group, a cycloalkylaminocarbonyl group, an arylaminocarbonyl group, a group obtained by combining these, and the like. Among them, alkyl groups, aryl groups, alkenyl groups or groups obtained by combining these are preferred.

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

P is an integer of 1-3. Among them, it is preferable that p is 3 from the viewpoint that the cured film has more excellent adhesion to the support. In addition, the p pieces of R ^X and the 3-p pieces of R ^Y may be the same or different.

In the above -(OR ^A ) _q -R ^Z , R ^Z represents a hydrogen atom, an alkyl group or an alkoxy group, and the number of carbon atoms in the alkyl group and the alkyl group in the alkoxy group is preferably 1 to 6, and may also be straight Any of chain, branch or cyclic.

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

<Preferable state 2 of the polyfunctional thiol compound> As the polyfunctional thiol compound, the compound represented by the following formula (2) is more preferable. [Chemical formula 5]

In formula (2), R ² and R ³ each independently represent a divalent linking group having 1 or more carbon atoms. The divalent linking group having 1 or more carbon atoms is not particularly limited, and examples thereof include a divalent aliphatic hydrocarbon group (preferably having 1 to 8 carbon atoms) and a divalent aromatic hydrocarbon group (preferably having a carbon number of 8). 6～12), -C(=O)-, -C(=O)-O-, -OC(=O)-O-, -C(=O)-NH-, -OC(=O), -CH=N-, -N(R)-(R: alkyl group), or a group obtained by combining these with the group or the like described as L ¹ in the above formula (1). In addition, R ² and R ³ may be the same or different from each other, and m pieces of R ² , n pieces of R ² , and n pieces of R ³ may be respectively the same or different.

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

In the above formula (2), M ¹ independently represents a single bond, -O-, -S-, -N(R ⁴ )-(R ⁴ : 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- or -CH=N-. In addition, the m pieces of M ¹ and the n pieces of M ¹ may be the same or different.

L ³ represents an m+n-valent linking group, and its state is as described above. In addition, R ¹ represents an interactive group different from a thiol group, and the form thereof is the same as that in the above-mentioned formula (1). In addition, n pieces of R ¹ may be the same or different, respectively.

The synthesis method of a polyfunctional thiol compound is not specifically limited, It can synthesize|combine by combining well-known methods. For example, a desired polyfunctional thiol can be synthesized by reacting a raw material compound having a plurality of thiol groups with a compound having a predetermined interactive group and a group capable of reacting with the above-mentioned thiol group. compound. In addition, as a group which can react with a thiol group, a carbon-carbon double bond group, a carbon-carbon triple bond group, an epoxy group, a carboxyl group, a halogen atom, an alkylsulfonate group can be mentioned. , aryl sulfonate, etc. More specifically, by reacting a (meth)acrylate compound having a predetermined interacting group with a raw material compound having a plurality of thiol groups by Michael addition, all the compounds can be synthesized. Desirable polyfunctional thiol compounds.

Table 1 below shows specific examples of the polyfunctional thiol compound. However, the polyfunctional thiol compound is not limited to these.

[Table 1-1]

[Table 1-2]

[Table 1-3]

[Table 1-4]

[Table 1-5]

[Table 1-6]

In Tables 1-1 to 1-6, "Me" represents a methyl group (-CH ₃ ). "OTs" means tosylate. In Tables 1-1 to 1-6, R ¹ to R ³ , L ³ and M ¹ are groups corresponding to the respective moieties in formula (2), and m and n are groups corresponding to m and n in formula (2) number.

[Chemical formula 6]

The symbols in Tables 1-1 to 1-6 indicate the following. *: Indicates the connection site of L ³ and M ¹ . ●: ^In the column ^of M1 and ^R2 , the connection site ^of M1 and R2 is shown. In addition, in the row of R ³ , the linking site of R ³ and the -S- group is shown. ○: Indicates a linking site to a thiol (-SH) group or an -S- group. The wavy lines of R ³ and R ¹ : indicate the connection site of R ³ and R ¹ . Up Arrow: Indicates the same meaning as the column immediately above.

[Photopolymerization Initiator] The curable composition contains a photopolymerization initiator. The photopolymerization initiator is not particularly limited as long as it can initiate the polymerization of the polymerizable compound, and known photopolymerization initiators can be used. As the photopolymerization initiator, for example, one having photosensitivity in the ultraviolet region to the visible light region is preferred. The photopolymerization initiator may be an activator that interacts with a sensitizer excited by light to generate active radicals, or may be an initiator that initiates cationic polymerization depending on the type of polymerizable compound. Preferably, the photopolymerization initiator contains at least one compound having a molar absorption coefficient of at least about 50 in a wavelength region of about 300 nm to 800 nm (more preferably, 330 nm to 500 nm).

As content of a photoinitiator, 1-9 mass % is preferable with respect to the total solid content of a curable composition. When content of a photoinitiator is 1-9 mass % with respect to the total solid content of a curable composition, the pattern shape of the cured film obtained by hardening a curable composition is more excellent. A photopolymerization initiator may be used individually by 1 type, and may use 2 or more types together. When two or more photopolymerization initiators are used at the same time, the total amount thereof is preferably within the above-mentioned range.

Examples of the photopolymerization initiator include halogenated hydrocarbon derivatives (for example, those containing a triazine skeleton, those having an oxadiazole skeleton, etc.), acylphosphine compounds such as acylphosphine oxide, and hexaarylbisimidazole. (hexaarylbiimidazole), oxime compounds such as oxime derivatives, organic peroxides, sulfur compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, and hydroxyacetophenone. Examples of the halogenated hydrocarbon compound containing the triazine skeleton include the compounds described in Wakabayashi et al., Bull. Chem. Soc. Japan, 42, 2924 (1969), and the compounds described in the specification of British Patent No. 1388492. , the compound described in Japanese Patent Laid-Open No. 53-133428, the compound described in the specification of German Patent No. 3337024, the compound described in J.Org.Chem.; 29, 1527 (1964) based on F.C.Schaefer et al. The compound described in Kokai Sho 62-58241, the compound described in JP 5-281728, the compound described in JP 5-34920, the compound described in the specification of US Pat. No. 4,212,976, etc.

From the viewpoint of exposure sensitivity, it is selected from the group consisting of trihalomethyltriazine compounds, benzyldimethylketal compounds, α-hydroxyketone compounds, α-amino ketone compounds, acylphosphine compounds, and phosphine oxide compounds , metallocene compounds, oxime compounds, triallyl imidazole dimers, onium compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and their derivatives, cyclopentadiene-benzene-iron complex Compounds of the group of compounds and their salts, halomethyloxadiazole compounds and 3-aryl-substituted coumarin compounds are preferred.

Among them, trihalogenated methyl triazine compound, α-amino ketone compound, acylphosphine compound, phosphine oxide compound, oxime compound, triallyl imidazole dimer, onium compound, benzophenone compound or phenethyl compound The ketone compound is more preferably, at least one compound selected from the group consisting of trihalomethyltriazine compound, α-amino ketone compound, oxime compound, triallylimidazole dimer and benzophenone compound for further better.

In particular, when a curable composition is used in the production of a light-shielding film, since it is necessary to form a fine pattern in a clear shape, curability and development without leaving a residue in an unexposed part are important. From such a viewpoint, it is particularly preferable to use an oxime compound as a photopolymerization initiator. In particular, when a fine pattern is formed, a stepper is used for exposure for curing, but the exposure may be damaged by halogen, and it is necessary to keep the amount of the photopolymerization initiator added low. Taking these points into consideration, it is particularly preferable to use an oxime compound as a photopolymerization initiator when forming a fine pattern. Specific examples of the photopolymerization initiator can be referred to, for example, paragraphs 0265 to 0268 of JP 2013-29760 A, the contents of which are incorporated in the present specification.

As a photopolymerization initiator, a hydroxyacetophenone compound, an aminoacetophenone compound, and an acylphosphine compound can also be preferably used. More specifically, for example, the aminoacetophenone-based initiator described in Japanese Patent Laid-Open No. 10-291969 and the acylphosphine-based initiator described in Japanese Patent No. 4225898 can also be used. Examples of the hydroxyacetophenone compound include IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, and IRGACURE-127 (trade names, all of which are manufactured by BASF). As the aminoacetophenone compound, commercially available IRGACURE-907, IRGACURE-369, and IRGACURE-379EG (trade names, all of which are manufactured by BASF Corporation) can be mentioned. As an aminoacetophenone compound, the compound described in Unexamined-Japanese-Patent No. 2009-191179 whose absorption wavelength is matched with the long-wavelength light source, such as 365 nm or 405 nm, can also be mentioned. As the acylphosphine compound, commercially available IRGACURE-819 and DAROCUR-TPO (trade names, both of which are manufactured by BASF Corporation) can be mentioned.

<Oxime compound> As a photopolymerization initiator, an oxime compound (oxime-type initiator) is mentioned more preferably. The above-mentioned curable composition in which the photopolymerization initiator is an oxime compound has more excellent exposure sensitivity. In addition, the oxime compound has high sensitivity and high polymerization efficiency, can cure the curable composition layer regardless of the colorant concentration, and is easy to design the high colorant concentration, so it is preferable. Specific examples of the oxime compound include the compounds described in JP 2001-233842 A, the compounds described in JP 2000-80068 A, and the compounds described in JP 2006-342166 A. Examples of the oxime compound include 3-benzyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, and 3-propionoxyiminobutane Alk-2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzyloxyimide Amino-1-phenylpropan-1-one, 3-(4-toluenesulfonyloxy)iminobutan-2-one and 2-ethoxycarbonyloxyimino-1-phenyl Propane-1-one, etc. In addition, those described in J.C.S.Perkin II (1979) pp.1653-1660, J.C.S.Perkin II (1979) pp.156-162, and Journal of Photopolymer Science and Technology (1995) pp.202-232 can also be cited. Compounds, compounds described in JP 2000-66385 A, compounds described in JP 2000-80068 A, JP 2004-534797 A, and JP 2006-342166 A. Commercially available products can also preferably use IRGACURE-OXE01 (manufactured by BASF), IRGACURE-OXE02 (manufactured by BASF), IRGACURE-OXE03 (manufactured by BASF), or IRGACURE-OXE04 (manufactured by BASF). In addition, TR-PBG-304 (manufactured by Changzhou Qiangli Electronic New Materials Co., Ltd.), ADEKA ARKLS NCI-831, ADEKA ARKLS NCI-930 (manufactured by ADEKA CORPORATION), or N-1919 (containing a carbazole-oxime ester skeleton) can also be used. Photoinitiator (manufactured by ADEKA CORPORATION)).

As oxime compounds other than those described above, compounds described in JP-A No. 2009-519904 in which an oxime is linked to the N-position of carbazole; and US Pat. No. 7,626,957 in which a heterosubstituent is introduced into the benzophenone moiety can also be used. Compounds described in the official gazette; compounds described in Japanese Patent Laid-Open No. 2010-15025 and U.S. Patent Publication No. 2009-292039 with a nitro group introduced into the pigment site; ketoxime compounds described in International Publication No. 2009-131189; Compounds described in U.S. Patent No. 7,556,910 containing a triazine skeleton and an oxime skeleton in the same molecule; compounds described in Japanese Patent Laid-Open No. 2009-221114 having maximum absorption at 405 nm and good sensitivity to g-ray light sources ;Wait. Preferably, for example, paragraphs 0274 to 0275 of JP 2013-29760 A can be referred to, the contents of which are incorporated in the present specification. Specifically, as the oxime compound, a compound represented by the following formula (OX-1) is preferable. In addition, the oxime compound may be an oxime compound in which the N-O bond of the oxime compound is (E) form, an oxime compound in (Z) form, or a mixture of (E) form and (Z) form.

[Chemical formula 7]

In formula (OX-1), R and B each independently represent a monovalent substituent, A represents a divalent organic group, and Ar represents an aryl group. In the formula (OX-1), the monovalent substituent represented by R is preferably a monovalent non-metallic atomic group. Examples of the monovalent non-metal atomic group include an alkyl group, an aryl group, an aryl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a heterocyclic group, an alkylthiocarbonyl group, and an arylthiocarbonyl group. These groups may have one or more substituents. Also, the aforementioned substituents may be further substituted with other substituents. As a substituent, a halogen atom, an aryloxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, an aryloxy group, an aryl group, an alkyl group, an aryl group, etc. are mentioned. In the formula (OX-1), the monovalent substituent represented by B is preferably an aryl group, a heterocyclic group, an arylcarbonyl group or a heterocyclic carbonyl group. These groups may have one or more substituents. Examples of the substituent include the aforementioned substituents. In the formula (OX-1), the divalent organic group represented by A is preferably an alkylene group, a cycloalkylene group or an alkynylene group having 1 to 12 carbon atoms. These groups may have one or more substituents. Examples of the substituent include the aforementioned substituents.

As the photopolymerization initiator, an oxime compound containing a fluorine atom can also be used. Specific examples of the fluorine atom-containing oxime compound include compounds described in JP 2010-262028 A; compounds 24, 36 to 40 described in JP 2014-500852 A; JP 2013-A Compound (C-3) described in Gazette No. 164471; etc. This content is incorporated into this manual.

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

[Chemical formula 8]

[Chemical formula 9]

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

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

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

In formula (4), R ¹ , R ³ and R ⁴ have the same meanings as R ¹ , R ³ and R ⁴ in formula (3), and R ⁵ represents -R ⁶ , -OR ⁶ , -SR ⁶ , -COR ⁶ , -CONR ⁶ R ⁶ , -NR ⁶ COR ⁶ , -OCOR ⁶ , -COOR ⁶ , -SCOR ⁶ , -OCSR ⁶ , -COSR ⁶ , -CSOR ⁶ , -CN, halogen atom or hydroxyl group, R ⁶ represents carbon Alkyl with 1-20 carbons, aryl with 6-30 carbons, aralkyl with 7-30 carbons or heterocyclic group with 4-20 carbons, X represents a direct bond or carbonyl, a represents 0-4 the integer.

In the above formulas (1) and (2), it is preferable that R ¹ and R ² each independently represent a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a cyclohexyl group or a phenyl group. R ³ is preferably methyl, ethyl, phenyl, tolyl or xylyl. R ⁴ is preferably an alkyl group or a phenyl group having 1 to 6 carbon atoms. R ⁵ is preferably methyl, ethyl, phenyl, tolyl or naphthyl. X is preferably a direct bond. In the above formulae (3) and (4), R ¹ is preferably methyl, ethyl, n-propyl, isopropyl, cyclohexyl or phenyl, each independently. R ³ is preferably methyl, ethyl, phenyl, tolyl or xylyl. R ⁴ is preferably an alkyl group or a phenyl group having 1 to 6 carbon atoms. R ⁵ is preferably methyl, ethyl, phenyl, tolyl or naphthyl. X is preferably a direct bond. Specific examples of the compounds represented by the formula (1) and the formula (2) include the compounds described in paragraphs 0076 to 0079 of JP-A-2014-137466, for example. This content is incorporated into this manual.

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

[Chemical formula 10]

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

[Polymerizable compound] The curable composition contains a polymerizable compound. The content of the polymerizable compound is preferably 1 to 40 mass %, more preferably 10 to 40 mass %, relative to the total solid content of the curable composition. When the content of the polymerizable compound is 10 to 40 mass % with respect to the total solid content of the curable composition, the curable composition has more excellent exposure sensitivity. In addition, a polymerizable compound may be used individually by 1 type, and may use 2 or more types together. When two or more types of polymerizable compounds are used simultaneously, the total amount thereof is preferably within the above-mentioned range.

The polymerizable compound is preferably a compound containing one or more ethylenically unsaturated bond-containing groups, more preferably two or more, more preferably three or more, and particularly preferably five or more . The upper limit is, for example, 15 or less. As a group containing an ethylenically unsaturated bond, a vinyl group, a (meth)allyl group, a (meth)acryloyl group, etc. are mentioned, for example.

The polymerizable compound may be, for example, any of chemical forms such as monomers, prepolymers, oligomers, mixtures thereof, and multimers thereof, and monomers are preferred. The molecular weight of the polymerizable compound is preferably 100 to 3,000, more preferably 250 to 1,500. The polymerizable compound is preferably a 3- to 15-functional (meth)acrylate compound, and more preferably a 3- to 6-functional (meth)acrylate compound. Examples of monomers and prepolymers include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) The amines and their multimers are preferably esters of unsaturated carboxylic acids and aliphatic polyol compounds, and amides of unsaturated carboxylic acids and aliphatic polyamine compounds, and their multimers. In addition, the addition reaction products of unsaturated carboxylates or amides containing nucleophilic substituents such as hydroxyl groups, amine groups, and mercapto groups and monofunctional or polyfunctional isocyanates or epoxides, and Dehydration-condensation reaction products of the above-mentioned unsaturated carboxylic acid esters or amides and monofunctional or polyfunctional carboxylic acids, and the like. In addition, the reaction products of unsaturated carboxylic acid esters or amides containing electrophilic substituents such as isocyanate groups and epoxy groups and monofunctional or polyfunctional alcohols, amines or thiols, halogenated or Reactants of unsaturated carboxylic acid esters or amides with a leaving substituent such as tosyloxy and monofunctional or polyfunctional alcohols, amines or thiols are also preferred. In addition, in place of the above-mentioned unsaturated carboxylic acid, a group of compounds substituted with vinylbenzene derivatives such as unsaturated phosphonic acid and styrene, vinyl ether, and allyl ether can also be used. As these specific compounds, the compounds described in paragraphs 0095 to 0108 of JP-A No. 2009-288705 can also be preferably used in the present invention.

The polymerizable compound contains one or more groups containing an ethylenically unsaturated bond and has a boiling point of 100° C. or higher under normal pressure. For example, reference can be made to the compounds described in paragraph 0227 of JP-A-2013-29760 and paragraphs 0254-0257 of JP-A-2008-292970, the contents of which are incorporated in the present specification.

The polymerizable compounds are dipeptaerythritol triacrylate (commercially available as KAYARAD D-330, PET-30, manufactured by Nippon Kayaku Co., Ltd.), dipivalerythritol tetraacrylate (commercially available as product, KAYARAD D-320, manufactured by Nippon Kayaku Co., Ltd.), dipivaloerythritol penta(meth)acrylate (as a commercial item, KAYARAD D-310, manufactured by Nippon Kayaku Co., Ltd. ), Dipionaerythritol hexa(meth)acrylate (as a commercial item, KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd.; A-DPH-12E, manufactured by Shin-Nakamura Chemical Co., Ltd.) And the structure of these (meth)acryloyl groups via ethylene glycol residues or propylene glycol residues (eg, SR454, SR499 commercially available from Sartomer Company) is preferred. Their oligomeric versions can also be used. In addition, NK Ester A-TMMT (neopentaerythritol tetraacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.), KAYARAD RP-1040 (manufactured by Nippon Kayaku Co., Ltd.), and the like can also be used. The state of a preferable polymerizable compound is shown below.

The polymerizable compound may have an acid group such as a carboxylic acid group, a sulfonic acid group, or a phosphoric acid group. The acid group-containing polymerizable compound is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and the unreacted hydroxyl group of the aliphatic polyhydroxy compound reacts with a non-aromatic carboxylic acid anhydride to have acid group polymerizability The compound is more preferable, and in the ester, it is further preferable that the aliphatic polyhydroxy compound is neotaerythritol and/or dipeoerythritol. As a commercial item, ARONIX TO-2349 by Toagosei Co., Ltd., M-305, M-510, and M-520 etc. are mentioned, for example.

As a preferable acid value of the polymerizable compound containing an acid group, it is 0.1-40 mgKOH/g, More preferably, it is 5-30 mgKOH/g. When the acid value of the polymerizable compound is 0.1 mgKOH/g or more, the development and dissolution properties are favorable, and when it is 40 mgKOH/g or less, the production and/or handling are advantageous. And by being in the said range, photopolymerization performance is favorable and it is excellent in curability.

Compounds containing caprolactone structures are also preferred forms of polymeric compounds. The compound containing a caprolactone structure is not particularly limited as long as it contains a caprolactone structure in the molecule, and examples thereof include trimethylolethane, ditrimethylolethane, trimethylol Polyhydric alcohols such as methylolpropane, ditrimethylolpropane, neopentaerythritol, dipepaerythritol, trinepentaerythritol, glycerol, diglycerol, trimethylol melamine, and (meth)acrylic acid and ε-hexyl ε-caprolactone modified polyfunctional (meth)acrylate obtained by esterification of lactone. Among them, a compound containing a caprolactone structure represented by the following formula (Z-1) is preferable.

[Chemical formula 11]

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), and the rest are A group represented by the following formula (Z-3).

[Chemical formula 12]

In formula (Z-2), R ¹ represents a hydrogen atom or a methyl group, m represents a number of 1 or 2, and * represents a bond.

[Chemical formula 13]

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

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

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

[Chemical formula 14]

In formulas (Z-4) and (Z-5), E each independently represents -((CH ₂ ) _y CH ₂ O)- or ((CH ₂ ) _y CH(CH ₃ )O)-, and y is each independently Day and day represent an integer of 0 to 10, and X each 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 each 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 each 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), m is preferably an integer of 0 to 6, more preferably an integer of 0 to 4. The total of each m is preferably an integer of 2 to 40, more preferably an integer of 2 to 16, and even more preferably an integer of 4 to 8. In formula (Z-5), n is preferably an integer of 0 to 6, more preferably an integer of 0 to 4. The total of each n is preferably an integer of 3 to 60, more preferably an integer of 3 to 24, and even more preferably an integer of 6 to 12. -((CH ₂ ) _y CH ₂ O)- or ((CH ₂ ) _y CH(CH ₃ )O)- in formula (Z-4) or formula (Z-5) is the terminal on the oxygen atom side and X The form of the bond is preferable.

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 Xs in formula (Z-5) are all acryl groups, a compound in which 6 Xs in formula (Z-5) are all acryl groups, and at least one of 6 Xs is a hydrogen atom. The state of the mixture of compounds is preferred. By setting it as such a structure, developability can be improved more.

The total content in the polymerizable compound of the compound represented by formula (Z-4) or formula (Z-5) is preferably 20 mass % or more, more preferably 50 mass % or more.

The compound represented by the formula (Z-4) or the formula (Z-5) can be synthesized by a previously known process, that is, the following process: Propylene oxide undergoes a ring-opening addition reaction to bond the ring-opening skeleton; and the terminal hydroxyl group of the ring-opening skeleton reacts with, for example, (meth)acryloyl chloride to introduce a (meth)acryloyl group . Each process is a well-known process, and those with ordinary knowledge in the art can easily synthesize the compound represented by the general formula (Z-4) or (Z-5).

Among the compounds represented by the formula (Z-4) or the formula (Z-5), a neopentaerythritol derivative and/or a dipuetaerythritol derivative are more preferable. Specifically, compounds represented by the following formulae (a) to (f) (hereinafter, also referred to as "exemplary compounds (a) to (f)") are exemplified, and among them, compounds (a) and (b) are exemplified. ), (e), (f) are preferred.

[Chemical formula 15]

[Chemical formula 16]

As a commercial item of the polymerizable compound represented by formulae (Z-4) and (Z-5), for example, SR-494, which is a tetrafunctional acrylate containing four ethoxy-extended chains manufactured by Sartomer Company, is mentioned. , Nippon Kayaku Co., Ltd. manufactured by Nippon Kayaku Co., Ltd. containing 6 pentyloxy chain 6-functional acrylate, namely DPCA-60, containing 3 isobutoxy chains of functional acrylate, namely TPA-330 and the like.

As the polymerizable compound, urethane acrylic acid described in Japanese Patent Publication No. 48-41708, Japanese Patent Publication No. 51-37193, Japanese Patent Publication No. 2-32293, and Japanese Patent Publication No. 2-16765 Esters; amines containing ethylene oxide skeletons described in Japanese Patent Publication No. 58-49860, Japanese Patent Publication No. 56-17654, Japanese Patent Publication No. 62-39417 and Japanese Patent Publication No. 62-39418 Carbamate compounds are also preferred. In addition, by using Japanese Patent Laid-Open No. 63-277653, Japanese Patent Laid-Open No. 63-260909, and Japanese Patent Laid-Open No. Hei 1-105238, the molecules containing an amine group structure and/or a thioether structure are used. Addition polymerizable compounds can obtain curable compositions with very excellent photospeed. Commercially available products include urethane oligomers UAS-10, UAB-140 (manufactured by Sanyo Kokusaku Pulp Co., Ltd.), and UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.) , DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600 and AI-600 (manufactured by Kyoeisha Chemical Co., Ltd.), etc.

The SP (Solubility Parameter) value of the polymerizable compound is preferably 9.50 or more, more preferably 10.40 or more, and even more preferably 10.60 or more. In this specification, the SP value is determined by the Hoy method unless otherwise specified (HL Hoy Journal of Painting, 1970, Vol. 42, 76-118). The SP value is shown without the unit, but the unit is cal ^1/2 cm ^-3/2 .

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

Formula (Q3) [Chemical Formula 17]

In the above formula (Q3), Ar ¹¹ to Ar ¹⁴ each independently represent an aryl group containing a benzene ring surrounded by a dotted line. X ¹ to X ⁴ each independently represent a polymerizable group-containing substituent, and carbon atoms in the substituent may be substituted with a hetero atom. a and b each independently represent an integer of 1 to 5, and c and d each independently represent an integer of 0 to 5. R ¹ to R ⁴ each independently represent a substituent, e, f, g, and h each independently represent an integer of 0 or more, and the upper limit of e, f, g, and h is a value that can be contained in Ar ¹¹ to Ar ¹⁴ , respectively. The number of substituents is obtained by subtracting a, b, c or d, respectively. Wherein, when Ar ¹¹ to Ar ¹⁴ are each independently a polycyclic aromatic hydrocarbon group containing a benzene ring surrounded by a dotted line as one of the fused rings, X ¹ to X ⁴ and R ¹ to R ⁴ may be independently substituted with The benzene ring surrounded by the dotted line may be substituted with a ring other than the benzene ring surrounded by the dotted line.

In the formula (Q3), the aryl group represented by Ar ¹¹ to Ar ¹⁴ and containing a benzene ring surrounded by a dotted line is preferably an aryl group having 6 to 14 carbon atoms, and an aryl group having 6 to 10 carbon atoms (for example, a phenyl group). , naphthyl) is more preferred, and phenyl (limited to the benzene ring surrounded by dotted lines) is further preferred.

In the formula (Q3), X ¹ to X ⁴ each independently represent a polymerizable group-containing substituent, and carbon atoms in the substituent may be substituted with a hetero atom. The polymerizable group-containing substituent represented by X ¹ to X ⁴ is not particularly limited, but is preferably a polymerizable group-containing aliphatic group. The polymerizable group-containing aliphatic group represented by X ¹ to X ⁴ is not particularly limited, but is preferably an alkylene group having 1 to 12 carbon atoms other than the polymerizable group, and has 2 to 2 carbon atoms. An alkylene group of 10 is more preferable, and an alkylene group having 2 to 5 carbon atoms is further preferable. In the polymerizable group-containing aliphatic groups represented by X ¹ to X ⁴ , when the aliphatic group is substituted by a hetero atom, it is substituted by -NR- (R is a substituent), an oxygen atom, and a sulfur atom. Preferably, the non-adjacent -CH ₂ - in the aliphatic group is substituted by an oxygen atom or a sulfur atom, and it is more preferred that the non-adjacent -CH ₂ - in the aliphatic group is substituted by an oxygen atom. Preferably, the aliphatic group containing a polymerizable group represented by X ¹ to X ⁴ is substituted by a heteroatom at ¹ to 2 places, more preferably ^at 1 place by a hetero atom. It is further preferable that one of the surrounding benzene rings adjacent to the aryl group is substituted with a heteroatom. The polymerizable group contained in the polymerizable group-containing aliphatic group represented by X ¹ to X ⁴ is a polymerizable group capable of radical polymerization or cationic polymerization (hereinafter, also referred to as radical polymerization, respectively). and cationic polymerizable groups) are preferred. As the radically polymerizable group, generally known radically polymerizable groups can be used, and preferred ones include ethylenically unsaturated bond-containing polymerizable groups capable of radical polymerization. Specifically, A vinyl group, a (meth)acryloyloxy group, etc. are mentioned. Among them, (meth)acryloyloxy is preferable, and acryloxy is more preferable. As the cationically polymerizable group, generally known cationically polymerizable groups can be used, and specific examples thereof include alicyclic ether groups, cyclic acetal groups, cyclic lactone groups, cyclic thioether groups, spiro Cyclic orthoester group, vinyloxy group, etc. Among them, an alicyclic ether group and a vinyloxy group are preferable, and an epoxy group, an oxetanyl group, and a vinyloxy group are particularly preferable. It is preferable that the above-mentioned polymerizable group contained in the substituent contained in Ar ¹¹ to Ar ¹⁴ is a radically polymerizable group. Two or more of Ar ¹¹ to Ar ¹⁴ contain a polymerizable group-containing substituent, preferably 2 to 4 of Ar ¹¹ to Ar ¹⁴ contain a polymerizable group-containing substituent, and 2 or more of Ar ¹¹ to Ar ¹⁴ It is more preferable that 3 substituents contain a polymerizable group, and it is more preferable that 2 of Ar ¹¹ to Ar ¹⁴ contain a substituent containing a polymerizable group. When Ar ¹¹ to Ar ¹⁴ are each independently a polycyclic aromatic hydrocarbon group containing a benzene ring surrounded by a dotted line as one of the fused rings, X ¹ to X ⁴ may be independently substituted with a benzene ring surrounded by a dotted line, or It may be substituted with a ring other than the benzene ring surrounded by the dotted line.

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

In formula (Q3), R ¹ to R ⁴ each independently represent a substituent. The substituents represented by R ¹ to R ⁴ are not particularly limited, and examples thereof include halogen atoms, haloalkyl groups, alkyl groups, alkenyl groups, acyl groups, hydroxyl groups, hydroxyalkyl groups, alkoxy groups, aryl groups, Heteroaryl and alicyclic groups, etc. Preferably, the substituent represented by R ¹ to R ⁴ is an alkyl group, an alkoxy group or an aryl group, preferably an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms or a phenyl group. , methoxy or phenyl is further preferred. In formula (Q3), when Ar ¹¹ to Ar ¹⁴ are each independently a polycyclic aromatic hydrocarbon group containing a benzene ring surrounded by a dotted line as one of the fused rings, R ¹ to R ⁴ may be independently substituted with a dotted line. The surrounded benzene ring may be substituted with a ring other than the benzene ring surrounded by the dotted line.

In the formula (Q3), e, f, g, and h each independently represent an integer of 0 or more, and the upper limit of e, f, g, and h are respectively subtracted from the number of substituents that can be contained in Ar ¹¹ to Ar ¹⁴ . The value obtained by going to a, b, c or d. Preferably, e, f, g, and h are independently 0 to 8, more preferably 0 to 2, and even more preferably 0. When Ar ¹¹ to Ar ¹⁴ are each independently a polycyclic aromatic hydrocarbon group containing a benzene ring surrounded by a dotted line as one of the fused rings, e, f, g and h are preferably 0 or 1, and 0 is more preferably .

As a compound represented by formula (Q3), 9,9 bis[4-(2-propenyloxyethoxy)phenyl] pyrene etc. are mentioned, for example. As the polymerizable compound containing a 9,9-bisaryl perylene skeleton, compounds described in Japanese Patent Laid-Open No. 2010-254732 can also be preferably used.

The polymerizable compound containing the cardo skeleton is not limited, and examples thereof include Oncoat EX series (manufactured by NAGASE & CO., LTD.) and Ogsol (manufactured by Osaka Gas Chemicals Co., Ltd.).

[Optional Components] <Colorant> It is preferable that the curable composition contains a colorant. The colorant is at least one selected from the group consisting of pigments and dyes, and may be a color colorant or a black colorant, but it is preferable to contain a black pigment. The content of the colorant in the curable composition is not particularly limited, but when the cured film obtained from the curable composition is used as a light-shielding film, from the viewpoint of obtaining more excellent light-shielding properties, the cured film is relatively The total solid content of the synthetic composition is preferably 50% by mass or more. The upper limit value of the content of the colorant is not particularly limited, but is usually preferably 70% by mass or less with respect to the total solid content of the curable composition. When the content of the colorant is below the upper limit value, the curable composition has more excellent coatability.

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

･Inorganic pigments The inorganic pigments are not particularly limited, and known inorganic pigments can be used. Examples of inorganic pigments include zinc white, lead white, zinc white, titanium oxide, chromium oxide, iron oxide, precipitated barium sulfate and barite powder, lead red, iron oxide red, chrome yellow, and zinc yellow (zinc yellow). 1 yellow, 2 zinc yellows), ultramarine blue, Prussian blue (potassium ferrocyanide) zircon gray, yellow, chrome titanium yellow, chrome green, peacock, Victoria green, iron blue (not related to Prussian blue) ), vanadium zirconium blue, chrome tin red, manganese red and orange red, etc. In addition, examples of black inorganic pigments include metal oxides containing one or two or more metal elements selected from the group consisting of Co, Cr, Cu, Mn, Ru, Fe, Ni, Sn, Ti, and Ag. compounds, metal nitrides and metal oxynitrides.

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 density even if the content is small. .) is preferred. Examples of metal pigments include metals containing one or two or more metal elements selected from the group consisting of Nb, V, Co, Cr, Cu, Mn, Ru, Fe, Ni, Sn, Ti, and Ag. oxides and metal nitrides. The inorganic pigment preferably contains at least one selected from the group consisting of titanium nitride, titanium oxynitride, niobium nitride, vanadium nitride, metallic pigments containing silver or tin, and metallic pigments containing silver and tin, More preferably, it contains at least one selected from the group consisting of titanium nitride, titanium oxynitride, niobium nitride and vanadium nitride. Niobium nitride and vanadium nitride may also be niobium oxynitride and vanadium oxynitride. Moreover, as an inorganic pigment, carbon black can also be used. Specific examples of carbon black include organic pigments such as C.I. Pigment Black 1 and other commercially available organic pigments and inorganic pigments such as C.I. Pigment Black 7, but are not limited to these.

In the curable composition, in addition to the pigments described as black pigments, pigments having infrared absorption properties can be used. As pigments having infrared absorption properties, tungsten compounds, metal borides, and the like are preferred, and among them, tungsten compounds are preferred because they are excellent in light-shielding properties at wavelengths in the infrared region. In particular, a tungsten compound is preferable from the viewpoint of excellent light transmittance in the light absorption wavelength region and visible light region of the photopolymerization initiator related to the curing efficiency by exposure.

Two or more of these pigments may be used simultaneously, and may be used together with the dyes described later. In order to adjust the color tone and improve the light-shielding properties in a desired wavelength region, for example, black pigments or pigments having infrared light-shielding properties are mixed with color pigments such as red, green, yellow, orange, violet, and blue, or dyes described later. state. It is preferable to mix a red pigment or dye, or a purple pigment or dye with a black pigment or a pigment with infrared light-shielding property, and it is more preferable to mix a red pigment with a black pigment or a pigment with infrared light-shielding property. Moreover, a near-infrared absorber and an infrared absorber to be described later may be added.

The black pigment preferably contains titanium black and/or niobium oxynitride. Titanium black is a black particle containing titanium atoms. Subsequent titanium oxide, titanium oxynitride or titanium nitride are preferred. The surface of the titanium black particles can be modified as necessary in order to improve dispersibility, suppress aggregation, and the like. It can be coated with silicon oxide, titanium oxide, germanium oxide, aluminum oxide, magnesium oxide, or zirconium oxide, and can also be treated with a water-repellent substance as shown in Japanese Patent Laid-Open No. 2007-302836. The titanium black is typically titanium black particles, and the primary particle diameter and the average primary particle diameter of each particle are both smaller, which is preferable. The same applies to niobium oxynitride. 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 diameter of a pigment can be measured by 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 (Dmax: the maximum length among 2 points on the outline of the particle image) and the maximum vertical length ( DV-max: When the image is sandwiched by two straight lines parallel to the maximum length, the shortest length between the two straight lines is connected vertically), and the geometric mean (Dmax×DV-max) ^1/2 is used as the particle size . The particle diameter of 100 particles is measured by this method, and the average primary particle diameter of the pigment represents the arithmetic mean value thereof.

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

As the colorant, titanium oxynitride, titanium nitride or niobium oxynitride is preferably used, and titanium nitride or niobium oxynitride is more preferable for the reason that the obtained cured film has better moisture resistance, and niobium oxynitride is Further preferred. This is considered to be because these colorants are hydrophobic.

Moreover, it is also preferable to contain titanium black as the to-be-dispersed body containing titanium black and Si atoms. In this form, titanium black is contained in the curable composition as a to-be-dispersed body, and the content ratio (Si/Ti) of Si atoms to Ti atoms in the to-be-dispersed body is preferably 0.05 or more in terms of mass, 0.05-0.5 is more preferable, and 0.07-0.4 is more preferable. Here, the said to-be-dispersed body contains both the state which titanium black is in the state of a primary particle, and the state which is agglomerate (secondary particle). In order to change the content ratio (Si/Ti) of the to-be-dispersed body (for example, to be 0.05 or more), the following method can be used. First, a dispersion is obtained by dispersing titanium oxide and silica particles with a dispersant, and the dispersion is subjected to reduction treatment at a high temperature (for example, 850 to 1,000° C.), whereby titanium black particles as the main component can be obtained. And contains the dispersion of Si and Ti. The above reduction treatment can also be performed in an atmosphere of a reducing gas such as ammonia. As titanium oxide, TTO-51N (trade name, manufactured by Ishihara Sangyo Kaisha, Ltd.) etc. are mentioned. As a commercial item of silica particle, AEROSIL (registered trademark) 90, 130, 150, 200, 255, 300, 380 (trade name, manufactured by Evonik) etc. are mentioned. Titanium oxide and silica particles can be dispersed with a dispersant. As a dispersing agent, what was demonstrated in the column of the dispersing agent mentioned later is mentioned. The above dispersion can also be carried out in a solvent. As a solvent, water and an organic solvent are mentioned. Those described in the column of the organic solvent mentioned later can be mentioned. Titanium black whose content ratio (Si/Ti) is adjusted to, for example, 0.05 or more can be produced by, for example, 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 sclerosing composition containing the dispersion is used. When the cured film is formed from the cured film, the residues derived from the curable composition outside the formation region of the cured film are reduced. In addition, the residue contains components derived from curable compositions such as titanium black particles and resin components. Although the reason for the decrease in the residues is not clear, the particle size of the dispersion object as described above tends to decrease (for example, the particle size is 30 nm or less), and the Si atom-containing component of the dispersion object 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 (especially titanium black) when forming the cured film. Titanium black has excellent light shielding properties for light in a wide wavelength range from ultraviolet light to infrared light, so the above-mentioned dispersion containing titanium black and Si atoms is used (the content ratio (Si/Ti) is 0.05 or more in terms of mass. which is preferred) to form a cured film that exhibits excellent light-shielding properties. In addition, the content ratio (Si/Ti) of Si atoms and Ti atoms in the to-be-dispersed body can be, for example, the method (1-1) or the method (1-2) described in the paragraph 0033 of Japanese Patent Laid-Open No. 2013-249417. to measure. When determining whether or not the content ratio (Si/Ti) of Si atoms to Ti atoms in the dispersed body contained in the cured film obtained by curing the curable composition is 0.05 or more, the Japanese special The method (2) described in paragraph 0035 of the Publication No. 2013-249417.

In the to-be-dispersed body containing titanium black and Si atoms, the above-mentioned titanium black can be used. In the dispersion, in order to adjust dispersibility, colorability, etc., one or two or more kinds of complex oxides including Cu, Fe, Mn, V, Ni, etc., cobalt oxide, iron oxide, carbon, etc., can be combined together with titanium black. Black, aniline black and other black pigments are used. At this time, it is preferable that the to-be-dispersed body containing titanium black accounts for 50 mass % or more of all the to-be-dispersed bodies. In the dispersion, other colorants (organic pigments and/or dyes, etc.) may be used together with titanium black as necessary in order to adjust light-shielding properties, etc., within a range that does not impair the effects of the present invention. Hereinafter, the material used for introducing Si atoms into the dispersion will be described. When introducing Si atoms into the dispersion object, a Si-containing substance such as silicon dioxide may be used. As the silica that can be used, precipitated silica, fumed silica, colloidal silica, synthetic silica, etc. can be mentioned, and these can be appropriately selected and used. Furthermore, when the particle size of the silica particles is smaller than the film thickness when forming the cured film, the light-shielding property is more excellent, so it is preferable to use the silica of the particle type. In addition, as an example of the fine particle type silica, for example, the silica described in paragraph 0039 of JP-A No. 2013-249417 can be mentioned, and these contents are incorporated in this specification.

The curable composition can use a tungsten compound and/or a metal boride as a pigment. Tungsten compounds and metal borides have higher absorption relative to infrared rays (light with a wavelength of about 800 to 1,200 nm) (that is, higher light-shielding properties (shielding properties) relative to infrared rays) and lower absorption relative to visible light The infrared shielding material. Therefore, when the curable composition contains a tungsten compound and/or a metal boride, a pattern with high light shielding properties in the infrared region and high light transmittance in the visible light region can be formed. Tungsten compounds and metal borides also absorb less light with wavelengths shorter than the visible region used in exposure of high-pressure mercury lamps, KrF, ArF, etc. for image formation. Therefore, by combining with the polymerizable compound, the photopolymerization initiator, and the alkali-soluble resin described later, an excellent pattern can be obtained, and when a pattern is formed, the development residue can be further suppressed.

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

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

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

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

Specific examples of the tungsten oxide-based compound represented by the general formula (I) include Cs _0.33 WO ₃ , Rb _0.33 WO ₃ , K _0.33 WO ₃ , Ba _0.33 WO ₃ , Cs _0.33 WO ₃ or Rb _0.33 WO ₃ , etc. More preferably, Cs _0.33 WO ₃ is more preferable.

Preferably, the tungsten compound is microparticles. 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. When the average primary particle size is in this range, the tungsten fine particles are less likely to block visible light due to light scattering, so that the light transmittance in the visible light region can be made more reliable. From the viewpoint of avoiding light scattering, the smaller the average primary particle size is, the better. However, the average primary particle size of the tungsten fine particles is usually 1 nm or more for reasons such as ease of handling during production.

Two or more types of tungsten compounds can be used.

A tungsten compound is available as a commercial item. When the tungsten compound is, for example, a tungsten oxide-based compound, the tungsten oxide-based compound can be obtained by heat-treating the tungsten compound in an inert gas atmosphere or a reducing gas atmosphere (see Japanese Patent 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.

Examples of the metal boride include lanthanum boride (LaB ₆ ), ammonium boride (PrB ₆ ), neodymium boride (NdB ₆ ), cerium boride (CeB ₆ ), yttrium boride (YB ₆ ), boride Titanium (TiB ₂ ), zirconium boride (ZrB ₂ ), hafnium boride (HfB ₂ ), vanadium boride (VB ₂ ), tantalum boride (TaB ₂ ), chromium boride (CrB, CrB ₂ ), boride One or more of molybdenum (MoB ₂ , Mo ₂ B ₅ , MoB), tungsten boride (W ₂ B ₅ ), etc., and lanthanum boride (LaB ₆ ) is preferred.

Preferably, the metal boride is fine particles. The average primary particle diameter of the metal boride fine particles is preferably 800 nm or less, more preferably 300 nm or less, and even more preferably 100 nm or less. When the average primary particle size is in this range, the metal boride fine particles are less likely to block visible light due to light scattering, so that the light transmittance in the visible light region can be made more reliable. From the viewpoint of avoiding light scattering, the smaller the average primary particle size is, the better. However, the average primary particle size of the metal boride fine particles is usually 1 nm or more for reasons such as ease of handling during production.

Two or more types of metal borides can be used.

The metal boride can be obtained as a commercial item, 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 usually used, and specific examples thereof include an electric furnace method, a thermoplasma method, and the like. Among these production methods, the thermoplasma method is preferable from the viewpoints of less contamination of impurities, easy uniformity of particle sizes, and high productivity. As a method of generating the thermoplasma, direct current arc discharge, multiphase arc discharge, high frequency (RF) plasma, hybrid plasma, etc. are mentioned, and a high frequency plasma with less contamination of impurities from electrodes is preferred. As a specific method for producing the titanium nitride-containing fine particles by 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. Thereby, a method for synthesizing titanium nitride-containing particles and the like. In addition, the thermoplasma method is not limited to the above.

The production method of the titanium nitride-containing particles is not particularly limited, and the production methods described in paragraphs <0037> to <0089> of International Publication No. WO 2010/147098 can be referred to. For example, it can be produced by using a component containing Fe and/or a component containing Si described later in place of the Ag powder of International Publication No. WO 2010/147098, and mixing the component with a titanium powder material (titanium particles) As a raw material, the titanium nitride-containing particles contained in the composition of the present invention are produced.

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

Titanium powder materials (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, Si atoms, and the like. When the titanium powder material contains Fe atoms, it is preferable that the content of Fe atoms exceeds 0.001 mass % with respect to the total mass of the titanium powder material. When the titanium powder material contains Si atoms, the content of Si atoms relative to the total mass of the titanium powder material is preferably more than 0.002 mass % and less than 0.3 mass %, more preferably 0.01-0.15 mass %, and further 0.02-0.1 mass % better. When the content of Si atoms exceeds 0.002 mass %, the pattern formability of the cured film is further improved. When the content of Si atoms is less than 0.3 mass %, the polarity of the outermost layer of the obtained titanium nitride-containing particle is further stabilized. Therefore, it is considered that the adsorption of the dispersing agent to the titanium nitride-containing particles when the titanium nitride-containing particles are dispersed is optimized, the undispersed matter of the titanium nitride-containing particles is reduced, and the generation of particles can be suppressed. 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, more preferably less than 0.1% by mass relative to the total mass of the titanium powder material, and does not substantially contain as Further preferred.

By obtaining the titanium nitride-containing particles by the thermoplasma method, the diffraction angle 2θ (details will be described later) of the peak derived from the (200) plane when CuKα rays are used as the X-ray source can be easily adjusted to exceed 42.6° and range below 43.5°.

The method for including Fe atoms in the titanium nitride-containing particles is not particularly limited, and examples thereof include a method of introducing Fe atoms at the stage of obtaining titanium particles (titanium powder) used as a raw material of the above-mentioned titanium nitride-containing particles. In more detail, when producing titanium by a reduction (Kroll) method or the like, as a reaction vessel, a material containing Fe atoms such as stainless steel is used, or a material containing Fe atoms is used as a material for a punch and a pulverizer when crushing titanium. In this way, Fe atoms can be attached to the surface of the titanium particles. In the production of the titanium nitride-containing particles by the thermoplasma method, components such as Fe particles and Fe oxides are added in addition to the titanium particles as the raw material, 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 as ions, metal compounds (including complexes), intermetallic compounds, alloys, oxides, composite oxides, nitrides, oxynitrides, sulfides and sulfur. Any form, such as things, is included. Fe atoms contained in the titanium nitride-containing particles may exist as impurities in the inter-lattice position, or may exist as impurities in an amorphous state at grain boundaries.

As a result of intensive research, the present inventors have found that the content of Fe atoms in the titanium nitride-containing particles is related to pattern formability and corrosion resistance of electrodes. Fe atoms contained in the titanium nitride-containing particles are excellent in adhesion to electrodes and substrates, and it is considered that titanium nitride in the titanium nitride-containing particles adheres to electrodes and substrates via Fe atoms. It is considered that Fe atoms remain on the electrode and the substrate after pattern formation of the cured film such as development treatment, and titanium nitride is easily removed. Therefore, it is presumed that the pattern formability of the cured film is improved by setting the content of Fe atoms in the titanium nitride-containing particles to a predetermined amount or more. On the other hand, when the content of Fe atoms contained in the titanium nitride-containing particles is too large, the amount of Fe atoms remaining on the electrode and the substrate increases, which is considered to be a cause of electrode corrosion. Therefore, it is presumed that the corrosion resistance of the electrode is improved by setting the content of Fe atoms in the titanium nitride-containing particles to a predetermined amount or less. The content of Fe atoms in the titanium nitride-containing particles is preferably more than 0.001 mass % and less than 0.4 mass % with respect to the total mass of the titanium nitride-containing particles. Among them, 0.01 to 0.2 mass % is more preferable, and 0.02 to 0.1 mass % is further preferable. When the content of Fe atoms exceeds 0.001 mass %, the pattern formability of the cured film is further improved. Since the content of Fe atoms is less than 0.4 mass %, the corrosion resistance of the electrode based on the cured film is further improved (the corrosion of the electrode by the cured film can be suppressed). That is, when the content of Fe atoms in the titanium nitride-containing particles is within the above-mentioned range, excellent patterning properties of the cured film and corrosion resistance of the electrodes can be obtained. The content of Fe atoms in the titanium nitride-containing particles can be measured by ICP (Inductively Coupled Plasma; high-frequency inductively coupled plasma) emission spectrometry.

It is preferable that the titanium nitride-containing particles further contain Si atoms (silicon atoms). Thereby, the pattern formability of a cured film is further improved. The reason why the pattern formability is improved by containing Si atoms is considered to be the same as that of Fe atoms described above. The content of Si atoms in the titanium nitride-containing particles relative to the total mass of the titanium nitride-containing particles is preferably more than 0.002 mass % and less than 0.3 mass %, more preferably 0.01 to 0.15 mass %, and further 0.02 to 0.1 mass % better. When the content of Si atoms exceeds 0.002 mass %, the pattern formability of the cured film is further improved. When the content of Si atoms is less than 0.3 mass %, the polarity of the outermost layer of the titanium nitride-containing particles is further stabilized. Thereby, it is considered that when the titanium nitride-containing particles are dispersed, the adsorption properties of the dispersing agent to the titanium nitride-containing particles are optimized, the undispersed matter of the titanium nitride-containing particles is reduced, and the generation of particles can be suppressed. The content of Si atoms in the titanium nitride-containing particles can be measured by the same method as that of Fe atoms described above.

The method of making the titanium nitride-containing particles contain Si atoms is not particularly limited, and examples thereof include a method of introducing Si atoms at the stage of obtaining the titanium particles (titanium powder) used as the raw material of the titanium nitride-containing particles. In more detail, when producing titanium by a reduction method or the like, a material containing Si atoms is used as a reaction vessel, or a material containing Si atoms is used as a material for a punch and a pulverizer when crushing titanium, thereby Si atoms can be attached to the surface of titanium particles. When the thermoplasma method is used for the production of the titanium nitride-containing particles, components such as Si particles and Si oxides are added in addition to the titanium particles as the raw material, 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 as ions, metal compounds (including complexes), intermetallic compounds, alloys, oxides, composite oxides, nitrides, oxynitrides, sulfides and sulfur oxides. Any form, such as things, is included. In addition, the Si atoms contained in the titanium nitride-containing particles may exist as impurities at inter-lattice positions, or may exist as impurities in an amorphous state at grain boundaries.

The content of titanium atoms (Ti atoms) in the titanium nitride-containing particles relative to the total mass of the titanium nitride-containing particles is preferably 10 to 85 mass %, more preferably 15 to 75 mass %, and 20 to 70 mass % for further better. 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 mass %, more preferably 5 to 50 mass %, and 10 to 40 mass % for further better. The content of nitrogen atoms can be analyzed by an inert gas fusion thermal conductivity method. The titanium nitride-containing particles contain titanium nitride (TiN) as the main component, which usually becomes conspicuous when oxygen is mixed during its synthesis, when the particle size is small, etc., but it can also be caused by oxidation of the particle surface. contains 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 an inert gas fusion infrared absorption method.

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

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

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

When the X-ray diffraction spectrum of the titanium compound is measured using CuKα rays as the X-ray source, the peak with the strongest intensity is the peak originating from the (200) plane for TiN, which appears in the vicinity of 2θ=42.5°, and the peak originating from (200) for TiO. ) surface peak appears around 2θ=43.4°. On the other hand, although it is not the peak with the strongest intensity, a peak originating from the (200) plane is observed in the vicinity of 2θ=48.1° for anatase-type TiO ₂ , and a peak originating from the (200) plane is observed in the vicinity of 2θ=39.2° for rutile-type TiO ₂ . to the peak originating from the (200) plane. Thereby, the more the crystal state containing many oxygen atoms, the more the peak position is shifted to 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°. From the viewpoint of excellent margin, 42.7° or more and less than 43.5° are more preferable, and from the viewpoint of excellent reproducibility of particle performance, 42.7° or more and less than 43.4° are more preferable. When titanium oxide TiO ₂ is contained as a sub-component, as the peak with the strongest intensity, a peak derived from anatase-type TiO ₂ (101) appears in the vicinity of 2θ=25.3°, and a peak derived from rutile-type TiO ₂ (110) appears in the vicinity of 2θ=25.3°. The peak appears around 2θ=27.4°. However, TiO ₂ is white, and it is a factor that reduces the light-shielding properties of the black matrix, so it is preferable to reduce it to such an extent that it is not observed as a peak.

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

The crystallite size is preferably 20 nm or more, and more preferably 20 to 50 nm. 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 is blue to blue-violet with a peak wavelength of 475 nm or less, and high light-shielding properties and ultraviolet sensitivity can be obtained. The black matrix. When the crystallite size is 20 nm or more, the ratio of the active particle surface to the particle volume is reduced, and a good balance is achieved, and the titanium nitride-containing particles are more excellent in heat resistance and/or durability.

･･Atoms of metal-containing nitride particles containing atom A In addition, metal-containing nitride particles can also be used as inorganic pigments, and a predetermined atom A is contained in the above-mentioned metal-containing nitride particles. Examples of metals in the metal-containing nitride particles include Nb, V, Cr, Y, Zr, Nb, Hf, Ta, W, and Re, and Nb or V is more preferred. As said atom A, B, Al, Si, Mn, Fe, Ni, Ag, etc. are mentioned, for example. When the metal-containing nitride particles contain the atom A, the content thereof is not particularly limited, but the content of the atom A in the metal-containing nitride particles is preferably 0.00005 to 10% by mass.

There is no restriction|limiting in particular as a manufacturing method of the metal-containing nitride particle containing the said atom A, A well-known method can be utilized. When metal-containing nitride particles are produced, a gas phase reaction method is usually used, and specific examples thereof include an electric furnace method, a thermoplasma method, and the like. Among these production methods, the thermoplasma method is preferable from the viewpoints of less contamination of impurities, easy uniformity of particle sizes, and high productivity. As a specific manufacturing method of the metal-containing nitride particle|grains by a thermoplasma method, the thing which uses a metal microparticle manufacturing apparatus (the same apparatus as the "black composite particle|grain manufacturing apparatus" mentioned later) is mentioned, for example. The metal particle production device 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 including a cooling function, a cyclone that classifies the generated metal particles, and metal recovery. The recovery part of the particles is constituted. In the present specification, the metal fine particles refer to particles containing a metal element having a primary particle diameter of 20 nm to 40 μm.

It does not specifically limit as a manufacturing method of the metal-containing nitride particle|grains using a metal microparticle manufacturing apparatus, A well-known method can be utilized. Among them, from the viewpoint of improving the yield of metal-containing nitride particles having a predetermined average primary particle diameter described below, the method for producing metal-containing nitride particles using a metal fine particle production apparatus preferably includes the following process. Process A: A process in which an inert gas without nitrogen is supplied into the plasma torch as a plasma gas to generate a thermoplasma flame. Process B: The process of supplying the metal raw material powder containing transition metal to the thermal plasma flame in the plasma torch to evaporate the above-mentioned metal raw material powder, thereby obtaining the gas phase raw material metal. Process C: The process of cooling the above-mentioned gas phase raw material metal to obtain metal particles containing transition metal. Process D: a process in which an inert gas containing nitrogen is supplied into a plasma torch as a plasma gas to generate a thermoplasma flame. Process E: A process of supplying metal particles containing transition metals to a thermal plasma flame in a plasma torch to evaporate the metal particles, thereby obtaining a gas phase raw metal. Process F: a process for obtaining metal-containing nitride particles by cooling the above-mentioned gas-phase raw material metal. After the process C and/or the process F, the manufacturing method of the metal-containing nitride particles may further include the following process G as required. Process G: The process of classifying the obtained particles. Furthermore, the following process A2 may be included before process A, between process A and process B, between process C and process D, or between process D and process E. Process A2: A process of mixing atom A with transition metal-containing metal raw material powder. Also, the following processes A3-1 to A3-3 may be included before the process A2. Process A3-1: A process of supplying an inert gas that does not contain nitrogen as a plasma gas to a plasma torch to generate a thermoplasma flame. Process A3-2: A process of supplying the raw material powder containing atoms A to the thermal plasma flame in the plasma torch to evaporate the raw material powder, thereby obtaining the gas-phase atoms A. Process A3-3: A process of cooling the gas phase atoms A to obtain atomized atoms A. Process G may also be included after process A3-3. In the present specification, the atomized atom A refers to a particle containing the atom A and having a primary particle diameter of 20 nm to 40 μm.

Moreover, it is preferable that the above-mentioned method for producing metal-containing nitride particles further includes the following process H after the process F (if the process G is included, after the process G after the process F). Process H: a process in which the metal-containing nitride particles obtained in Process F (or Process G) are exposed to a mixed environment of water vapor and nitrogen to perform nitridation treatment. According to needs, the above-mentioned method for manufacturing metal nitride particles may further include a process G after the process H. As shown in FIG. Hereinafter, the preferred state of each process will be described in detail.

Process A Process A is a process in which an inert gas without nitrogen is supplied into the plasma torch as a plasma gas to generate a thermoplasma flame. The method for generating the thermoplasma flame is not particularly limited, and examples include a DC arc discharge method, a multiphase arc discharge method, a high-frequency plasma method, and a mixed plasma method. The plasma method is preferred. The method for generating the thermoplasma flame by the high-frequency plasma method is not particularly limited. For example, supplying plasma gas into a plasma torch including a high-frequency oscillation coil and a quartz A method of obtaining a thermoplasmic flame by applying a high-frequency current to the coil. As the plasma gas in the process A, an inert gas that does not contain nitrogen gas can be used. Argon gas, hydrogen gas, etc. are mentioned as an inert gas which does not contain nitrogen. The inert gas that does not contain nitrogen gas may be used alone or in combination of two or more.

Process A2 Process A2 is a process in which atoms A are mixed into transition metal-containing metal raw material powders. The mixing method of the raw material metal powder and atom A is not particularly limited, and a known method can be used. For example, the above-described material supply device for supplying the metal raw material powder into the plasma torch may include mixing and dispersing functions. Specifically, the material supply device described in paragraphs 0047 to 0058 of International Publication No. WO 2010/147098 can be used, and the contents are incorporated in this specification. The manufacturing method of metal-containing nitride particles may further include the following processes A3-1 to A3-3 before the process A2.

Process B Process B is a process of supplying transition metal-containing metal raw material powder to a thermoplasma flame in a plasma torch to evaporate the metal raw material powder, thereby obtaining a gas-phase raw metal. The method of supplying the metal raw material powder to the thermoplasma flame in the plasma torch is not particularly limited, but it is preferable to use a carrier gas spray from the viewpoint that the obtained raw material metal in the gas phase is in a more uniform state. As the carrier gas, it is preferable to use an inert gas that does not contain nitrogen. The state of the inert gas not containing nitrogen is as described above. When the method for producing metal-containing nitride particles includes the above-mentioned process A2, it is preferable that the metal raw material powder is maintained in a uniformly dispersed state before the metal raw material powder is supplied into the plasma torch.

Process C Process C is a process of cooling the raw metal in the gas phase to obtain metal particles containing transition metals. It does not specifically limit as a cooling method, It is preferable to use the chamber which has a cooling function. By introducing the raw material metal in the gas phase obtained in the process B into a chamber having the above-mentioned cooling function, and rapidly cooling in the chamber, metal fine particles of the desired particle size described below can be generated. The generated metal particles are recovered by, for example, a recovery unit. As the environment in the chamber, an inert gas that does not contain nitrogen is preferred. The state of the inert gas not containing nitrogen is as described above. In addition, by going through the above-mentioned processes A to C, metal particles containing a transition metal can be obtained. Metal particles containing transition metals are easily evaporated in process E. When the metal raw material powder contains impurities, the above-mentioned impurities can also be removed by going through the above-mentioned processes A to C.

Process D Process D is a process in which an inert gas containing nitrogen is supplied into a plasma torch as a plasma gas to generate a thermoplasma flame. As an inert gas containing nitrogen, nitrogen gas and nitrogen containing an inert gas are mentioned. Argon gas, hydrogen gas, etc. are mentioned as an inert gas. The nitrogen containing the inert gas is not particularly limited, and the nitrogen content is usually about 10-90 mol%, preferably about 30-60 mol%. Other states are the same as process A.

Process E Process E is a process in which metal particles containing transition metals are supplied to a thermal plasma flame in a plasma torch to vaporize the metal particles, thereby obtaining raw metal in gas phase. As a method of supplying the metal particles to the thermoplasma flame in the plasma torch, as described above, as the carrier gas, an inert gas containing nitrogen is preferable. The state of the inert gas containing nitrogen is as described above. In the process E, the raw metal that becomes the metal particles in the process A to the process C is supplied to the thermoplasma flame, so that the raw metal in the gas phase is easily obtained, and the state of the raw metal in the gas phase becomes more uniform.

Process F Process F is a process for obtaining metal-containing nitride particles of transition metal-containing nitride by cooling the raw metal in the gas phase. The preferred aspect of the cooling method is as described above, but as the environment in the chamber, an inert gas containing nitrogen is preferred. Preferred aspects of the inert gas containing nitrogen are as described above.

Process G Process G is a process of classifying the obtained metal particles and/or metal-containing nitride particles. It does not specifically limit as a classification method, For example, a cyclone can be used. The cyclone has a conical container, and has the function of generating a swirling flow in the container and classifying particles by centrifugal force. The classification is preferably carried out in an atmosphere of inert gas. The state of the inert gas is as described above.

Process H Process H is a process in which metal-containing nitride particles are exposed to a mixed environment of water vapor and nitrogen to perform nitridation treatment. By going through this process, the content of the metal nitride in the metal nitride-containing particles can be increased. The method of exposing the metal-containing nitride particles to a mixed environment of water vapor and nitrogen is not particularly limited. The method of standing or stirring for a predetermined time is more preferable from the viewpoint of stabilizing the surface and grain boundaries of the metal nitride particles. Regarding the mixing ratio of water vapor and nitrogen, in the atmosphere, the relative humidity is preferably 25 to 95%. The time of standing or stirring is preferably 0.5 to 72 hours, and the temperature at this time is preferably 10 to 40°C.

Processes A3-1 to A3-3 Processes A3-1 to A3-3 are processes (A3-1) in which an inert gas without nitrogen is supplied into the plasma torch as a plasma gas to generate a thermal plasma flame. A process (A3-2) of supplying raw material powder containing atom A in a thermoplasma flame to vaporize the above raw material powder to obtain atomic A in the gas phase (A3-2), and cooling the gas phase atom A to obtain particles containing atom A (A3-2) A3-3). The states in each process are as in the above-mentioned process A, process B (instead of metal powder containing transition metal, use raw material powder containing atom A) and process C (instead of metal particles containing transition metal, obtain atomized atom A) .) has been described in. By going through the above-mentioned process, the atom A is atomized, and in the process E, the atom A becomes easy to evaporate. In addition, by going through the above-mentioned process, impurities (metal components other than atom A, etc.) contained in the raw material powder containing atom A can be removed.

Preferred aspect of the method for producing metal-containing nitride particles containing atom A As a preferred aspect of the method for producing metal-containing nitride particles containing atom A, a method having the following processes in order is exemplified. Process A: A process in which an inert gas without nitrogen is supplied into the plasma torch as a plasma gas to generate a plasma flame. Process B: The process of supplying the metal raw material powder containing transition metal to the thermal plasma flame in the plasma torch to evaporate the above-mentioned raw metal powder, thereby obtaining the raw material metal in the gas phase. Process C: a process for obtaining metal particles containing transition metals by cooling the raw metal in the gas phase. Process G: The process of classifying the obtained particles. Process A3-1: A process of supplying an inert gas that does not contain nitrogen as a plasma gas to a plasma torch to generate a thermoplasma flame. Process A3-2: A process for obtaining atomic A in the gas phase by supplying the raw material powder containing atom A to the thermal plasma flame in the plasma torch to evaporate the raw material powder. Process A3-3: A process of cooling the atoms A in the gas phase to obtain atomized atoms A. Process G: The process of classifying the obtained particles. Process A2: A process in which atoms A (in this case, atomized atoms A) are mixed into metal raw material powder (in this case, metal particles) containing a transition metal. Process D: a process in which an inert gas containing nitrogen is supplied into a plasma torch as a plasma gas to generate a thermoplasma flame. Process E: The process of supplying metal particles containing transition metals to the thermal plasma flame in the plasma torch to evaporate the metal particles, thereby obtaining the raw metal in the gas phase. Process F: a process for obtaining metal-containing nitride particles by cooling the above-mentioned gas-phase raw material metal. Process G: The process of classifying the obtained particles. Process H: a process in which the metal-containing nitride particles obtained in the process G are exposed to a mixed environment of water vapor and nitrogen to perform nitridation treatment. In the above series of processes, the order of the processes A to C and the processes A3-1 to A3-3 can be replaced. That is, the processes A to C may be performed after the processes A3-1 to A3-3.

According to a preferred aspect of the method for producing metal-containing nitride particles containing atoms A, impurities contained in the metal raw material powder and raw material particles can be removed, and metal-containing nitride particles having a desired average primary particle diameter can be produced . The reason for this is presumed that the transition metal and/or atom A are ionized by plasma treatment, and when the ions are cooled, the transition metal, atom A, and impurities are each reacted with melting points to be atomized. At this time, the atomization of atoms with a lower melting point is faster, and the atomization of atoms with a higher melting point is slower. Therefore, as described above, it is presumed that the particles (processes B and C, and processes A3-2 and A3-3) that have undergone a single plasma treatment are likely to be single-component (single-crystal). By classifying the single-component particles obtained as described above, the impurity particles can be removed due to the difference in density and/or particle size of the transition metal particles and/or atomic A particles and the impurity particles. The above-mentioned classification can be performed, for example, by using a cyclone separator or the like and appropriately setting classification conditions.

The metal raw material powder and the purification of the raw material powder can be used in the above-mentioned process B as the transition metal-containing metal raw material powder (hereinafter, simply referred to as "metal raw material powder".) and the atom A-containing raw material powder (hereinafter, simply referred to as "metal raw material powder". "raw material powder"), there is no particular limitation, high-purity ones are preferred. The content of the transition metal in the metal raw material powder is not particularly limited, but is preferably 99.99% or more, and more preferably 99.999% or more. The content of atom A in the raw material powder is also the same.

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

The method for producing metal-containing nitride particles may further include the following process A0 before the process B (when the process A2 is included, it is before the process A2). Process A0: Process for removing impurities from metal raw material powder and/or raw material powder.

Process A0 In process A0, the method (separation and purification method) for removing impurities from the raw metal powder and/or raw material powder is not particularly limited. The method described in the paragraph can also be used for other raw metal powders and/or raw material powders according to the method.

Coating of Metal-Nitride-Containing Particles The metal-nitride-containing particles may be metal-nitride-containing particles coated with an inorganic compound. That is, the metal-containing nitride particles may be coated metal-containing nitride particles having metal-containing nitride particles and a coating layer formed using an inorganic compound to coat the metal-containing nitride particles. The curable composition containing metal nitride-containing particles coated with an inorganic compound has more excellent dispersion stability. The inorganic compound is not particularly limited, and examples thereof include oxides such as SiO ₂ , ZrO ₂ , TiO ₂ , GeO ₂ , Al ₂ O ₃ , Y ₂ O ₃ , and P ₂ O ₅ , as well as aluminum hydroxide and zirconium hydroxide. and other hydroxides. Among them, aluminum hydroxide is preferable from the viewpoint of being easy to form a thinner film and easy to form a film with a higher coverage. When it is intended to control the refractive index of the metal-containing nitride particles, silicon oxide is preferred as the low-refractive index coating, and zirconium hydroxide is preferred as the high-refractive index coating. The method for coating the metal-containing nitride particles with an inorganic compound is not particularly limited, and the method for producing the metal-containing nitride particles preferably includes the following inorganic compound coating process.

Inorganic compound coating process The inorganic compound coating process is a process of coating the above-mentioned metal nitride-containing particles with oxides and/or hydroxides. It does not specifically limit as a coating method, For example, the following wet coating method etc. are mentioned.

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

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

As a third wet coating method, in the presence of metal nitride particles, a slurry containing an ionic liquid is prepared using urea and aluminum chloride. After the metal-containing nitride particles are taken out from the slurry and dried, the metal-containing nitride particles are fired, whereby metal-containing nitride particles coated with hydroxide containing aluminum hydroxide can be obtained.

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

(Dye) As the dye, for example, JP 64-90403 A, JP 64-91102 A, JP 1-94301 A, JP 6-11614 A, JP 6-11614 A can be used. No. 2,592,207, US Patent No. 4,808,501, US Patent No. 5,667,920, US Patent No. 5,059,50, JP 5-333207, JP 6-35183, JP 6-51115 , the pigment disclosed in Japanese Patent Laid-Open No. 6-194828, etc. In terms of chemical structures, pyrazole azo compounds, pyrromethylene compounds, aniline azo compounds, triphenylmethane compounds, anthraquinone compounds, benzylidene compounds, oxocyanine compounds, pyrazolotrims can be used azole azo compounds, pyridone azo compounds, cyanine compounds, phenothiazine compounds, pyrrolopyrazole methimine compounds, etc. As dyes, dye polymers can also be used. Examples of the dye multimer include compounds described in JP 2011-213925 A and JP 2013-041097 A. A polymerizable dye having polymerizability in the molecule can be used, and as a commercial item, for example, RDW series manufactured by Wako Pure Chemical Industries, Ltd. can be mentioned.

(Infrared Absorber) The colorant may further contain an infrared absorber. The infrared absorber refers to a compound having absorption in the wavelength region of the infrared region (preferably a wavelength of 650 to 1,300 nm). The infrared absorber is preferably a compound having a maximum absorption wavelength in the wavelength region of 675 to 900 nm. Examples of colorants having such spectroscopic properties include pyrrolopyrrole compounds, copper compounds, cyanine compounds, phthalocyanine compounds, imine compounds, thiol complex compounds, transition metal oxide compounds, and Acid cyanine compounds, naphthalocyanine compounds, quartane compounds, dithiol metal complex compounds, ketonium compounds, and the like. As the phthalocyanine compound, naphthalocyanine compound, imino compound, cyanine compound, squaraine compound, and ketonium compound, compounds disclosed in paragraphs 0010 to 0081 of JP 2010-111750 A can be used, the contents of which are incorporated herein. in the manual. The cyanine compound can be referred to, for example, "Functional Pigment, Nobu Ogawara / Ken Matsuoka / Tejiro Kitao / Kodansha Scientific Ltd.", which is incorporated in this specification.

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

As the compound having a maximum absorption wavelength in the wavelength region of 675 to 900 nm, at least one selected from the group consisting of cyanine compounds, pyrrolopyrrole compounds, squaraine compounds, phthalocyanine compounds and naphthalocyanine compounds is preferred good. The infrared absorber is preferably a compound in which 1% by mass or more is dissolved in water at 25°C, and a compound in which 10% by mass or more is dissolved in water at 25°C is more preferable. By using this compound, solvent resistance is optimized. For the pyrrolopyrrole compound, reference can be made to paragraph numbers 0049 to 0062 of JP 2010-222557 A, the contents of which are incorporated in the present specification. For cyanine compounds and squaraine compounds, refer to Paragraph Nos. 0022 to 0063 of International Publication No. WO 2014/088063, Paragraph Nos. 0053 to 0118 of International Publication No. 2014/030628, and Paragraph No. 0028 of JP-A No. 2014-59550 ~0074, Paragraph Nos. 0013 to 0091 of International Publication No. 2012/169447, Paragraph Nos. 0019 to 0033 of Japanese Patent Laid-Open No. 2015-176046, Paragraph Nos. 0053 to 0099 of Japanese Patent Laid-Open No. 2014-63144, Japanese Patent Laid-Open Publication No. 0053-0099 Paragraph Nos. 0085 to 0150 of Japanese Patent Application Laid-Open No. 2014-52431, Paragraph Nos. 0076 to 0124 of Japanese Patent Application Laid-Open No. 2014-44301, Paragraph Nos. 0045 to 0078 of Japanese Patent Application Laid-Open No. 2012-8532, Japanese Patent Application Laid-Open No. 2015-172102 Paragraph Nos. 0027 to 0067 of Japanese Patent Application Laid-Open No. 2015-172004, Paragraph Nos. 0029 to 0067 of Japanese Patent Application Laid-Open No. 2015-172004, Paragraph Nos. 0029 to 0085 of Japanese Patent Application Laid-Open No. 2015-40895, Paragraph Nos. 0022 to Japanese Patent Application Laid-Open No. 2014-126642 0036, Paragraph Nos. 0011 to 0017 of Japanese Patent Laid-Open Publication No. 2014-148567, Paragraph Nos. 0010 to 0025 of Japanese Patent Laid-Open Publication No. 2015-157893, Paragraph Nos. 0013 to 0026 of Japanese Patent Laid-Open Publication No. 2014-095007, Paragraph Nos. 0013 to 0047 of Japanese Patent Application Laid-Open No. 2014-80487 and Paragraph Nos. 0007 to 0028 of Japanese Patent Application Laid-Open No. 2013-227403 are incorporated herein by reference.

通式1中，A¹ 及A² 分別獨立地表示芳基、雜芳基或以下述通式1-A表示之基團。 通式1-A [化學式19]

通式1-A中，Z^1A 表示形成含氮雜環之非金屬原子團，R^2A 表示烷基、烯基或芳烷基，d表示0或1，波浪線表示連結鍵。 通式2 [化學式20]

通式2中，R^1a 及R^1b 分別獨立地表示烷基、芳基或雜芳基， R² ～R⁵ 分別獨立地表示氫原子或取代基，R² 與R³ 、R⁴ 與R⁵ 可分別鍵結而形成環， R⁶ 及R⁷ 分別獨立地表示氫原子、烷基、芳基、雜芳基、-BR^A R^B 或金屬原子，R^A 及R^B 分別獨立地表示氫原子或取代基， R⁶ 可與R^1a 或R³ 共價鍵結或配位鍵結， R⁷ 可與R^1b 或R⁵ 共價鍵結或配位鍵結。 通式3 [化學式21]

通式3中，Z¹ 及Z² 分別獨立地為形成可以稠合之5員或6員的含氮雜環之非金屬原子團， R¹⁰¹ 及R¹⁰² 分別獨立地表示烷基、烯基、炔基、芳烷基或芳基， L¹ 表示包含奇數個次甲基之次甲基鏈， a及b分別獨立地為0或1， a為0時，碳原子與氮原子以雙鍵鍵結，b為0時，碳原子與氮原子以單鍵鍵結， 式中以Cy表示之部位為陽離子部時，X¹ 表示陰離子，c表示為了維持電荷的平衡而所需之數，式中以Cy表示之部位為陰離子部時，X¹ 表示陽離子，c表示為了維持電荷的平衡而所需之數，式中以Cy表示之部位的電荷在分子內被中和時，c為0。The infrared absorber is preferably at least one selected from the group consisting of compounds represented by the following general formulas 1 to 3. Formula 1 [Chemical Formula 18]

In the general formula 1, A ¹ and A ² each independently represent an aryl group, a heteroaryl group, or a group represented by the following general formula 1-A. General formula 1-A [Chemical formula 19]

In the general formula 1-A, Z ^1A represents a non-metallic atomic group forming a nitrogen-containing heterocycle, R ^2A represents an alkyl group, an alkenyl group or an aralkyl group, d represents 0 or 1, and a wavy line represents a connecting bond. Formula 2 [Chemical Formula 20]

In general formula 2, R ^1a and R ^1b each independently represent an alkyl group, an aryl group or a heteroaryl group, R ² to R ⁵ each independently represent a hydrogen atom or a substituent, R ² and R ³ , R ⁴ and R ⁵ Can be bonded to form a ring, R ⁶ and R ⁷ each independently represent a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group, -BR ^A R ^B or a metal atom, and R ^A and R ^B each independently represent a hydrogen atom Or a substituent, R ⁶ can be covalently or coordinately bound to R ^1a or R ³ , and R ⁷ can be covalently or coordinately bound to R ^1b or R ⁵ . Formula 3 [Chemical Formula 21]

In the general formula 3, Z ¹ and Z ² are each independently a non-metallic atomic group that forms a 5- or 6-membered nitrogen-containing heterocycle that can be fused, and R ¹⁰¹ and R ¹⁰² are each independently an alkyl group, an alkenyl group, and an alkyne. group, aralkyl group or aryl group, L ¹ represents a methine chain containing an odd number of methine groups, a and b are independently 0 or 1, when a is 0, a carbon atom and a nitrogen atom are bonded by a double bond , when b is 0, the carbon atom and the nitrogen atom are bonded by a single bond. In the formula, when the part represented by Cy is the cation part, X ¹ represents the anion, and c represents the number required to maintain the balance of electric charges. When the part represented by Cy is an anion part, X ¹ represents a cation, and c represents the number required to maintain the balance of charges. In the formula, when the charge of the part represented by Cy is neutralized in the molecule, c is 0.

(Pigment Derivative) The curable composition may contain a pigment derivative. The pigment derivative is preferably a compound having a structure in which a part of the organic pigment is substituted with an acidic group, a basic group, or an imidomethyl phthalate group. As the pigment derivative, from the viewpoint of the dispersibility and dispersion stability of the colorant A, a pigment derivative having an acidic group or a basic group is preferable. It is particularly preferred that the pigment derivative has a basic group. The combination of the resin (dispersant) and the pigment derivative is preferably an acidic dispersant and the pigment derivative has a basic group.

Examples of organic pigments for constituting pigment derivatives include dioxopyrrolopyrrole-based pigments, azo-based pigments, phthalocyanine-based pigments, anthraquinone-based pigments, quinacridone-based pigments, and dioxazine-based pigments , Perone-based pigments, perylene-based pigments, thioindigo-based pigments, isoindoline-based pigments, isoindolinone-based pigments, quinophthalone-based pigments, Shihlin-based pigments, and metal complex-based pigments. As the acidic group of the pigment derivative, a sulfonic acid group, a carboxylic acid group and a salt thereof are preferable, a carboxylic acid group and a sulfonic acid group are more preferable, and a sulfonic acid group is further preferable. As the basic 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 is preferably 1 to 30% by mass, more preferably 3 to 20% by mass, based on the mass of the pigment. Only one type of pigment derivatives may be used, or two or more types may be used simultaneously.

<Polymerization inhibitor> The curable composition may contain a polymerization inhibitor. By containing the polymerization inhibitor, the curable composition has more excellent stability over time. In addition, in this specification, time-dependent stability means that the cured film having an excellent pattern shape can be obtained even when the curable composition is stored for a predetermined period of time after the preparation of the curable composition. The polymerization inhibitor has the effect of suppressing the reaction between the polyfunctional thiol compound and the polymerizable compound in the curable composition during storage, and it is presumed that the above-mentioned effects can be obtained. The content of the polymerization inhibitor is preferably 0.001 to 1% by mass, more preferably 0.005 to 1% by mass, and even more preferably 0.05 to 1% by mass relative to the total solid content of the curable composition. When the content of the polymerization inhibitor is within the above range, the curable composition has more excellent stability over time.

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

Examples of the phenolic compound include phenol, 4-methoxyphenol, hydroquinone, 2-tertiary butylhydroquinone, catechol, 4-tertiary butylcatechol, 2,6- Di-tertiary butylphenol, 2,6-di-tertiary butyl 4-methylphenol, 2,6-di-tertiary butyl 4-ethylphenol, 4-hydroxymethyl-2,6- Di-tertiary butylphenol, neotaerythritol tetrakis (3,5-di-tertiary butyl 4-hydroxyhydrocinnamate), 4-methoxy-1-naphthol and 1,4 - Dihydroxynaphthalene, etc.

As a phenolic compound, the phenolic compound represented by formula (IH-1) is preferable.

[Chemical formula 22]

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

As R ₁ to R ₅ in the formula (IH-1), a hydrogen atom, an alkyl group having 1 to 5 carbon atoms (eg, methyl group and ethyl group, etc.), an alkoxy group having 1 to 5 carbon atoms (eg, methyl group) An oxy group, an ethoxy group, etc.), an alkenyl group having 2 to 4 carbon atoms (eg, a vinyl group, etc.), or a phenyl group are preferable. Among them, it is more preferable that R ₁ and R ₅ are independently hydrogen atoms or tertiary butyl groups, R ₂ and R ₄ are more preferably hydrogen atoms, and R ₃ is hydrogen atoms, alkyl groups with 1 to 5 carbon atoms or carbon atoms. An alkoxy group of numbers 1 to 5 is more preferable.

As a quinone type compound, 1, 4- benzoquinone, 1, 2- benzoquinone, 1, 4- naphthoquinone etc. are mentioned, for example.

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

[Chemical formula 23]

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

As the polymerization inhibitor, each of the above-mentioned compounds may be used alone, or two or more of them may be used simultaneously, or three or more of them may be used simultaneously. The polymerization inhibitor preferably contains a phenolic compound. Among them, it is more preferable that the polymerization inhibitor contains two or more phenolic compounds. Curable compositions containing different phenolic compounds have more excellent effects of the present invention. The polymerization inhibitor preferably contains a phenol-based compound and a hindered amine-based compound. The curable composition containing the phenol-based compound and the hindered amine-based compound has more excellent effects of the present invention.

<Solvent> It is preferable that the curable composition contains a solvent. As a solvent, water and an organic solvent are mentioned. The curable composition preferably contains an organic solvent. When the curable composition contains a solvent, the solid content of the curable composition is preferably 10 to 30% by mass. When the solid content of the curable composition is equal to or more than the lower limit value, the viscosity is low, and the coatability is optimized. Furthermore, by reducing the concentration of the more reactive compound, the stability over time is optimized. When the solid content of the curable composition is equal to or less than the upper limit value, the viscosity is maintained at a low temperature, and the coatability is optimized. Moreover, the colorant with heavier specific gravity is not easy to settle, and the stability over time is optimized.

(Organic Solvent) When the curable composition contains an organic solvent, the content of the organic solvent is preferably 70 to 90% by mass relative to the total mass of the curable composition. Moreover, an organic solvent may be used individually by 1 type, and may use 2 or more types together. When two or more kinds of organic solvents are used at the same time, the total amount thereof is preferably in the above-mentioned range.

The organic solvent is not particularly limited, and examples thereof include acetone, methyl ethyl ketone, cyclohexane, dichloroethane, tetrahydrofuran, toluene, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl 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 monoisopropyl ether , ethylene glycol monobutyl ether acetate, 3-methoxypropanol, methoxyethoxyethanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, Diethylene glycol diethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxypropyl acetate, N,N-dimethylformamide, dimethylsulfoxide, γ- Butyrolactone, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, methyl 3-methoxypropionate, 2-heptanone, ethyl Carbitol acetate, butyl carbitol acetate, ethyl acetate, butyl acetate, methyl lactate and ethyl lactate, etc.

When two or more organic solvents are contained, they are selected from the group consisting of the above-mentioned methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethyl acetate Glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclopentanone, ethyl carbitol acetate, butyl carbitol acetate , propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate are preferably constituted by two or more of the group.

(Water) The curable composition may contain water. Water may be intentionally added, or may be unavoidably contained in the curable composition by adding each component contained in the curable composition. The content of water is preferably 0.01 to 1 mass % with respect to the total mass of the curable composition. When content of water is in the said range, generation|occurence|production of a pinhole at the time of manufacture of a cured film will be suppressed, and the moisture resistance of a cured film will be improved.

<Dispersant> It is preferable that the curable composition contains a dispersant. The dispersant helps to improve the dispersibility of the colorant. In this specification, a dispersing agent is a component different from the binder resin mentioned later.

When the curable composition contains a dispersant, the content of the dispersant is preferably 0.05 to 50% by mass, more preferably 0.05 to 30% by mass, based on the total solid content of the curable composition. When content of a dispersing agent is 0.05-30 mass % with respect to the total solid content of a curable composition, the pattern shape of the cured film obtained by hardening a curable composition is more excellent. A dispersing agent may be used individually by 1 type, and may use 2 or more types together. When two or more dispersants are used at the same time, the total amount is preferably within the above range.

As the dispersant, for example, a known pigment dispersant can be appropriately selected and used. Among them, polymer compounds are preferred. As the dispersing agent, polymer dispersing agents [for example, polyamide amine and its salt, polycarboxylic acid and its salt, high molecular weight unsaturated acid ester, modified polyurethane, modified polyester, Modified poly(meth)acrylate, (meth)acrylic copolymer, naphthalenesulfonic acid formaldehyde condensate], polyoxyethylene alkyl phosphate, polyoxyethylene alkyl amine and pigment derivatives, etc. Polymer compounds can be further classified into linear polymers, terminal-modified polymers, graft-type polymers and block-type polymers according to their structures.

(Polymer compound) The polymer compound is adsorbed on the surface of the to-be-dispersed body such as colorants (for example, inorganic pigments), and plays a role of preventing the re-agglomeration of the to-be-dispersed body. Therefore, it is preferable to contain a terminal-modified polymer, a graft-type polymer, and a block-type polymer that are fixed to the surface of the pigment.

Preferably, the polymer compound contains a structural unit including a graft chain. In the present specification, the "structural unit" has the same meaning as the "repeating unit". This polymer compound containing a structural unit including a graft chain has affinity with a solvent due to the graft chain, so it is the dispersibility of colorants such as black pigments and the dispersion stability after time (time stability) Excellent. The polymer compound containing a structural unit including a graft chain has affinity with a polymerizable compound or other resins that can be used together due to the presence of the graft chain. As a result, residues are less likely to be generated during alkali development. When the graft chain becomes longer, the steric repulsion effect is improved, and the dispersibility of black pigments and the like is improved. On the other hand, when the graft chain is too long, the adsorption force to color pigments such as black pigments decreases, and the dispersibility of black pigments and the like tends to decrease. Therefore, the graft chains are preferably those having 40 to 10,000 atoms other than hydrogen atoms, more preferably those having 50 to 2,000 atoms other than hydrogen atoms, and those having 60 to 500 atoms other than hydrogen atoms. for further better. Here, the graft chain means the root of the main chain of the copolymer (the atom bonded to the main chain in the group branched from the main chain) to the end of the group branched from the main chain.

It is preferable that the graft chain contains a polymer structure. Examples of such a polymer structure include a poly(meth)acrylate structure (for example, a poly(meth)acrylic structure), a polyester structure, and a polyurethane structure. Ester structure, polyurea structure, polyamide structure and polyether structure. In order to improve the interaction between the graft chain and the solvent, and thereby improve the dispersibility of black pigments, etc., the graft chain contains a structure selected from the group consisting of polyester structure, polyether structure and poly(meth)acrylate structure The graft chain of at least one kind is preferred, and the graft chain containing at least any one of a polyester structure or a polyether structure is more preferred.

The graft chain-containing macromonomer is not particularly limited, and a reactive double-bonding group-containing macromonomer can be appropriately used.

AA-6 (trade name, Toagosei Company, Limited. manufactured), AA-10 (trade name, manufactured by Toagosei Company, Limited.), AB-6 (trade name, manufactured by Toagosei Company, Limited.), AS-6 (trade name, manufactured by Toagosei Company, Limited.), AN- 6 (trade name, manufactured by Toagosei Company, Limited.), AW-6 (trade name, manufactured by Toagosei Company, Limited.), AA-714 (trade name, manufactured by Toagosei Company, Limited.), AY-707 (trade name, manufactured by Toagosei Company, Limited. Manufactured by Toagosei Company, Limited.), AY-714 (trade name, manufactured by Toagosei Company, Limited.), AK-5 (trade name, manufactured by Toagosei Company, Limited.), AK-30 (trade name, manufactured by Toagosei Company, Limited. manufactured), AK-32 (trade name, manufactured by Toagosei Company, Limited.), Blemmer PP-100 (trade name, manufactured by NOF CORPORATION), Blemmer PP-500 (trade name, manufactured by NOF CORPORATION), Blemmer PP-800 (trade name, manufactured by NOF CORPORATION) name, manufactured by NOF CORPORATION), Blemmer PP-1000 (trade name, manufactured by NOF CORPORATION), Blemmer 55-PET-800 (trade name, manufactured by NOF CORPORATION), Blemmer PME-4000 (trade name, manufactured by NOF CORPORATION), Blemmer PSE -400 (trade name, manufactured by NOF CORPORATION), Blemmer PSE-1300 (trade name, manufactured by NOF CORPORATION), Blemmer 43PAPE-600B (trade name, manufactured by NOF CORPORATION), and the like. Among them, AA-6 (trade name, manufactured by Toagosei Company, Limited.), AA-10 (trade name, manufactured by Toagosei Company, Limited.), AB-6 (trade name, manufactured by Toagosei Company, Limited.), AS -6 (trade name, manufactured by Toagosei Company, Limited.), AN-6 (trade name, manufactured by Toagosei Company, Limited.), Blemmer PME-4000 (trade name, manufactured by NOF CORPORATION) and the like are preferable.

Preferably, the dispersant contains at least one structure selected from the group consisting of polymethyl acrylate, polymethyl methacrylate, and cyclic or chain polyester. More preferably, the dispersant contains at least one structure selected from the group consisting of polymethyl acrylate, polymethyl methacrylate and chain polyester. It is further preferable that the dispersant contains at least one structure selected from the group consisting of a polymethyl acrylate structure, a polymethyl methacrylate structure, a polycaprolactone structure and a polyvalerolactone structure. The dispersing agent may contain the above-mentioned structure alone in one dispersing agent, or may contain a plurality of such structures in one dispersing agent. Here, the polycaprolactone structure refers to what contains a structure in which ε-caprolactone is ring-opened as a repeating unit. The polyvalerolactone structure refers to a structure containing ring-opening of δ-valerolactone as a repeating unit. As a specific example of the dispersing agent containing a polycaprolactone structure, the thing in which j and k in following formula (1) and following formula (2) are 5 is mentioned. Moreover, as a specific example of the dispersing agent containing a polyvalerolactone structure, the thing in which j and k in following formula (1) and following formula (2) are 4 is mentioned. As a specific example of the dispersing agent containing a polymethyl acrylate structure, X ⁵ in the following formula (4) is a hydrogen atom, and R ⁴ is a methyl group. Moreover, as a specific example of the dispersing agent containing a polymethyl methacrylate structure, X ⁵ in following formula (4) is a methyl group, and R ⁴ is a methyl group.

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

[Chemical formula 24]

In Formulas (1) to (4), W ¹ , W ² , W ³ and W ⁴ each independently represent an oxygen atom or NH. Preferably, W ¹ , W ² , W ³ and W ⁴ are oxygen atoms. In formulas (1) to (4), X ¹ , X ² , X ³ , X ⁴ and X ⁵ each independently represent a hydrogen atom or a monovalent organic group. From the viewpoint of limitations in synthesis, it is preferable that 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), and each independently It is more preferably a hydrogen atom or a methyl group, and even more preferably a methyl group.

In Formulas (1) to (4), Y ¹ , Y ² , Y ³ and Y ⁴ each independently represent a divalent linking group, and the structure of the linking group is not particularly limited. Specific examples of the divalent linking group represented by Y ¹ , Y ² , Y ³ and Y ⁴ include the following (Y-1) to (Y-21). In the structures shown below, A and B respectively represent bonding sites. Among the structures shown below, (Y-2) or (Y-13) are more preferable in view of the simplicity of synthesis.

[Chemical formula 25]

In Formulas (1) to (4), Z ¹ , Z ² , Z ³ and Z ⁴ each independently represent a monovalent organic group. The structure of the organic group is not particularly limited, and specifically, an alkyl group, a hydroxyl group, an alkoxy group, an aryloxy group, a heteroaryloxy group, an alkylsulfide group, an arylsulfide group, a heteroarylsulfide group, and Amines, etc. Among these, as the organic groups represented by Z ¹ , Z ² , Z ³ and Z ⁴ , those having a steric repulsion effect are preferred from the viewpoint of improving dispersibility, and each independently has 5 to 24 carbon atoms. Alkyl group or alkoxy group is more preferable, wherein, branched alkyl group with carbon number of 5 to 24, cyclic alkyl group with carbon number of 5 to 24 or alkoxy group with carbon number of 5 to 24 is more preferable. . In addition, the alkyl group contained in the alkoxy group may be linear, branched, or cyclic.

In Formulas (1) to (4), n, m, p, and q are each independently an integer of 1 to 500. In Formula (1) and Formula (2), j and k each independently represent an integer of 2 to 8. From the viewpoint of the stability over time and developability of the curable composition, j and k in the formulas (1) and (2) are preferably integers of 4 to 6, and 5 is the most optimal.

In formula (3), R ³ represents a branched or straight-chain 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, the plural R ^3s present may be the same or different from each other. In formula (4), R ⁴ represents a hydrogen atom or a monovalent organic group, and the monovalent organic group is not particularly limited in structure. R ⁴ is preferably a hydrogen atom, an alkyl group, an aryl group or a heteroaryl group, more preferably a hydrogen atom or an alkyl group. When R ⁴ is an alkyl group, a straight-chain 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 are preferred, and those having 1 to 20 carbon atoms are preferred. A straight-chain alkyl group is more preferable, and a straight-chain alkyl group having 1 to 6 carbon atoms is further preferable. In formula (4), when q is 2 to 500, X ⁵ and R ⁴ present in plural in the graft copolymer may be the same or different from each other.

The polymer compound may contain two or more different structures and a structural unit of a graft chain. That is, the molecule of the polymer compound may contain structural units represented by formulae (1) to (4) having different structures from each other. In formulae (1) to (4), n, m, p, and q are respectively When representing an integer of 2 or more, in the formula (1) and the formula (2), a structure in which j and k are different from each other may be included in the side chain, and in the formula (3) and the formula (4), there are plural ones in the molecule. R ³ , R ⁴ and X ⁵ may be the same or different from each other.

As the structural unit represented by the formula (1), the structural unit represented by the following formula (1A) is more preferable from the viewpoint of the stability over time and developability of the curable composition. As the structural unit represented by the formula (2), the structural unit represented by the following formula (2A) is more preferable from the viewpoint of the stability over time and developability of the curable composition.

[Chemical formula 26]

In formula (1A), X ¹ , Y ¹ , Z ¹ and n have the same meanings as X ¹ , Y ¹ , Z ¹ and n in formula (1), and the preferred ranges are also the same. In formula (2A), X ² , Y ² , Z ² and m have the same meanings as X ² , Y ² , Z ² and m in formula (2), and the preferred ranges are also the same.

As the structural unit represented by the formula (3), the structural unit represented by the following formula (3A) or formula (3B) is more preferable from the viewpoint of the stability over time and developability of the curable composition.

[Chemical formula 27]

In formula (3A) or (3B), X ³ , Y ³ , Z ³ and p have the same meanings as X ³ , Y ³ , Z ³ and p in formula (3), and the preferred ranges are also the same.

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

In the polymer compound, the structural unit containing the graft chain (for example, the structural unit represented by the above-mentioned formula (1) to formula (4)) is 2 to 90% of the total mass of the polymer compound in terms of mass. It is preferable to be included in the range, and it is more preferable to be included in the range of 5 to 30%. When the structural unit containing a graft chain is included in this range, the dispersibility of the black pigment is high, and the developability at the time of forming a cured film is favorable.

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

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

The ClogP value is the value calculated by the program "CLOGP" available from Daylight Chemical Information System, Inc. This program provides the "calculated logP" value calculated by the Fragment Approach of Hansch, Leo (see below). The fragment method divides the chemical structure into partial structures (fragments) based on the chemical structure of the compound, and totals 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 specification, the ClogP value means using the value calculated by the program CLOGP v4.82. A. J. Leo, Comprehensive Medicinal Chemistry, Vol.4, C. Hansch, P. G. Sammnens, J. B. Taylor and C. A. Ramsden, Eds., p.295, Pergamon Press, 1990 C. Hansch & A. J. Leo. SUbstituent Constants For Correlation Analysis in Chemistry and Biology. John Wiley & Sons. A.J. Leo. Calculating logPoct from structure. Chem. Rev., 93, 1281-1306, 1993.

logP represents the common logarithm of the partition coefficient P (Partition Coefficient), which is a quantitative value that expresses how an organic compound is distributed in the equilibrium of the two-phase system of oil (usually 1-octanol) and water. It is represented by the following formula. logP=log(Coil/Cwater) In the formula, Coil represents the molar concentration of the compound in the oil phase, and Cwater represents the molar concentration of the compound in the water phase. If the value of logP increases in the positive direction (plus) between 0, it means that the oil solubility increases, and if the absolute value increases in the negative direction (minus), it means that the water solubility increases, which has a negative correlation with the water solubility of organic compounds, as It is widely used as a parameter to estimate the hydrophilicity and hydrophobicity of organic compounds.

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

[Chemical formula 28]

In formulae (i) to (iii), R ¹ , R ² and R ³ each independently represent a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, etc.) or an alkyl group having 1 to 6 carbon atoms (eg 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. It is more preferable that R ² and R ³ are 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. The divalent linking group includes a divalent aliphatic group (eg, an alkylene group, a substituted alkylene group, an alkenylene group, a substituted alkenylene group, an alkynylene group, a substituted alkynylene group), a divalent Aromatic group (for example, aryl-extended group, substituted aryl-extended group), divalent heterocyclic group, oxygen atom (-O-), sulfur atom (-S-), imino group (-NH-), substituted alkylene An amine group (-NR ³¹ -, wherein R ³¹ is an aliphatic group, an aromatic group or a heterocyclic group), a carbonyl group (-CO-), a combination thereof, and the like.

The divalent aliphatic group may have a cyclic structure or a branched structure. The carbon number of the aliphatic group is preferably 1 to 20, more preferably 1 to 15, and even more preferably 1 to 10. The aliphatic group may be an unsaturated aliphatic group or a saturated aliphatic group, and a saturated aliphatic group is preferred. Also, the aliphatic group may have a substituent. As an example of a substituent, a halogen atom, an aromatic group, a heterocyclic group, etc. are mentioned.

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

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

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

Z includes aliphatic groups (for example, alkyl groups, substituted alkyl groups, unsaturated alkyl groups, substituted unsaturated alkyl groups), aromatic groups (for example, aryl groups, substituted aryl groups, aryl groups, substituted aryl groups) ), heterocyclyl, or a combination thereof. These groups may contain oxygen atom (-O-), sulfur atom (-S-), imino group (-NH-), substituted imino group (-NR ³¹ -, wherein R ³¹ is an aliphatic group , aromatic or heterocyclic group), carbonyl group (-CO-).

The aliphatic group may have a cyclic structure or a branched structure. The carbon number of the aliphatic group is preferably 1 to 20, more preferably 1 to 15, and even more preferably 1 to 10. The aliphatic group also includes a ring-assembled hydrocarbon group and a cross-linked cyclic hydrocarbon group, and examples of the ring-assembled hydrocarbon group include a bicyclohexyl group, a perhydronaphthyl group, a biphenyl group, and a 4-cyclohexylphenyl group. Examples of the cross-linked cyclic hydrocarbon ring include pinane, bornane, norpinane, norbornane, bicyclooctane (bicyclo[2.2.2]octane) 2-cyclic hydrocarbon rings such as alkane ring and bicyclo[3.2.1]octane ring, etc.), homobledane, adamantane, tricyclo[5.2.1.0 ^2,6 ]decane and tricyclo[4.3.1.1 ^2,5 ] 3-cyclic hydrocarbon rings such as undecane ring, and tetracyclo[4.4.0.1 ^{2,5.1 7,10} ] dodecane and perhydro-1,4-methylene-5,8- 4-cyclic hydrocarbon rings such as methylene naphthalene ring, etc. The cross-linked cyclic hydrocarbon ring also includes fused cyclic hydrocarbon rings, for example, perhydronaphthalene (decahydronaphthalene), perhydroanthracene, perhydrophenanthrene, perhydroacenaphthene, perhydroindene, perhydroindene and perhydropyridine It is a fused ring with a plurality of 5-8 membered cycloalkane rings. The aliphatic group is preferably a saturated aliphatic group rather than an unsaturated aliphatic group. The aliphatic group may have a substituent. Examples of the substituent include a halogen atom, an aromatic group, and a heterocyclic group. However, an aliphatic group does not have an acid group as a substituent.

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

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

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

In the present invention, as the monomer represented by the above-mentioned general formula (i), R ¹ , R ² and R ³ are hydrogen atoms or methyl groups, L is a single bond or an alkylene group, or a divalent monomer including an oxyalkylene structure. A compound in which a linking group, X is an oxygen atom or an imino group, and Z is an aliphatic group, a heterocyclic group or an aromatic group is preferable. The monomer represented by the formula (ii) is preferably a compound in which R ¹ is a hydrogen atom or a methyl group, L is an alkylene group, and Z is an aliphatic group, a heterocyclic group or an aromatic group. The monomer represented by the formula (iii) is preferably a compound 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.

Examples of representative compounds represented by formulae (i) to (iii) include radically polymerizable compounds selected from the group consisting of acrylates, methacrylates, and styrenes. As examples of the representative compounds represented by the formulae (i) to (iii), the compounds described in paragraphs 0089 to 0093 of JP-A No. 2013-249417 can be referred to, the contents of which are incorporated in the present specification.

In the polymer compound, the hydrophobic structural unit is preferably contained in the range of 10 to 90%, and more preferably contained in the range of 20 to 80%, in terms of mass, relative to the total mass of the polymer compound. When the content is within the above range, favorable pattern formation can be achieved.

・Functional groups that can interact with colorants such as black pigments The polymer compounds can introduce functional groups that can interact with colorants such as black pigments. Among them, it is preferable that the polymer compound further contains a structural unit containing a functional group that can interact with colorants such as black pigments. As a functional group which can interact with coloring agents, such as this black pigment, an acid group, a basic group, a coordinating group, a reactive functional group, etc. are mentioned, for example. When the polymer compound contains an acid group, a basic group, a coordinating group or a reactive functional group, it contains a structural unit containing an acid group, a structural unit containing a basic group, and a structural unit containing a coordinating group, respectively. Or it is preferable to contain a reactive structural unit. In particular, when the polymer compound further contains an alkali-soluble group such as a carboxylic acid group as an acid group, developability for pattern formation by alkali development can be imparted to the polymer compound. That is, by introducing an alkali-soluble group into the polymer compound, in the curable composition, the polymer compound serving as a dispersant that contributes to the dispersion of colorants such as black pigments has alkali solubility. The curable composition containing such a polymer compound is excellent in the light-shielding property of the exposed part, and the alkali developability of the unexposed part is improved. Since the polymer compound has a structural unit containing an acid group, the polymer compound tends to be easily integrated with a solvent and the applicability is also improved. It is presumed that this is because the acid group in the structural unit containing the acid group easily interacts with colorants such as black pigments, the polymer compound stably disperses colorants such as black pigments, and the polymer compounds that disperse colorants such as black pigments The viscosity becomes lower, so that the polymer compound itself is easily and stably dispersed.

The structural unit containing the alkali-soluble group as an acid group may be the same structural unit as the structural unit containing the above-mentioned graft chain, or may be a different structural unit, but is a structural unit different from the above-mentioned hydrophobic structural unit (ie. , not equivalent to the above hydrophobic structural units).

Examples of functional groups that can interact with colorants such as black pigments, that is, acid groups, include carboxylic acid groups, sulfonic acid groups, phosphoric acid groups, or phenolic hydroxyl groups. At least one of carboxylic acid groups, sulfonic acid groups, and phosphoric acid groups One type is preferable, and the carboxylic acid group is more preferable from the viewpoints of good adsorption force for colorants such as black pigments and high dispersibility of the colorant. That is, it is preferable that the polymer compound further has a structural unit containing at least one of a carboxylic acid group, a sulfonic acid group, and a phosphoric acid group.

The polymer compound may have one or two or more structural units containing an acid group. The polymer compound may contain a structural unit with an acid group, or may not contain the aforementioned structural unit. When it does, the content of the structural unit with an acid group is converted by mass relative to the total mass of the polymer compound. Preferably, it is 10 to 60% from a viewpoint of suppressing the damage of the image intensity by alkali development.

As functional groups that can interact with colorants such as black pigments, that is, basic groups, there are, for example, primary amine groups, secondary amine groups, tertiary amine groups, heterocycles containing N atoms, and amide groups. The tertiary amine group is preferred from the viewpoint of good adsorption force of colorants such as black pigments and high dispersibility of the pigment. The polymer compound can contain one or more of these basic groups. The polymer compound may contain a structural unit with a basic group, or may not contain the aforementioned structural unit. When it contains, the content of the structural unit with a basic group is converted by mass, relative to the total mass of the polymer compound, 0.01% or more and 50% or less is preferable, and from the viewpoint of suppressing inhibition of developability, 0.01% or more and 30% or less are more preferable.

Examples of functional groups that can interact with colorants such as black pigments, that is, coordinating groups and functional groups having reactivity include acetylacetoxyl, trialkoxysilyl, isocyanate, Acid anhydride and acyl chloride, etc. Acetylacetoxy is preferred from the viewpoints of good adsorption force for colorants such as black pigments and high dispersibility of the pigment. The polymer compound may have one kind or two or more kinds of these groups. The polymer compound may contain the following structural units, or may not contain the aforementioned structural units, wherein the aforementioned structural units contain a coordinating group or contain a reactive functional group. The total mass of the polymer compound is preferably 10% or more and 80% or less, and more preferably 20% or more and 60% or less from the viewpoint of suppressing inhibition of developability.

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

[Chemical formula 29]

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

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

L ₁ in formulas (iv) to (v) represents a single bond or a divalent linking group. Examples of the divalent linking group include divalent aliphatic groups (eg, alkylene, substituted alkylene, alkenylene, substituted alkenylene, alkynylene, and substituted alkynylene), 2 valent aromatic groups (for example, aryl-extended and substituted aryl-extended groups), divalent heterocyclic groups, oxygen atoms (-O-), sulfur atoms (-S-), imino groups (-NH-), A substituted imine bond (-NR ³¹ '-, wherein R ³¹ ' is an aliphatic group, an aromatic group or a heterocyclic group), a carbonyl bond (-CO-), a combination thereof, and the like.

The divalent aliphatic group may have a cyclic structure or a branched structure. The carbon number of the aliphatic group is preferably 1 to 20, more preferably 1 to 15, and even more preferably 1 to 10. The aliphatic group is preferably a saturated aliphatic group rather than an unsaturated aliphatic group. The aliphatic group may have a substituent. As an example of a substituent, a halogen atom, a hydroxyl group, an aromatic group, and a heterocyclic group are mentioned.

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

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

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

In formulas (iv) to (vi), Z ₁ represents a functional group that can interact with colorants such as black pigments in addition to the graft chain, carboxylic acid groups and tertiary amine groups are preferred, and carboxylic acid groups are more preferred. good.

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

As the monomer represented by the formula (iv), R ¹¹ , R ¹² and R ¹³ are each independently a hydrogen atom or a methyl group, L ₁ is an alkylene group or a divalent linking group containing an oxyalkylene structure, X ₁ Preferably, the compound is an oxygen atom or an imino group, and Z ₁ is a carboxylic acid group. The monomer represented by the formula (v) is preferably a compound in which 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. Furthermore, as the monomer represented by the formula (vi), R ¹⁴ , R ¹⁵ and R ¹⁶ are each independently a hydrogen atom or a methyl group, L ₁ is a single bond or an alkylene group, and Z ₁ is a carboxylic acid group. is better.

Hereinafter, representative examples of the monomers (compounds) represented by the formulae (iv) to (vi) are shown. Examples of the monomers include the reaction 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 compound, reaction product of compound containing addition polymerizable double bond and hydroxyl group in molecule and phthalic anhydride, reaction product of compound containing addition polymerizable double bond and hydroxyl group in molecule and tetrahydroxyphthalic anhydride, Reaction product of compound containing addition polymerizable double bond and hydroxyl group in molecule and trimellitic anhydride, reaction product of compound containing addition polymerizable double bond and hydroxyl group and pyromellitic anhydride, acrylic acid, acrylic acid dimer, acrylic acid Oligomers, maleic acid, itaconic acid, fumaric acid, 4-vinyl benzoic acid, vinyl phenol and 4-hydroxybenzyl acrylamide, etc.

From the viewpoints of interaction with colorants such as black pigments, dispersion stability, and permeability to developing solutions, the content of structural units containing functional groups capable of interacting with colorants such as black pigments is relative to the amount of the polymer compound. The total mass is preferably 0.05% by mass to 90% by mass, more preferably 1.0% by mass to 80% by mass, and even more preferably 10% by mass to 70% by mass.

・Other Structural Units Furthermore, in order to improve various properties such as image strength, the polymer compound may further contain a graft chain structural unit, a hydrophobic structural unit, and a black Colorants such as pigments have different structural units of functional groups that interact with each other and have other structural units with various functions (for example, structural units containing the following functional groups, etc., the above-mentioned functional groups have affinity with the dispersion medium used for dispersion) . As such other structural unit, the structural unit derived from radical polymerizable compounds, such as acrylonitrile and methacrylonitrile, is mentioned, for example. The polymer compound can use one or more of these other structural units, and the content of these other structural units, in terms of mass, is preferably 0% or more and 80% or less, preferably 10% or more and 60%, relative to the total mass of the polymer compound. The following is better. When the content is within the above range, sufficient pattern formability can be maintained.

・Physical properties of the polymer compound The acid value of the polymer compound is preferably in the range of 0 mgKOH/g or more and 250 mgKOH/g or less, more preferably in the range of 10 mgKOH/g or more and 200 mgKOH/g or less, and 20 mgKOH/g or more and 120 mgKOH The range below /g is more preferable. When the acid value of the polymer compound is 160 mgKOH/g or less, pattern peeling in image development at the time of forming a cured film is more effectively suppressed. When the acid value of the polymer compound is 10 mgKOH/g or more, the alkali developability is more favorable. In addition, when the acid value of the polymer compound is 20 mgKOH/g or more, precipitation of colorants such as black pigments can be further suppressed, the number of coarse particles can be reduced, and the temporal stability of the curable composition can be further improved.

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

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

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

Specific examples of the polymer compound include "DA-7301" manufactured by Kusumoto Chemicals, Ltd., "Disperbyk-101 (polyamidoamine phosphate) manufactured by BYK Chemie, Inc., 107 (carboxylate), 110 (acid group-containing copolymer), 111 (phosphoric acid-based 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 (urethane type), EFKA4330～4340 (block copolymer), 4400～4402 ( Modified polyacrylate), 5010 (polyester amide), 5765 (high molecular weight polycarboxylate), 6220 (fatty acid polyester), 6745 (phthalocyanine derivative), 6750 (azo pigment derivative)”, "AJISPER PB821, PB822, PB880, PB881" manufactured by Ajinomoto Fine-Techno Co., Inc., "Flowlen TG-710 (urethane oligomer)" manufactured by Kyoeisha Chemical Co., Ltd., "polyflow" No.50E, No.300 (acrylic copolymer)", "disparon KS-860, 873SN, 874, #2150 (aliphatic polyvalent carboxylic acid), #7004 (polyetherester) manufactured by Kusumoto Chemicals, Ltd. , DA-703-50, DA-705, DA-725", "DEMOL RN, N (formalin naphthalene sulfonate condensation polymer), MS, C, SN-B (formalin aromatic sulfonate condensation polymer) manufactured by Kao Corporation compound)", "HOMOGENOL L-18 (polymer polycarboxylic acid)", "EMULGEN920, 930, 935, 985 (polyoxyethylene nonyl phenyl ether)", "ACETAMIN86 (stearylamine acetate)", Lubrizol "Solsperse 5000 (phthalocyanine derivatives), 22000 (azo pigment derivatives), 13240 (polyesteramine), 3000, 12000, 17000, 20000, 27000 (polymers with functional parts at the terminal)" manufactured by Japan Limited , 24000, 28000, 32000, 38500 (graft copolymer)", "NIKKOL T106 (polyoxyethylene sorbitan monooleate)" manufactured by Nikko Chemicals Co., Ltd., MYS-IEX (polyoxyethylene sorbitan monooleate) stearate)”, Kawaken Fi "HINOACT T-8000E" manufactured by ne Chemicals Co., Ltd., etc., "Organoorganosiloxane polymer KP341" manufactured by Shin-Etsu Chemical Co., Ltd., "W001" manufactured by Yusho Co., Ltd. : Cationic surfactant", polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol Nonionic surfactants such as alcohol laurate, polyethylene glycol distearate, sorbitan fatty acid ester, anionic surfactants such as "W004, W005, W017", Morishita Sangyo Co., Ltd .Manufactured "EFKA-46, EFKA-47, EFKA-47EA, EFKA Polymer 100, EFKA Polymer 400, EFKA Polymer 401, EFKA Polymer 450", "Disperse Aid 6, Disperse Aid 8" manufactured by SAN NOPCO LIMITED , Disperse Aid 15, Disperse Aid 9100" and other polymer dispersants, "ADEKA Pluronic L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, P-123", and "Ionet (trade name) S-20" manufactured by Sanyo Chemical Industries, Ltd., and the like. In addition, Acrylic base FFS-6752, Acrylic base FFS-187, Akurikyua-RD-F8, and Cyclomer P can also be used. Examples of commercially available amphoteric resins include 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., etc. These polymer compounds may be used alone or in combination of two or more.

As specific examples of the polymer compound, reference can be made to the polymer compounds described in paragraphs 0127 to 0129 of JP 2013-249417 A, the contents of which are incorporated in the present specification.

As the dispersing agent, in addition to the above-mentioned polymer compounds, graft copolymers of paragraphs 0037 to 0115 of JP-A No. 2010-106268 (corresponding to the columns of paragraphs 0075 to 0133 of US 2011/0124824 ) can also be used. The contents can be cited and incorporated into this manual. In addition to the above, it is also possible to use the polymer compounds of paragraphs 0028 to 0084 of JP 2011-153283 A (corresponding to the columns of paragraphs 0075 to 0133 of US 2011/0279759 ) including the following constituents, the constituents containing an acidic group The content of the side chain structure bonded through the linking group can be cited and 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. When the content of the binder resin is 0.3 to 25 mass % with respect to the total solid content of the curable composition, the pattern shape of the cured film obtained by curing the curable composition is more excellent. One type of binder resin may be used alone, or two or more types may be used simultaneously. When two or more kinds of binder resins are used at the same time, it is preferable that the total amount thereof is within the above-mentioned range.

As the binder resin, a linear organic polymer is preferably used. As such a linear organic polymer, a well-known thing can be used arbitrarily. In order to realize water development or weak alkaline water development, it is better to choose a linear organic polymer that is soluble or swellable in water or weak alkaline water. Among them, as the binder resin, alkali-soluble resins (resins containing groups that promote alkali-solubility) are particularly preferred. As the binder resin, at least one group that promotes alkali solubility can be contained in the molecule of a linear organic polymer (preferably a molecule with a (meth)acrylic copolymer or a styrene copolymer as the main chain) Appropriate selection of alkali-soluble resins. From the viewpoint of heat resistance, polyhydroxystyrene-based resins, polysiloxane-based resins, (meth)acrylic resins, (meth)acrylamide-based resins, (meth)acrylic acid/(meth)acrylamide Amine copolymer resins, epoxy resins, and polyimide resins are preferred, and from the viewpoint of controlling developability, (meth)acrylic resins, (meth)acrylamide resins, and (meth)acrylic resins are preferred. /(meth)acrylamide copolymer resin or polyimide resin is more preferable. As a group which promotes alkali solubility (henceforth, an acid group is also called), a carboxylic acid group, a phosphoric acid group, a sulfonic acid group, a phenolic hydroxyl group, etc. are mentioned, for example. Among them, what is soluble in an organic solvent and can be developed by a weak alkaline aqueous solution is preferable, and an alkali-soluble resin containing a structural unit derived from (meth)acrylic acid is mentioned as a more preferable one. Only one kind of these acid groups may be sufficient, or two or more kinds may be sufficient as them.

As a binder resin, the radical polymer containing a carboxylic acid group in a side chain is mentioned, for example. As a radical polymer containing a carboxylic acid group in a side chain, for example, Japanese Unexamined Patent Publication No. 59-44615, Japanese Unexamined Patent Publication No. 54-34327, Japanese Unexamined Patent Publication No. 58-12577, and Japanese Unexamined Patent Publication No. 54-25957 , Japanese Patent Laid-Open No. 54-92723, Japanese Patent Laid-Open No. 59-53836 and Japanese Patent Laid-Open No. 59-71048. Examples of the radical polymer containing a carboxylic acid group in a side chain include a resin obtained by copolymerizing a carboxylic acid group-containing monomer alone or by copolymerizing an acid anhydride unit obtained by copolymerizing an acid anhydride-containing monomer alone or by copolymerizing it. Hydrolyzed, half-esterified or half-amidated resin, and epoxy acrylate modified by unsaturated monocarboxylic acid and acid anhydride, etc. Examples of the carboxylic acid group-containing monomer include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, and 4-carboxystyrene. An acidic cellulose derivative containing a carboxylic acid group in a side chain can also be mentioned as an example. As an acid anhydride containing monomer, maleic anhydride etc. are mentioned. In addition, it is useful to add a cyclic acid anhydride to a hydroxyl group-containing polymer. In addition, the acetal-modified polyvinyl alcohol-based binder resin containing an acid group is described in European Patent No. 993966, European Patent No. 1204000, and Japanese Patent Laid-Open No. 2001-318463. The acetal-modified polyvinyl alcohol-based binder resin containing an acid group has an excellent balance of film strength and developability, which is preferable. Furthermore, as the water-soluble linear organic polymer, polyvinylpyrrolidone, polyethylene oxide, and the like are useful. In addition, in order to increase the strength of the cured film, alcohol-soluble nylon and polyether, which is a reaction product of 2,2-bis-(4-hydroxyphenyl)-propane and epichlorohydrin, are also useful. The polyimide resin described in International Publication No. 2008/123097 is also useful.

Among these, [benzyl (meth)acrylate/(meth)acrylic acid/other addition polymerizable vinyl monomers as needed] copolymer and [(meth)acrylate/(meth)acrylic acid] /Other addition polymerizable vinyl monomers as needed] The copolymer is preferable because it is excellent in the balance of film strength, sensitivity, and developability. Examples of commercially available products include Acrylic base FF-187, FF-426 (manufactured by FUJIKURA KASEI CO., LTD.), Akurikyua-RD-F8 (manufactured by NIPPON SHOKUBAI CO., LTD.), and DAICEL-ALLNEX LTD. Manufactured Cyclomer P (ACA) 230AA et al.

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

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

(Acid group-containing structural unit) As the acid group-containing structural unit, it is preferable to contain one or more structural units selected from structural units derived from monomers represented by the following formulae (vii) to (ix).

[Chemical formula 30]

In formulas (vii) to (ix), R ²¹ , R ²² and R ²³ 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 (eg, methyl, ethyl, propyl, etc.). In formula (vii) to formula (ix), R ²¹ , R ²² and R ²³ are preferably each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and are more preferably a hydrogen atom or a methyl group each independently. good. In the formula (vii), it is particularly preferable that R ²¹ and R ²³ are each a hydrogen atom.

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

L ₂ in formulas (vii) to (ix) represents a single bond or a divalent linking group. Examples of the divalent linking group include divalent aliphatic groups (eg, alkylene, substituted alkylene, alkenylene, substituted alkenylene, alkynylene, and substituted alkynylene), 2 valent aromatic groups (for example, aryl-extended and substituted aryl-extended groups), divalent heterocyclic groups, oxygen atoms (-O-), sulfur atoms (-S-), imino groups (-NH-), A substituted imine bond (-NR ⁴¹ '-, wherein R ⁴¹ ' is an aliphatic group, an aromatic group or a heterocyclic group), a carbonyl bond (-CO-), a combination thereof, and the like.

The divalent aliphatic group may have a cyclic structure or a branched structure. The carbon number of the aliphatic group is preferably 1 to 20, more preferably 1 to 15, and even more preferably 1 to 10. The aliphatic group is preferably a saturated aliphatic group rather than an unsaturated aliphatic group. The aliphatic group may have a substituent. As an example of a substituent, a halogen atom, a hydroxyl group, an aromatic group, and a heterocyclic group are mentioned.

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

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

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

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

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

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

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

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

<Surfactant> It is preferable that the curable composition contains a surfactant. The surfactant contributes to improving the coatability of the curable composition.

When the curable composition contains a surfactant, the content of the surfactant is preferably 0.001 to 2.0% by mass relative to the total solid content of the curable composition. Surfactant may be used individually by 1 type, and may use 2 or more types together. When two or more types of surfactants are used at the same time, the total amount is preferably within the above range.

As a surfactant, a fluorine type surfactant, a nonionic type surfactant, a cation type surfactant, an anion type surfactant, a silicone type surfactant, etc. are mentioned, for example.

For example, when the curable composition contains a fluorine-based surfactant, the liquid properties (especially, fluidity) of the curable composition are further improved. That is, when a film is formed using a curable composition containing a fluorine-based surfactant, by reducing the interfacial tension between the surface to be coated and the coating liquid, the wettability to the surface to be coated is improved, and the The coatability of the surface to be coated is improved. Therefore, even when a thin film of about several μm is formed with a small amount of liquid, a uniform film with less uneven thickness can be formed more preferably, which is effective in this respect.

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

Examples of fluorine-based surfactants include Megafac F171, Megafac F172, Megafac F173, Megafac F176, Megafac F177, Megafac F141, Megafac F142, Megafac F143, Megafac F144, Megafac R30, Megafac F437, Megafac F475, Megafac F479, Megafac F482, Megafac F554, Megafac F780 (above, manufactured by DIC CORPORATION), Fluorad FC430, Fluorad FC431, Fluorad FC171 (above, manufactured by Sumitomo 3M Limited), Surflon S-382, Surflon SC-101, Surflon SC-103, Surflon SC -104, Surflon SC-105, Surflon SC-1068, Surflon SC-381, Surflon SC-383, Surflon S-393, Surflon KH-40 (above, manufactured by ASAHI GLASS CO., LTD.), PF636, PF656, PF6320 , PF6520, PF7002 (manufactured by OMNOVA), etc. As the fluorine-based surfactant, a block polymer can also be used, and specific examples thereof include compounds described in JP-A-2011-89090. As a fluorine-type surfactant, the compound (F-1) represented by the following formula can also be mentioned. In the compound (F-1), the structural units represented by (A) and (B) in the formula are 62 mol% and 38 mol%, respectively. In the structural unit represented by formula (B), a, b, and c satisfy the relationship of a+c=14 and b=17, respectively. In addition, the weight average molecular weight of the following compound is, for example, 15,311.

[Chemical formula 31]

Specific examples of nonionic surfactants include glycerin, trimethylolpropane, trimethylolethane, and ethoxylates and propoxylates thereof (eg, glycerol propoxylate, glycerin ethoxylates, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol Dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester (Pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2, Tetronic 304, 701, 704, 901 manufactured by BASF , 904, 150R1), Solsperse20000 (manufactured by Japan Lubrizol Corporation), etc. In addition, Pionin D-6112-W manufactured by TAKEMOTO OIL & FAT CO., LTD, and NCW-101, NCW-1001, and NCW-1002 manufactured by Wako Pure Chemical Industries, Ltd. can also be used.

Specific examples of the cationic surfactant include phthalocyanine derivatives (trade name, EFKA-745, manufactured by MORISSHITA & CO., LTD.), chitosiloxane polymer KP341 (Shin-Etsu Chemical Co., Ltd.), (meth)acrylic (co)polymer polyflow No.75, No.90, No.95 (Kyoeisha Chemical Co., Ltd.), W001 (Yusho Co., Ltd.), and the like.

As an anionic surfactant, W004, W005, W017 (Yusho Co., Ltd.) etc. are mentioned specifically,.

Examples of silicone-based surfactants include "Toray Silicone DC3PA", "Toray Silicone SH7PA", "Toray Silicone DC11PA", "Toray Silicone SH21PA", and "Toray Silicone SH28PA" manufactured by Dow Corning Toray Co., Ltd. ", "Toray Silicone SH29PA", "Toray Silicone SH30PA", "Toray Silicone SH8400", "TSF-4440", "TSF-4300", "TSF-4445", "TSF-4460" manufactured by Momentive Performance Materials Inc. , "TSF-4452", "KP341", "KF6001", "KF6002" manufactured by Shin-Etsu Chemical Co., Ltd., "BYK307", "BYK323", "BYK330" manufactured by BYK Corporation, etc.

<Silane coupling agent> A silane coupling agent means a compound containing a hydrolyzable group and other functional groups in the molecule. In addition, a hydrolyzable group such as an alkoxy group is bonded to a silicon atom. The hydrolyzable group refers to a substituent which is directly bonded to a silicon atom and can generate a siloxane bond by a hydrolysis reaction and/or a condensation reaction. As a hydrolyzable group, a halogen atom, an alkoxy group, an alkenyloxy group, and an alkenyloxy group are mentioned, for example. When the hydrolyzable group contains carbon atoms, the number of carbon atoms is preferably 6 or less, more preferably 4 or less. An alkoxy group having 4 or less carbon atoms or an alkenyloxy group having 4 or less carbon atoms is particularly preferred. When forming a cured film on a substrate, in order to improve the adhesion between the substrate and the cured film, it is preferable that the silane coupling agent does not contain fluorine atoms and silicon atoms (except for the silicon atoms bound by the hydrolyzable groups). Contains fluorine atom, silicon atom (excluding the silicon atom to which the hydrolyzable group is bonded), an extended alkyl group substituted by a silicon atom, a straight-chain alkyl group having 8 or more carbon atoms, and a branched-chain alkyl group having 3 or more carbon atoms is better.

The silane coupling agent preferably contains a group represented by the following formula (Z). * indicates bond position. Formula (Z)*-Si-(R _Z1 ) ₃ In the formula (Z), R _Z1 represents a hydrolyzable group, which is as defined above.

The silane coupling agent preferably contains at least one curable functional group selected from the group consisting of (meth)acryloyloxy, epoxy, and oxetanyl. The sclerosing functional group can be directly bonded to the silicon atom, or can also be bonded to the silicon atom through a linking group. Moreover, a radical polymerizable group is also mentioned as a preferable aspect of the curable functional group contained in the said silane coupling agent.

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

As one of the preferable aspects of the silane coupling agent, the silane coupling agent X represented by the formula (W) can be mentioned. The formula (W) R _Z2 -Lz-Si-(R _Z1 ) ₃ R _z1 represents a hydrolyzable group, and is as defined above. R _z2 represents a hardenable functional group, and is defined as above, and the preferred range is also as above. Lz represents a single bond or a divalent linking group. When Lz represents a divalent linking group, examples of the divalent linking group include an alkylene group which can be substituted by a halogen atom, an aryl group which can be substituted by a halogen atom, -NR ¹² -, -CONR ¹² -, -CO ^- , _-CO2- , _SO2NR12- , -O-, -S-, _-SO2- , or a combination thereof. Among them, at least one selected from the group consisting of an alkylene group that can be substituted by a halogen atom of 2 to 10 carbon atoms and an aryl group that can be substituted by a halogen atom of 6 to 12 carbon atoms, or a combination of these groups. Combination of at least one group selected from the group consisting of -NR ¹² -, -CONR ¹² -, -CO-, -CO ₂ -, SO ₂ NR ¹² -, -O-, -S- and SO ₂ - The group is preferably, the group including the alkylene group, -CO ₂ -, -O-, -CO-, -CONR ¹² - or the combination of these groups which can be substituted by the halogen atom of carbon number 2-10 is better. Here, the above R ¹² represents a hydrogen atom or a methyl group.

Examples of the silane coupling agent X include N-β-aminoethyl-γ-aminopropyl-methyldimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBM-602), N-β-aminoethyl-γ-aminopropyl-methyldimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBM-602), -β-Aminoethyl-γ-aminopropyl-trimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBM-603), N-β-aminoethyl-γ-aminopropyl- Triethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBE-602), γ-aminopropyl-trimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBM- 903), γ-aminopropyl-triethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBE-903), 3-methacryloyloxypropyltrimethoxysilane (Shin- manufactured by Etsu Chemical Co., Ltd., trade name KBM-503) and glycidoxyoctyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBM-4803) and the like.

As another preferable aspect of a silane coupling agent, the silane coupling agent Y which has at least a silicon atom, a nitrogen atom, and a hardenable functional group in a molecule|numerator, and contains the hydrolyzable group which couple|bonded with a silicon atom is mentioned. The silane coupling agent Y only needs to have at least one silicon atom in the molecule, and the silicon atom can bond with the following atoms and substituents. These may be the same atom and substituent, or may be different. The atoms and substituents that can be bonded include hydrogen atoms, halogen atoms, hydroxyl groups, alkyl groups having 1 to 20 carbon atoms, alkenyl groups, alkynyl groups, aryl groups, amine groups that may be substituted with alkyl groups and/or aryl groups, Silyl group, alkoxy group having 1 to 20 carbon atoms, aryloxy group, etc. These substituents may be further substituted by silyl groups, alkenyl groups, alkynyl groups, aryl groups, alkoxy groups, aryloxy groups, thioalkoxy groups, amine groups substituted with alkyl and/or aryl groups, halogen atoms, sulfonic groups amide group, alkoxycarbonyl group, amide group, urea group, ammonium group, alkylammonium group, carboxylic acid group or its salt, sulfo group or its salt, etc. are substituted. In addition, at least one hydrolyzable group is bonded to the silicon atom. The definition of the hydrolyzable group is as described above. The silane coupling agent Y may contain a group represented by the formula (Z).

The silane coupling agent Y has at least one nitrogen atom in the molecule, and the nitrogen atom preferably exists in the form of a secondary amino group or a tertiary amino group, that is, the nitrogen atom contains at least one organic group as a substituent. better. Moreover, as a structure of an amino group, it may exist in a molecule|numerator in the form of the partial structure of a nitrogen-containing heterocyclic ring, and may exist as a substituted amino group, such as aniline. Among them, the organic group includes an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a combination thereof. These may further have a substituent, and examples of the substituent which can be introduced include a silyl group, an alkenyl group, an alkynyl group, an aryl group, an alkoxy group, an aryloxy group, a thioalkoxy group, an amino group, a halogen atom, Sulfonamide group, alkoxycarbonyl group, carbonyloxy group, amide group, urea group, alkoxyammonium group, alkylammonium group, carboxylic acid group or its salt, sulfo group and the like. The nitrogen atom is preferably bonded to the sclerosing functional group via an arbitrary organic linking group. As a preferable organic linking group, the substituent which can introduce|transduce the said nitrogen atom and the organic group which couple|bonded with it can be mentioned.

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

The molecular weights of the silane coupling agent X and the silane coupling agent Y are not particularly limited, and the above-mentioned range is exemplified (preferably 270 or more).

The content of the silane coupling agent in the curable composition is preferably 0.1 to 10% by mass, more preferably 0.5 to 8% by mass, and even more preferably 1.0 to 6% by mass relative to the total solid content in the curable composition .

The curable composition may contain one type of silane coupling agent alone, or may contain two or more types. When the curable composition contains two or more types of silane coupling agents, the total of the silane coupling agents may be within the above range.

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

<Thermal polymerization initiator> The curable composition may contain a thermal polymerization initiator. From the viewpoints of the stability and curability of the photosensitive resin composition, the half-life temperature for one minute of the thermal polymerization initiator is preferably 120 to 300°C, more preferably 150 to 250°C, and even more preferably 150 to 230°C Best, 170～200℃ is particularly good. As long as the 1-minute half-life temperature of the thermal polymerization initiator is equal to or higher than the above lower limit value, the coating film will not be hardened excessively at the time of drying, and developability will be favorable. Curability is favorable as the 1-minute half-life temperature of a thermal polymerization initiator is below the said lower limit. From the viewpoint of volatility, the molecular weight of the thermal polymerization initiator is preferably 100 or more, more preferably 150 or more, further more preferably 200 or more, and particularly preferably 250 or more. For example, the upper limit is preferably 1,000 or less, and more preferably 500 or less. When the molecular weight of the thermal polymerization initiator is at least the above lower limit value, the volatilization of the thermal polymerization initiator at the time of drying of the coating film can be effectively suppressed, and the curability is good.

As the thermal polymerization initiator, a compound which generates a radical by heat (hereinafter, also simply referred to as a thermal radical generator) or a compound which generates an acid by heat (hereinafter, also abbreviated as a thermal acid generator) can be used. In particular, a thermal radical generator is preferable. The thermal radical generator can promote the radical polymerization of ethylenically unsaturated groups, so when a compound containing an ethylenically unsaturated bond-containing group is used as the crosslinking agent, it can more effectively promote the crosslinking agent. Polymerization, can harden in a shorter time. In addition, the reaction in which the polymerization reaction is initiated and accelerated by the thermal acid generator is the ring-opening polymerization of epoxy. Since the polymerization rate of epoxy ring-opening polymerization is slow compared with radical polymerization, hardenability may not be fully accelerated|stimulated.

(Thermal radical generator) As a thermal radical generator, a well-known thermal radical generator can be used. The thermal free radical generator generates free radicals by thermal energy, and is a compound that initiates or promotes the polymerization reaction of the crosslinking agent. Examples of thermal radical generators include aromatic ketones, onium salt compounds, organic peroxides, sulfur compounds, hexaarylbisimidazole compounds, ketoxime ester compounds, borate compounds, and adinium compounds , metallocene compounds, active ester compounds, compounds with carbon-halogen bonds and azo compounds. Among them, azo-based compounds are more preferable.

[Manufacturing method of curable composition] The manufacturing method of a curable composition includes the following mixing and dispersion processes. It is preferable to include a static process and/or a filtration process. Hereinafter, preferred aspects of each process will be described in detail.

[Mixing and Dispersing Process] The mixing and dispersing process is a process for obtaining a curable composition by mixing the above-mentioned components by well-known mixing methods (eg, mixer, homogenizer, high-pressure emulsifier, wet pulverizer, and wet disperser). . In the mixing and dispersing process, the components constituting the curable composition may be blended at one time, or the components may be blended sequentially after being dissolved or dispersed in an organic solvent. The input sequence and operating conditions at the time of cooperation are not particularly limited. The mixing and dispersing process may include the process of making the dispersion.

(Process of Making Dispersion Liquid) The process of making dispersion liquid is a process of mixing colorant, dispersant and solvent, and dispersing colorant by the above method to make dispersion liquid. A curable composition can be produced by mixing other components with the produced dispersion. In the process of producing the dispersion liquid, as the mechanical force for dispersing the pigment, compression, pressing, impact, cutting, pitting, etc. can be mentioned. Specific examples of these treatments include bead milling, sand mixing, roll milling, high-speed impeller, sand milling, jet mixing, high-pressure wet micronization, and ultrasonic dispersion. In addition, the "Encyclopedia of Dispersion Technology, issued by Information Corporation, July 15, 2005" and "Suspension (Solid/Liquid Dispersion System)-Centered Dispersion Technology and Practical Application in Industry" can be preferably used. A comprehensive collection of documents, issued by the Publishing Department of the Management Development Center, on October 10, 1978" for processing and dispersing machines. In the process of making the dispersion, the micronization of the pigment based on the salt milling process can be performed. The raw materials, equipment, processing conditions, etc. used in the salt grinding process can be used, for example, those described in Japanese Patent Application Laid-Open No. 2015-194521 and Japanese Patent Application Laid-Open No. 2012-046629. It is preferable that the manufacturing method of a curable composition contains the process of obtaining the said coloring agent by the thermoplasma method. The process of obtaining the colorant is carried out before mixing the above-mentioned ingredients. The state of the specific manufacturing process of the colorant based on the thermoplasma method is as described above.

<Standing process> The colorant can be subjected to the following resting process before being supplied to the mixing and dispersing process or the process of preparing the dispersion liquid. The standing process is that the colorant obtained by the thermoplasma method is not exposed to the atmosphere after its manufacture, but is left standing in a sealed container with controlled oxygen concentration for a specified time (12-72 hours is preferred, 12- 48 hours is more preferable, and 12-24 hours is further preferable). At this time, it is preferable that the content of moisture in the sealed container is controlled.

In this case, the oxygen (O ₂ ) concentration and the moisture content in the sealed container are preferably 100 ppm or less, more preferably 10 ppm or less, and even more preferably 1 ppm or less. The oxygen (O ₂ ) concentration and the moisture content in the sealed container can be adjusted by adjusting the oxygen concentration and the moisture content in the inert gas supplied into the sealed container. As the inert gas, nitrogen gas and argon gas are preferably used, and among them, nitrogen gas is more preferably used. The surface and grain boundaries of the colorant become stable after the above-mentioned standing process. Thereby, generation|occurrence|production of the pinhole of the cured film obtained by hardening a curable composition can be suppressed. In addition, the above-mentioned resting process can be replaced by the process H described in the manufacturing method of the colorant, and it is preferable to replace by the process H from the viewpoint that the curable composition has more excellent effects of the present invention.

<Filtering process> The filtering process is a process of filtering the curable composition produced by the above-mentioned mixing and dispersing process through a filter. In the filtration process, foreign matter and/or defects can be removed from the hardening composition. As a filter, as long as it is conventionally used for filtering purposes, it can be used without particular limitation. For example, filtration based on fluorine resins such as PTFE (polytetrafluoroethylene), polyamide resins such as nylon, and polyolefin resins (including high density and ultra-high molecular weight) such as polyethylene and polypropylene (PP) can be mentioned. device. Among these raw materials, polypropylene (containing high-density polypropylene) and nylon are preferred. The appropriate pore size of the filter is about 0.1 to 7.0 μm, preferably about 0.2 to 2.5 μm, more preferably about 0.2 to 1.5 μm, and even more preferably about 0.3 to 0.7 μm. By setting it as this range, the filter clogging of the pigment can be suppressed, and fine foreign matter such as impurities and aggregates contained in the pigment can be surely removed. When using filters, it is also possible to combine different filters. In this case, the filtration by the first filter may be performed only once, or may be performed twice or more. When filtration is performed two or more times by combining different filters, it is preferable that the pore diameter after the second filtration is the same as or larger than the pore diameter of the first filtration. It is also possible to combine the first filters with different pore sizes within the above range. The pore size here can be found in the filter manufacturer's nominal value. As a commercially available filter, for example, it is possible to select from various filters provided by NIHON PALL LTD., ADVANTEC TOYO KAISHA, LTD., Nihon Entegris K.K. (former Mykrolis Corpration), KITZ MICRO FILTER CORPORATION, and the like. The second filter can be formed of the same material or the like as the first filter described above. The suitable pore diameter of the second filter is about 0.2 to 10.0 μm, preferably about 0.2 to 7.0 μm, and more preferably about 0.3 to 6.0 μm.

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

The film thickness of the light-shielding film is not particularly limited, but from the viewpoint that the light-shielding film has more excellent effects of the present invention, the film thickness after drying is preferably 0.2 μm or more and 50 μm or less, and 0.3 μm or more and 10 μm. It is more preferably not more than 0.3 μm and not more than 5 μm. The above-mentioned curable composition has a high optical density per unit volume (high light-shielding property), so that the film thickness can be further reduced as compared with a conventional curable composition using a black pigment. The size of the light-shielding film (the length of one side of the light-shielding film provided around the light-receiving portion of the sensor) is preferably 0.001 mm or more and 10 mm or less, and 0.05 mm or more, from the viewpoint that the light-shielding film has more excellent effects of the present invention. 7 mm or less is more preferable, and 0.1 mm or more and 3.5 mm or less are more preferable.

THE MANUFACTURING METHOD OF A CURED FILM Next, the manufacturing method of a cured film (light-shielding film) is demonstrated. Hereinafter, the manufacturing method will be described in detail for each process.

The manufacturing method of a cured film includes the following curable composition layer formation process and exposure process. Preferably, the manufacturing method of the cured film further includes a developing process. Curable composition layer forming process: a process of forming a curable composition layer on a support. Exposure process: the process of exposing the above-mentioned curable composition layer. Development process: The process of developing the cured composition layer after exposure to form a patterned cured film (light-shielding film).

Specifically, the above-mentioned curable composition is applied directly or through another layer on a substrate to form a curable composition layer (curable composition layer forming process), exposed through a predetermined mask pattern, and only exposed to light The irradiated coating film is partially cured (exposure process) and developed with a developer (development process), whereby the above-mentioned cured film can be produced. Hereinafter, each of the above-mentioned processes will be described.

<The curable composition layer formation process> The curable composition layer formation process is a process of forming a curable composition layer on a support body (henceforth a "substrate"). Among them, the coating process including coating the curable composition on the support to form the curable composition layer is preferably, including directly coating the curable composition on the support, so as to form the curable composition on the support The coating process of the material layer is better. Examples of the substrate include alkali-free glass, soda glass, Pyrex (registered trademark) glass, and quartz glass used in liquid crystal display devices, and photoelectric conversion elements used in solid-state imaging elements to which transparent conductive films are attached. Substrates (eg, silicon substrates, etc.), CCD (Charge Coupled Device) substrates, and CMOS (Complementary Metal-Oxide Semiconductor) substrates, etc. In order to improve adhesion to the upper layer, prevent diffusion of substances, or planarize the surface of the substrate, the support may be provided with an undercoat layer (hereinafter, also referred to as "support with undercoat layer").

As a method of applying the curable composition to the substrate, various application methods such as a slit coating method, an ink jet method, a spin coating method, a casting coating method, a roll coating method, and a screen printing method can be applied.

When manufacturing a color filter containing a black matrix for a solid-state imaging element, the coating film thickness of the curable composition is preferably 0.35 μm or more and 1.5 μm or less, and 0.40 μm or more and 1.0 μm from the viewpoint of resolution. More preferably, it is below μm.

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

<Exposure process> The exposure process is a process of exposing the curable composition layer (coating film) formed in the curable composition layer forming process through a mask, and only partially curing the light-irradiated coating film. The exposure is preferably performed by irradiation with actinic rays or radiation, especially ultraviolet rays such as g rays, h rays, and i rays, and more preferably a high-pressure mercury lamp. The exposure amount is not particularly limited, and can be appropriately selected depending on the type of pigment used and/or the shape of the mask pattern. For example, for the coating film formed from the curable composition containing the black pigment described in the examples, the lower limit of the exposure amount is preferably 50 mJ/cm ² or more, more preferably 80 mJ/cm ² or more . The upper limit of the exposure amount is preferably 1,500 mJ/cm ² or less, and more preferably less than 500 mJ/cm ² . If the exposure amount is 80 mJ/cm ² or more and less than 500 mJ/cm ² , the manufacturing method of the cured film (light-shielding film) has more excellent stability and productivity. In addition, the lower limit of the exposure amount is preferably 50 mJ/cm ² or more, more preferably 80 mJ/cm ² or more, for the coating films formed from the curable compositions containing the color pigments described in the examples. . The upper limit of the exposure amount is preferably 1,500 mJ/cm ² or less, more preferably less than 500 mJ/cm ² , further preferably less than 400 mJ/cm ² , and particularly preferably less than 300 mJ/cm ² . If the exposure amount is 80 to less than 300 mJ/cm ² , the method for producing a cured film has more excellent stability and productivity. From the viewpoint of improving the resolution, exposure by an i-ray stepper is preferable in the formation of a light shielding film for a solid-state imaging element.

<Development process> The development process is a process of developing the exposed curable composition layer. Through the development process, a patterned cured film can be obtained. Preferably, the manufacturing method of the above-mentioned cured film includes a developing process and the following cleaning process. In the development process, an alkali development treatment (development process) is performed, so that the unirradiated part of the light in the exposure process is dissolved in the alkali aqueous solution. Thereby, only the photohardened portion (the portion of the coating film irradiated with light) remains. When producing a light-shielding color filter containing a black matrix for a solid-state imaging element as a developing solution, an organic alkali developing solution that does not damage the circuit of the substrate and the like is preferable. The development temperature is usually preferably 20 to 30°C, and the development time is preferably 20 to 90 seconds.

As an alkaline aqueous solution, an inorganic type developing solution and an organic type developing solution are mentioned, for example. Examples of the inorganic developer include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, sodium silicate, or sodium metasilicate dissolved in a concentration of 0.001 to 10% by mass, preferably 0.01 to 10% by mass. 1 mass % alkaline aqueous solution. Examples of the organic developer include aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, or 1,8- Organic basic compounds such as diazabicyclo-[5.4.0]-7-undecene are dissolved in an alkaline aqueous solution having a concentration of 0.001 to 10% by mass, preferably 0.01 to 1% by mass. To the alkaline aqueous solution, for example, an appropriate amount of a water-soluble organic solvent such as methanol and ethanol and/or a surfactant can be added. In addition, as a development method, for example, a spin-on immersion development method, a shower development method, or the like can be used.

<Cleaning process> The cleaning process is a process of cleaning (rinsing) the developed curable composition layer with pure water or the like. There is no restriction|limiting in particular as a cleaning method, A well-known cleaning method can be utilized.

In addition, the manufacturing method of the said cured film may include a baking process after heating the cured film and/or a curing process of exposing the whole surface of the cured film after the development process.

Color filters containing a hardened film (black matrix) are suitable for solid-state imaging devices such as CCD image sensors and/or CMOS image sensors. It is especially suitable for high-resolution CCD image sensors and/or CMOS image sensors of more than 1 million pixels. That is, the color filter containing the said cured film is suitable for a solid-state imaging element. The color filter may include a structure in which a cured film for forming each color pixel is embedded in a space divided into a lattice shape by a partition wall, for example. The said cured film (black matrix) is arrange|positioned between the light-receiving part of each pixel which comprises a CCD image sensor and/or a CMOS image sensor, etc., and the microlens for condensing light, for example.

[Solid-State Imaging Device] The solid-state imaging device includes the above-described cured film (black matrix). The solid-state imaging element includes a black matrix, and it is preferable to include a color filter including a patterned film including pixels of other colors (three colors or four colors) as required. The solid-state imaging element is not particularly limited as long as it includes the above-mentioned black matrix and functions as a solid-state imaging element. A plurality of photodiodes in the light-receiving region and light-receiving elements such as polysilicon include the solid-state imaging element of the black matrix on the surface opposite to the light-receiving element-forming surface of the substrate. The color filter may have a structure in which a cured film forming each color pixel is embedded in a space divided into a lattice shape by a partition wall, for example. In this case, it is preferable that the partition wall has a low refractive index with respect to each color pixel. As an example of an imaging element having such a structure, the solid-state imaging element described in Japanese Patent Application Laid-Open No. 2012-227478 and Japanese Patent Application Laid-Open No. 2014-179577 can be mentioned.

[Image Display Device] The cured film described above can be preferably used for an image display device (eg, a liquid crystal display device, an organic electroluminescence display device, and the like).

The definition of an image display device and the details of each image display device are described in, for example, "Electronic Display Device (Akio Sasaki, published by Kogyo Chosakai Publishing Co., Ltd. in 1990)" and "Display Device (Ibuki Junsho). published by Sangyo Book Co., Ltd. in Heisei 1)" etc. The liquid crystal display device is described, for example, in "Second Generation Liquid Crystal Display Technology (Edited by Tatsuo Uchida, published in 1994 by Kogyo Chosakai Publishing Co., Ltd.)." The said cured film is suitable for the liquid crystal display device of the aspect of the said "2nd generation liquid crystal display technology", for example.

As one aspect of the liquid crystal display device containing the above-mentioned cured film, for example, at least one color filter, a liquid crystal layer, and a liquid crystal drive mechanism (including a simple matrix drive method and a liquid crystal drive mechanism including a simple matrix drive method and a source matrix drive mode) liquid crystal display device. The above-mentioned liquid crystal display device includes a plurality of pixel groups, and each pixel constituting the pixel group includes a color filter separated from each other by the above-mentioned cured film (black matrix).

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

The color filter containing the said cured film is suitable for the liquid crystal display device of a color TFT (Thin Film Transistor) system. The liquid crystal display device of the color TFT method is described in, for example, "Color TFT Liquid Crystal Display (published by KYORITSU SHUPPAN CO., LTD., 1996)". Moreover, the above-mentioned color filter is also suitable for horizontal electric field driving methods such as IPS (In Plane Switching); pixel division methods such as MVA (Multi-domain Vertical Alignment); etc. The viewing angle is enlarged The liquid crystal display device, STN (Super-Twist Nematic), TN (Twisted Nematic), VA (Vertical Alignment), OCS (on-chip spacer) ), FFS (fringe field switching), and R-OCB (Reflective Optically Compensated Bend).

The above-described color filter is suitable for a bright and high-definition COA (Color-filter On Array) type liquid crystal display device. For COA-type liquid crystal display devices, in addition to the usual required properties for color filters, properties required for interlayer insulating films, ie, low dielectric constant and peeling solution resistance, are sometimes required. The COA-type liquid crystal display device including the above-mentioned color filter has more excellent resolution or more excellent durability. In addition, in order to satisfy the required characteristics of low dielectric constant, a resin coating film may be further contained on the color filter layer.

These image display methods are described, for example, on page 43 of "EL, PDP, and LCD Displays - Latest Trends in Technology and Markets - (Published by TORAY Research Center, Inc., 2001)". In addition, in the above, EL is an abbreviation for Electroluminescence, PDP is an abbreviation for Plasma Display Panel, and LCD is an abbreviation for liquid crystal display.

The said liquid crystal display device consists of various members, such as an electrode substrate, a polarizing film, a retardation film, a backlight, a spacer, and a viewing angle protection film, in addition to the said color filter. The above-described color filter can be applied to a liquid crystal display device composed of these known members. These components are described in, for example, "'94 Liquid Crystal Display Peripheral Materials and Chemicals Market (Issued by Kentaro Shima CMC-Group. 1994)" and "2003 Current Situation and Future Prospects of Liquid Crystal Related Markets (Volume 2) (Fuji Omorayoshi). Chimera Research Institute, Inc., issued in 2003)". The backlight is described in SID meeting Digest 1380 (2005) (A. Konno et.al) and/or Monthly Display December 2005 issue, pages 18 to 24 (Yoshihiro Shima), SID meeting Digest 1380 (2005) 25 to 30 Page (Takaaki Yagi) et al.

The above cured film is suitable for portable devices such as personal computers, tablet computers, mobile phones, smart phones and digital cameras; OA (Office Automation) devices such as multi-function printers and scanners; surveillance cameras, barcode readers and automatic Industrial equipment such as ATM (automated teller machine), high-speed cameras, and identity authentication using face image authentication; vehicle-mounted camera equipment; medical camera equipment such as endoscopes, capsule endoscopes, and catheters; Biosensors, biosensors, cameras for military reconnaissance, cameras for stereo maps, meteorological and oceanographic observation cameras, terrestrial resource reconnaissance cameras, and astronomical and deep space target exploration cameras and other aerospace equipment The light-shielding member and light-shielding layer of the optical filter and module used in the invention are further suitable for the anti-reflection member and the anti-reflection layer.

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

The above cured film is suitable as an optical filter and an optical film used in a quantum dot display. Moreover, the said cured film is suitable as a member which provides a light-shielding function and an antireflection function. Examples of quantum dot displays include US Patent Application Publication No. 2013/0335677, US Patent Application Publication No. 2014/0036536, US Patent Application Publication No. 2014/0036203, and US Patent Application Publication No. 2014/0035960 recorder. [Example]

Hereinafter, the present invention will be described in more detail based on examples. The materials, usage amounts, ratios, processing contents, processing steps, etc. shown in the following examples can be appropriately changed within the scope of not departing from the gist of the present invention. Therefore, the scope of the present invention is not limitedly construed by the embodiments shown below.

另外，上述式中，“Et”表示乙基（-CH₂ CH₃ ），以下相同。[Synthesis of Polyfunctional Thiol Compound S-15] The polyfunctional thiol compound S-15 represented by the following formula was synthesized by the following method. [Chemical formula 32]

_In addition, in the said _formula , "Et" represents an ethyl group (-CH2CH3), and it is the same below.

Under a nitrogen atmosphere, neotaerythritol tetrakis(3-mercaptopropionate) (manufactured by TCI Corporation) (2.00 g) and acrylic acid (0.295 g) were dissolved in tetrahydrofuran (THF) (10.0 g) (hereinafter, the obtained The liquid is called "reaction liquid"). Next, the internal temperature of the said reaction liquid was cooled to 5 degreeC or less. Triethylamine (0.450 g) was added to the cooled reaction liquid. Then, the liquid temperature of the reaction liquid was heated up to 50 degreeC. After the temperature was raised, the reaction solution was stirred for 3 hours. Ethyl acetate (50 g) and 1N hydrochloric acid (50 g) were added to the stirred reaction solution. Then, the reaction liquid was liquid-separated into an aqueous phase and an organic phase. Next, after washing the organic phase with water (50 g) and adding sodium sulfate to the resulting organic phase, solid matter was filtered from the organic phase, and the resulting filtrate was concentrated under reduced pressure to obtain S-15 (2.01 g) (product rate 87.6%). The structure of the obtained S-15 was identified by ¹ H-NMR (nuclear magnetic resonance). The identification results are shown below.

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

[Synthesis of polyfunctional thiol compound S-16] The polyfunctional thiol compound S-16 represented by the following formula was synthesized by the following method. [Chemical formula 33]

Under a nitrogen atmosphere, neotaerythritol tetrakis(3-mercaptopropionate) (manufactured by TCI Corporation) (2.00 g) and 2-hydroxyethyl acrylate (0.475 g) were dissolved in tetrahydrofuran (10.0 g) to obtain The reaction solution. Next, the internal temperature of the said reaction liquid was cooled to 5 degreeC or less. Triethylamine (0.450 g) was added to the cooled reaction liquid. Then, the liquid temperature of the reaction liquid was heated up to 50 degreeC. After the temperature was raised, the reaction solution was stirred for 3 hours. Then, hexane (50 g) was added to the reaction liquid, and the supernatant liquid component of the reaction liquid after adding hexane was removed. Hexane (50 g) was further added to the reaction liquid from which the supernatant liquid component was removed, and the supernatant liquid component of the reaction liquid after further addition of hexane was removed. Then, the solvent remaining in the reaction liquid was removed by distillation under reduced pressure to obtain S-16 (2.01 g) (yield: 88.8%). The structure of the obtained S-16 was identified by ¹ H-NMR. The identification results are shown below.

( ¹ H-NMR 300MHz deuterated chloroform): 1.35 (t, 3H), 2.64-2.71 (m, 10H), 2.73-2.82 (m, 10H), 3.79-3.87 (m, 2H), 4.09 (s, 8H) ), 4.22-4.29 (m, 2H).

另外，上述式中“Me”表示甲基（-CH₃ ），以下相同。[Synthesis of Polyfunctional Thiol Compound S-17] The polyfunctional thiol compound S-17 represented by the following formula was synthesized by the following method. [Chemical formula 34]

In addition, in the said formula, "Me" represents a methyl group ( _-CH3 ), and it is the same below.

Under a nitrogen atmosphere, neotaerythritol tetrakis(3-mercaptopropionate) (manufactured by TCI) (2.00 g) and 2-(dimethylamino)ethyl acrylate (0.586 g) were dissolved in tetrahydrofuran (10.0 g) g) to obtain a reaction solution. Next, the internal temperature of the said reaction liquid was cooled to 5 degreeC or less. Triethylamine (0.450 g) was added to the cooled reaction liquid. Then, the liquid temperature of the reaction liquid was heated up to 50 degreeC. After the temperature was raised, the reaction solution was stirred for 3 hours. Then, hexane (50 g) was added to the reaction liquid, and the supernatant liquid component of the reaction liquid after adding hexane was removed. Hexane (50 g) was further added to the reaction liquid from which the supernatant liquid component was removed, and the supernatant liquid component of the reaction liquid after further addition of hexane was removed. Then, the solvent remaining in the reaction liquid was removed by distillation under reduced pressure to obtain S-17 (2.15 g) (yield: 83.1%). The structure of the obtained S-17 was identified by ¹ H-NMR. The identification results are shown below.

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

[Synthesis of polyfunctional thiol compound S-26] The polyfunctional thiol compound S-26 represented by the following formula was synthesized by the following method. [Chemical formula 35]

Under a nitrogen atmosphere, neotaerythritol tetrakis(3-mercaptopropionate) (manufactured by TCI) (2.00 g) and 3-(trimethoxysilyl)propyl acrylate (1.92 g) were dissolved in tetrahydrofuran (10.0 g) g) to obtain a reaction solution. Next, the internal temperature of the said reaction liquid was cooled to 5 degreeC or less. Triethylamine (0.450 g) was added to the cooled reaction liquid. Then, the liquid temperature of the reaction liquid was heated up to 50 degreeC. After the temperature was raised, the reaction solution was stirred for 3 hours. Then, hexane (50 g) was added to the reaction liquid, and the supernatant liquid component of the reaction liquid after adding hexane was removed. Hexane (50 g) was further added to the reaction liquid from which the supernatant liquid component was removed, and the supernatant liquid component of the reaction liquid after further addition of hexane was removed. Then, the solvent remaining in the reaction liquid was removed by distillation under reduced pressure to obtain S-26 (2.23 g) (yield: 75.4%). The structure of the obtained S-26 was identified by ¹ H-NMR. The identification results are shown below.

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

[Synthesis of polyfunctional thiol compounds S-8, 20, 22, 24, 25, 64 to 66, 69, 71, 73 to 75, 88 to 90, and 112 to 114] The polyfunctional thiol compounds S-8, 20, 22, 24, 25, 64-66, 69, 71, 73-75, 88-90, and 112-114 were synthesized by the same method as above. In addition, the structures of the respective polyfunctional thiol compounds identified by ¹ H-NMR are shown in Tables 1-1 to 1-6.

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

<Composition> Organic solvent 1 (cyclohexanone)･･･17.12 parts by mass of alkali-soluble resin 1 (benzyl methacrylate/methacrylic acid (47/53 [mass ratio]), 30 mass % propylene glycol monomethyl ether solution, Mw=11,000)･･･1.23 parts by mass of alkali-soluble resin 2 (ACRYCURE RD-F8 (manufactured by NIPPON SHOKUBAI CO., LTD.)) 0.23 parts by mass of polymerizable compound (radical polymerizable compound, Shin-Nakamura Chemical Co., Ltd., NK Ester A-DPH-12E)･･･1.96 parts by mass of a polymerization inhibitor (p-methoxyphenol)･･･0.0007 parts by mass of a photopolymerization initiator (IRGACURE OXE02)･･･0.975 parts by mass Functional thiol compound (polyfunctional thiol compound described in Table 2 below)･･･0.35 parts by mass of fluorine-based surfactant (manufactured by DIC CORPORATION, trade name: Megafac F-475, 1 mass % propylene glycol monomethyl ether ethyl Acid acid solution)･･･2.50 parts by mass Color colorant 1: Dye solution 1 (dye solution prepared by the following method)･･･24.57 parts by mass Color colorant 2: Pigment dispersion liquid P1 (by the following method Prepared C.I. Pigment Blue 15:6 dispersion, solid content concentration 11.8% by mass)･･･51.40 parts by mass

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

[Chemical formula 36]

[Preparation of Dye Solution 1] The dye solution 1 was prepared by mixing the following components. Organic solvent (cyclohexanone)･･･21.55 parts by mass of dye (Structure A-1 below)･･･3.02 parts by mass [Chemical formula 37]

[Preparation of Pigment Dispersion Liquid P1] Pigment dispersion liquid P1 was prepared by the following procedure. Will include CI Pigment Blue 15:6 (blue pigment, hereinafter also referred to as "PB15:6") 19.4 parts by mass (average primary particle size 55 nm), pigment dispersant DISPERBYK-161 (solid content concentration 30 mass %, manufactured by BYK) 2.95 Parts by mass, Alkali-soluble resin 1 (benzyl methacrylate/methacrylic acid (47/53 [mass ratio]), 30 mass % propylene glycol monomethyl ether solution, Mw=11,000) 2.95 parts by mass in terms of solid content ( A mixed solution of 9.93 parts by mass of the solution) and 165.3 parts by mass of propylene glycol monomethyl ether was mixed with a beads mill (zirconia bead diameter: 0.3 mm) for 3 hours and dispersed. After that, further dispersion treatment was performed at a flow rate of 500 g/min under a pressure of 2000 kg/cm ³ using a high-pressure disperser NANO-3000-10 (manufactured by Beryu Co., Ltd.) with a decompression mechanism. This dispersion treatment was repeated 10 times to obtain a CI Pigment Blue 15:6 dispersion liquid as the pigment dispersion liquid P1. About the obtained pigment dispersion liquid P1, the average primary particle diameter of the pigment was measured by the dynamic light scattering method (Microtrac Nanotrac UPA-EX150 (made by Nikkiso Co., Ltd.)), and it was 24 nm.

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

[PERFORMANCE EVALUATION] The exposure sensitivity was evaluated by the following method about the curable composition of each Example and a comparative example. And the adhesiveness to the glass base material of the pattern formed by the following method on the glass base material was evaluated by the following method using the said curable composition. The evaluation results are collectively shown in Table 2 below.

[Exposure Sensitivity] After spin-coating the curable compositions of the respective Examples and Comparative Examples on a glass substrate, it was dried to form a coating film (curable composition layer) having a thickness of 1.0 μm on the glass substrate. ). The spin coating conditions were applied at 300 rpm for 5 seconds, followed by the application at 800 rpm for 20 seconds, and the drying conditions were dried at 100° C. for 80 seconds. Next, using a test mask with a line width of 2.0 μm, a proximity exposure machine equipped with an ultra-high pressure mercury lamp (manufactured by Hitachi High-Technologies Corporation) was used to expose the obtained samples at various exposure amounts of 10 mJ/cm ² to 2,000 mJ/cm ² . The coating film (curable composition layer) is exposed to light to harden the curable composition layer in a pattern. Next, using a 60 mass % CD-2000 (manufactured by FUJIFILM Electronic Materials Co., Ltd.) developer, the cured film after exposure was developed under the conditions of 25° C. and 60 seconds to obtain a patterned cured film. After that, the obtained patterned cured film was rinsed with running water for 20 seconds, and then air-dried. The exposure sensitivity was evaluated by the exposure amount at which the pattern line width after development of the region irradiated with light in the exposure process became the minimum of 1 μm or more. The smaller the value of the exposure sensitivity, the better the exposure sensitivity of the curable composition. In addition, the exposure sensitivity is preferably less than 300 mJ/cm ² in practical use under the above test conditions. The results are collectively shown in Table 2.

[Adhesion] Whether or not a pattern defect occurred in the patterned cured film produced by the above-mentioned exposure sensitivity test was observed by SEM (Scanning Electron Microscope), and evaluated based on the following criteria. The results are collectively shown in Table 2.

- Evaluation Criteria - A: No pattern defect was observed at all. B: There are 1 to 3 pattern defects per 1.0 μm square pattern. C: There are 4 or more and 10 or less pattern defects per 1.0 μm square pattern. D: There are 11 or more pattern defects per 1.0 μm square pattern. In addition, the evaluation "B" or more is the actual use range.

[Table 2]

From the results shown in Table 2, it was found that the curable compositions of Examples 1 to 23 (curable compositions containing color colorants) containing the prescribed polyfunctional thiol compounds had excellent exposure sensitivity, and had excellent contact with the support. excellent adhesion. On the other hand, the curable composition of Comparative Example 1 containing no polyfunctional thiol compound did not obtain the above-mentioned effects. The polyfunctional thiol compounds of Comparative Example 2 and Comparative Example 3 containing a polyfunctional thiol compound having no interactive group did not obtain the above-mentioned effects. Compared with the curable composition of Example 1, the curable compositions of Examples 2, 10, 18, and 21 in which m of the polyfunctional thiol compound represented by the formula (2) is 3 or more have more excellent exposure sensitivity . Compared with the curable composition of Example 10 in which m+n is equal and m/n is larger than that of Example 18, the obtained cured film has more excellent adhesion to the support. The interacting group different from the thiol group is a carboxylic acid group or a salt thereof, a hydroxyl group, an amino group, a pyridyl group, a phosphoric acid group or a salt thereof, a sulfonic acid group or a salt thereof, or -Si(R ^X ) _p (R ^Y ) Compared with the curable compositions of Examples 2 to 6, 8 and 9 of _3-p , the cured films obtained have better adhesion to the support than those of Example 7 in which the interacting group is a phenyl group .

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

[Examples 57 and 58] In the preparation of the curable composition of Example 1, the content of the polymerizable compound was changed from 1.96 parts by mass to 1.5 parts by mass (Example 57) and 3.0 parts by mass (Example 58), As a result of evaluating in the same manner as described above, the same results as in Example 1 were obtained.

[Preparation of Curable Compositions of Examples 24 to 54, 59 and Comparative Examples 4 to 6] The polyfunctional thiol compounds shown in the columns of Table 4 and the respective components were mixed in the group compositions described in Table 3 , the curable compositions of Examples 24 to 54 and 59 and Comparative Examples 5 and 6 were prepared. The curable composition of Comparative Example 4 was prepared in the same manner as in Example 24 except that the polyfunctional thiol compound was not added. It adjusted with an organic solvent so that the final solid content of each curable composition might become 28 mass %. In addition, an organic solvent was used so that the mass ratio in each curable composition was PGMEA (propylene glycol monomethyl ether acetate)/butyl acetate/cyclohexanone=27/18/27.

[table 3]

<Colorant> Each colorant was produced by the following method.

(Titanium nitride-containing particles (TiN-1)) First, Ti particles (TC-200, manufactured by TOHO TECHNICAL SERVICE CO., LTD.) were subjected to plasma treatment in Ar gas to form Ti nanoparticles . The Ti nanoparticles after the plasma treatment were allowed to stand for 24 hours under the conditions of an O ₂ concentration of 50 ppm or less and 30° C. in an Ar gas atmosphere. After that, it was left to stand at 30° C. for 24 hours in a state in which O ₂ gas was introduced into an Ar atmosphere so that the O ₂ concentration became 100 ppm (pretreatment of Ti particles). Then, the obtained Ti nanoparticles were classified using a TTSP separator manufactured by Hosokawa Micron Corporation under the condition that the yield became 10%, thereby obtaining Ti particle powder. The primary particle diameter of the obtained powder was observed by TEM, and the average particle diameter of 100 particles was obtained by arithmetic mean, and the result was 120 nm. The titanium nitride-containing particle TiN-1 was produced by using the apparatus according to the black composite fine particle production apparatus described in FIG. 1 of International Publication No. 2010/147098. Specifically, in the black composite particle production 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 from the plasma gas supply source, argon gas of 50 L/min and The mixed gas of nitrogen 50L/min produced an argon-nitrogen thermal plasma flame in the plasma torch. A carrier gas of 10 L/min was supplied from the spray gas supply source of the material supply device. With respect to the Ti particles obtained as described above, Fe powder (JIP270M, manufactured by JFE Steel Corporation) and Si powder (Silicon powder SI006031) were mixed so that the respective mass ratios were Ti/Fe/Si=balance/0.05/0.05. This mixture is supplied to a thermoplasmic flame in a plasma torch together with argon as a carrier gas, and is evaporated in the thermoplasmic flame to be highly dispersed in a 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 5 m/sec, and the supply amount was 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 were obtained.

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

X-ray diffraction of titanium nitride-containing particles TiN-1 was carried out by a wide-angle X-ray diffraction method (manufactured by Rigaku Corporation, trade name "RU-200R") by filling a powder sample into a standard sample holder made of aluminum. measured. As measurement conditions, the X-ray source was set to CuKα rays, the output was set to 50kV/200mA, the slit system was set to 1°-1°-0.15mm-0.45mm, the measurement step (2θ) was set to 0.02°, and the scanning speed was set to is 2°/min. Furthermore, the diffraction angle 2θ of the peak derived from the TiN (200) plane observed in the vicinity of the diffraction angle 2θ (42.6°) was measured. Then, from the half width of the peak originating from the (200) plane, the crystallite size of the constituent 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, X-ray diffraction peaks due to TiO ₂ were not observed at all.

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

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

(Production of Titanium Black A-1) 100 g of titanium oxide MT-150A (trade name, manufactured by TAYCA CORPORATION) having an average particle diameter of 15 nm was weighed, and a BET (Brunauer, Emmett, Teller) specific surface area of 300 m ² /g of dioxide was weighed. 25 g of silicon particles AEROSIL300 (registered trademark) 300/30 (manufactured by Evonik Corporation) and 100 g of Disperbyk190 (trade name, manufactured by BYK Corporation) were weighed, and these were added to 71 g of ion-exchanged water to obtain a mixture. Then, using MAZERSTAR KK-400W manufactured by KURABO, the mixture was treated at a revolution speed of 1,360 rpm and an autorotation speed of 1,047 rpm for 30 minutes, whereby a homogeneous mixture aqueous solution was obtained. This mixture aqueous solution was filled in a quartz container, and heated to 920° C. in an oxygen atmosphere using a small rotary kiln (manufactured by MOTOYAMA CO., LTD.). After that, the inside of the small rotary kiln was replaced with nitrogen, and ammonia gas was flowed at 100 mL/min for 5 hours at the same temperature, thereby performing nitridation reduction treatment. The powder collected after the end was pulverized by a mortar to obtain titanium black containing Si atoms and having a powdery specific surface area of 73 m ² /g [a dispersion containing titanium black particles and Si atoms] (hereinafter, marked as "titanium black"). black A-1").

(Preparation of Fe atom-containing niobium nitride-containing particles (NbN)) Fe atom-containing niobium nitride-containing particles were prepared 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, the above-mentioned metal raw material powder was subjected to plasma treatment in an Ar gas to form Nb nanoparticles. The conditions of the above-mentioned plasma treatment are in accordance with the following plasma treatment (1).

･Plasma treatment (1) Plasma treatment (1) was performed by the following method. Plasma treatment (1) was performed under the following conditions using the apparatus according to the above-mentioned black composite particle production apparatus.・High-frequency voltage applied to the high-frequency oscillation coil: Frequency about 4MHz, voltage about 80kVA ・Plasma gas: Argon gas (supply rate 100L/min) ・Carrier gas: Argon gas (supply rate 10L/min) ・In the chamber Environment: Argon gas (supply volume 1,000l/min, flow velocity in chamber 5m/sec) ・Environment in cyclone: Argon gas, internal pressure 50kPa ・Supply velocity of material from chamber to cyclone: 10m/s (average value)

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

Next, the Nb nanoparticles and Fe nanoparticles obtained above are mixed to obtain raw metal powders. This raw material metal powder was plasma-treated in nitrogen gas to obtain niobium nitride-containing particles. The conditions of the above-mentioned plasma treatment are in accordance with the following plasma treatment (2).

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

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

(Production of Fe atom-containing vanadium nitride-containing particles (VN)) In the production of Fe atom-containing niobium nitride-containing particles, instead of Niobium (powder) <100-325mesh> manufactured by Mitsuwa Chemicals Co., Ltd., Vanadium nitride-containing particles (VN) containing Fe atoms were produced by the same method except that metal vanadium powder VHO manufactured by TAIYO KOKO Co., LTD. was used. The content of iron (Fe) atoms in the obtained vanadium nitride-containing particles was measured by ICP emission spectrometry, and as a result, it was 50 mass ppm.

<Dispersant> As the dispersant, the dispersant A having the following structure was used. The numerical value described in each structural unit represents the mass % of each structural unit with respect to all structural units.

・Dispersant A [Chemical formula 38]

<Binder resin> As the binder resin, the following resin A was used. The numerical value described in each structural unit represents the mole % of each structural unit with respect to all structural units. In addition, in the formula of resin A, each abbreviation shows the following. BzMA: Benzyl methacrylate MMA: Methyl methacrylate

・Resin A

･聚合性化合物M2：PET-30（新戊四醇三丙烯酸酯，Nippon Kayaku Co., Ltd.製造）<Polymerizable compound> ・Polymerizable compound M1: Dipionaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd., trade name "KAYARAD", refer to the following formula) [Chemical formula 39]

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

<Photopolymerization initiator> ・OXE-01: Irgacure OXE01 (trade name, manufactured by BASF JAPAN LTD., equivalent to an oxime compound.) [Chemical formula 40]

・OXE-02: Irgacure OXE02 (trade name, manufactured by BASF JAPAN LTD., equivalent to an oxime compound.) [Chemical formula 41]

・PI-3: Photopolymerization initiator having the following structure (equivalent to an oxime compound.)

[Chemical formula 42]

・NCI-831 (trade name, manufactured by ADEKA CORPORATION, equivalent to an oxime compound.) [Chemical formula 43]

・IRG-379: IRGACURE 379EG (trade name, manufactured by BASF JAPAN LTD., equivalent to an oxime compound.) [Chemical formula 44]

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

[Chemical formula 45]

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

[Preparation of Colorant Dispersion Liquid] First, a colorant, a dispersant, and an organic solvent were mixed for 15 minutes with a mixer (EUROSTAR manufactured by IKA) to obtain a mixed liquid of the above-mentioned components. Next, the obtained mixed liquid was subjected to dispersion treatment using NPM-Pilot manufactured by SHINMARU ENTERPRISES CORPORATION under the following conditions to obtain a colorant dispersion liquid.

<Dispersion conditions> ・Bead diameter: φ0.05mm, (zirconia beads manufactured by NIKKATO CORPORATION, YTZ) ・Bead filling rate: 65% by volume ・Peripheral grinding speed: 10 m/sec ・Peripheral speed of separator: 13 m/s ・Performance Mixed liquid volume for dispersion treatment: 15kg ・Circulation flow rate (pump supply rate): 90kg/hour ・Processing liquid temperature: 19～21℃ ・Cooling water: water ・Processing time: about 22 hours

[Performance Evaluation] [Exposure Sensitivity] On a Si substrate whose surface was treated with SiO ₂ , each curable composition was used, and the rotational speed was adjusted so that a cured film having a thickness of 1.5 μm was obtained, and formed by spin coating. A coating film (hardenable composition layer) is formed. The formed coating film was dried by heat treatment (prebaking) at 100° C. for 2 minutes on a hot plate. Using an i-ray stepper (FPA3000i5+ manufactured by Canon Inc.), the above-mentioned pre-baked substrate with a coating film (curable composition layer) was passed through a mask having a line pattern of 200 μm in length and 20 μm in width. Exposure was recorded on the above-mentioned coating film. The coating film after exposure was subjected to spin-on immersion development for 30 seconds using Coater Developer ACT8 manufactured by Tokyo Electron Limited and using tetramethylammonium hydroxide as a developer. After the development, a shower rinsing process was performed with pure water for 20 seconds. The minimum exposure amount maintained without peeling the pattern after development was evaluated as exposure sensitivity. In addition, the exposure sensitivity is preferably less than 500 mJ/cm ² in practical use under the above-mentioned test conditions. The results are collectively shown in Table 4.

[Adhesion] Whether or not a pattern defect occurred in the patterned cured film produced by the above-mentioned exposure sensitivity test was observed by SEM (Scanning Electron Microscope), and evaluated based on the following criteria. The results are collectively shown in Table 4.

- Evaluation Criteria - A: No pattern defect was observed at all. B: There are 1 to 3 pattern defects per 1.0 μm square pattern. C: There are 4 or more and 10 or less pattern defects per 1.0 μm square pattern. D: There are 11 or more pattern defects per 1.0 μm square pattern. In addition, the evaluation "B" or more is the actual use range.

[Pattern shape] Post-baking (temperature: 220° C., time: 300 seconds) was performed on the pattern-shaped cured film produced in the evaluation of the above-mentioned exposure sensitivity. The pattern shape of the cured film after post-baking was measured with a length-measuring SEM (Scanning Electron Microscope). Specifically, the film thickness at the edge of the line pattern and the film thickness at the center were measured, and the ratio (film thickness at the pattern edge/film thickness at the center) was calculated, and evaluated based on the following criteria. In addition, evaluation "2" or more is the actual use range.・7: The ratio is more than 0.98 and 1.00 or less, and the difference in film thickness between the center part and the edge part of the pattern is not observed by SEM observation.・6: The ratio is more than 0.96 and 0.98 or less, and a slight difference in film thickness at the center part and the edge part of the pattern is observed.・5: The ratio is more than 0.94 and 0.96 or less, and a difference in film thickness between the center part and the edge part of the pattern is observed.・4: The ratio is more than 0.92 and 0.94 or less, and the film thickness at the edge is thin and slightly deformed, but it is a level that does not pose a problem in practical use.・3: The ratio is more than 0.90 and 0.92 or less, and the film thickness at the end portion is thin and deformed, but it is a level that does not pose a problem in practical use.・2: The ratio is more than 0.80 and 0.90 or less, and the film thickness at the edge is thin, but it is a level that can be used practically.・1: The ratio is 0.80 or less, and the film thickness at the edge is thin and outside the allowable range.

[Developability] When exposing to the patterned cured film prepared in the evaluation of the above-mentioned exposure sensitivity, a region (unexposed portion) that was shielded by a mask and not irradiated with light was observed by SEM (magnification: 20,000 times). The presence or absence of residues was evaluated for developability. The evaluation criteria are as follows, and Table 4 shows the results comprehensively.

- Evaluation Criteria - A: No residue was observed in the unexposed part at all. B: One or more and three or less residues are observed per 1.0 μm square unexposed portion. C: 4 or more and 10 or less residues are observed per 1.0-micrometer-square unexposed part. D: 11 or more residues were observed per unexposed portion of 1.0 μm square. In actual use, "C" or higher is preferable, and "A" and "B" are evaluated as having excellent performance.

[Table 4]

From the results shown in Table 4, it was found that the curable compositions (curable compositions containing black pigments) of Examples 24 to 54 and 59 containing the prescribed polyfunctional thiol compounds had excellent exposure sensitivity and had Excellent adhesion to the body. On the other hand, the curable composition of Comparative Example 4 which does not contain a polyfunctional thiol compound does not have the above-mentioned effects. The polyfunctional thiol compounds of Comparative Example 5 and Comparative Example 6 containing a polyfunctional thiol compound having no interactive group did not have the above-mentioned effects. Compared with the curable composition of Example 24, the curable compositions of Examples 25 to 54 and 59 in which m of the polyfunctional thiol compound represented by the formula (2) is 3 or more have more excellent exposure sensitivity. A sclerosing composition in which the interactive group different from the thiol group is a hydroxyl group (Example 26), an amine group (Example 27) or a pyridyl group (Example 31), and the interactive group different from the thiol group Compared with the curable composition whose group is phenyl group (Example 30) or Si group (Example 32), it has more excellent developability. A sclerosing composition in which the interacting group different from the thiol group is a carboxylic acid group (Example 25), a phosphoric acid group (Example 28) or a sulfonic acid group (Example 29), and the interaction group different from the thiol group Compared with the curable composition in which the active group is a hydroxyl group (Example 26), an amino group (Example 27) or a pyridyl group (Example 31), it has further excellent developability. It is presumed that this is due to the difference in solubility of the unexposed part due to the difference in the interactive group different from the thiol group. Compared with the curable composition of Example 41 in which m+n is equal and m/n is larger, the curable composition of Example 33 has a more excellent pattern shape and has a more excellent adhesion to the support. Compared with the curable composition of Example 59, the curable compositions of Examples 33, 47, 48, 49 and 50 in which the photopolymerization initiator was an oxime compound had more excellent exposure sensitivity.

In addition, in Table 4, the upward arrow indicates the same as the column immediately above, and "-" indicates that the curable composition does not contain this component.

A curable composition was produced and evaluated in the same manner as in Example 33, except that the polymerizable compound M2 was used instead of the polymerizable compound M1, and the same results as in Example 33 were obtained.

In place of the polymerizable compound M1, a mixture of the polymerizable compounds M1 and M2 was used (the content-to-mass ratio of M1 and M2 in the mixture is the content-mass ratio of M1: the content-mass of M2=1:1, the above-mentioned mixture relative to the curable composition The total content was the same as the content of the polymerizable compound M1 in Example 33.), except that a curable composition was produced and evaluated in the same manner as in Example 33, and the same results as in Example 33 were obtained. .

[Preparation of Carbon Black Dispersion (CB Dispersion) and Evaluation of Curable Composition] In the preparation of the above-described colorant dispersion, the colorant was carbon black (trade name "Color Black S170", Degussa-Hüls AG). A carbon black dispersion (CB dispersion) was obtained by the same method except that the average primary particle size was 17 nm, the BET specific surface area was 200 m ² /g, and carbon black was produced by the gas black method.

In the preparation of the curable composition of Example 33, instead of the colorant dispersion liquid added so that the curable composition contained 58% by mass of titanium nitride-containing particles TiN-1, TiN containing titanium nitride-containing particles was used. -1 Mixture of the colorant dispersion and the above-mentioned CB dispersion (titanium nitride-containing particles TiN-1 in the curable composition: carbon black in the curable composition = 45:13 (mass ratio), the above curable Except that the total content of the titanium nitride-containing particles TiN-1 and carbon black in the composition was 58% by mass), a curable composition was prepared in the same manner and evaluated using this. As a result of the evaluation, it was found that the same evaluation (including exposure sensitivity and adhesion) as in Example 33 was obtained.

[Preparation of Color Pigment Dispersion (PY Dispersion) and Evaluation of Curable Composition] In the preparation of the above-mentioned colorant dispersion, the colorant was Pigment Yellow 150 (manufactured by Hangzhou Star-up Pigment Co., Ltd., A color pigment dispersion (PY dispersion) was obtained by the same method except for the trade name 6150 Pigment Yellow 5GN).

In the preparation of the curable composition of Example 33, instead of the colorant dispersion liquid added so that the curable composition contained 58% by mass of titanium nitride-containing particles TiN-1, TiN containing titanium nitride-containing particles was used. The mixture of the colorant dispersion liquid of -1 and the above-mentioned PY dispersion liquid (titanium nitride-containing particles TiN-1 in the curable composition: Pigment yellow 150 in the curable composition = 45:13 (mass ratio), curable Except that the total content of titanium nitride-containing particles TiN-1 and Pigment Yellow 150 in the composition was 58% by mass), a curable composition was prepared and evaluated in the same manner. As a result of the evaluation, it was found that the same evaluation (including exposure sensitivity and adhesion) as in Example 33 was obtained. Moreover, as a cured film, it is a film with a darker black.

[Preparation of Color Pigment Dispersion (PR Dispersion)] In the preparation of the above-mentioned colorant dispersion, a color was obtained by the same method except that the colorant was C.I. Pigment Red 254 (manufactured by Ciba Specialty Chemicals). Pigment dispersion (PR dispersion).

[Preparation of Color Pigment Dispersion (PB Dispersion)] In the preparation of the above-mentioned colorant dispersion, a color was obtained by the same method except that the colorant was C.I. Pigment Blue 15:6 (manufactured by DIC CORPORATION). Pigment dispersion (PB dispersion).

[Preparation of Color Pigment Dispersion (PV Dispersion)] In the preparation of the above-mentioned colorant dispersion, a color pigment dispersion was obtained by the same method except that the colorant was C.I. Pigment Violet 23 (manufactured by Clariant). (PV dispersion).

In the preparation of the curable composition of Example 33, the above-mentioned titanium nitride-containing particle TiN was used in place of the colorant dispersion liquid added so that the curable composition contained 58% by mass of the titanium nitride-containing particles TiN-1. -1. Mixture of PY, PR, PB and PV dispersion (ratio of titanium nitride-containing particles TiN-1, PY, PR, PB and PV in curable composition; titanium nitride-containing particles TiN-1:PY :PR:PB:PV=70:17:37:36:10 (mass ratio), the total content of titanium nitride-containing particles TiN-1, PY, PR, PB and PV in the curable composition is 58% by mass ), except that the curable composition was prepared in the same way and evaluated. As a result of the evaluation, it was found that the same evaluation (including exposure sensitivity and adhesion) as in Example 33 was obtained, and a film excellent in light-shielding properties in the infrared region was obtained.

In the preparation of the curable composition of Example 33, the above-mentioned titanium nitride-containing particle TiN was used in place of the colorant dispersion liquid added so that the curable composition contained 58% by mass of the titanium nitride-containing particles TiN-1. Mixture of -1 and compound SQ-23 shown below (ratio of titanium nitride-containing particles TiN-1 and compound SQ-23 in curable composition; titanium nitride-containing particles TiN-1: compound SQ-23= A curable composition was prepared in the same manner, except that the total content of the titanium nitride-containing particles TiN-1 and the compound SQ-23 in the curable composition was 50:8 (mass ratio) of 58 mass %.) , and evaluated with this. As a result of the evaluation, it was found that the same evaluation (including exposure sensitivity and adhesion) as in Example 33 was obtained, and a film excellent in light-shielding properties in the infrared region was obtained.

In the preparation of the curable composition of Example 33, the above-mentioned titanium nitride-containing particle TiN was used in place of the colorant dispersion liquid added so that the curable composition contained 58% by mass of the titanium nitride-containing particles TiN-1. A mixture of -1 and the following compound A-52 (ratio of titanium nitride-containing particles TiN-1 and compound A-52 in curable composition; titanium nitride-containing particles TiN-1: compound A-52=50: 8 (mass ratio), the total content of titanium nitride-containing particles TiN-1 and compound A-52 in the curable composition is 58 mass %.), a curable composition was prepared in the same manner, and used together This was evaluated. As a result of the evaluation, it was found that the same evaluation (including exposure sensitivity and adhesion) as in Example 33 was obtained, and a film excellent in light-shielding properties in the infrared region was obtained.

･Compound SQ-23 [Chemical formula 46]

･Compound A-52 (In addition, in the following formula, Ph represents a phenyl group.) [Chemical formula 47]

In Example 1, the evaluation was carried out in the same manner except that the surfactant F-1 was not used. As a result of the evaluation, it was found that the same results as in Example 1 were obtained.

none

none

Claims (30)

A curable composition comprising a polyfunctional thiol compound, a polymerizable compound and a photopolymerization initiator, wherein the polyfunctional thiol compound is a compound represented by formula (2),

In the formula, R ² represents a divalent linking group having 1 or more carbon atoms, m represents an integer of 2 to 14, n represents an integer of 1 to 15, and M ¹ independently represents a single bond, -O-, -S-, -N(R ⁴ )-, -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- or -CH=N-, R ⁴ represents a monovalent organic group, L ³ represents an m+n-valent linking group, and R ¹ represents a group selected from the group consisting of hydroxyl group, NR _a R _a -, pyridyl group, pyridinium group, ammonium group, phosphonium group, and carboxylic acid group or its salt, phosphoric acid group or its salt, sulfonic acid group or its salt, unsubstituted aryl group, -Si(R ^X ) _p (R ^Y ) _3-p and -(OR ^A ) _q -R ^Z of the group At least one; in addition, p represents an integer of 1 to 3, R ^X represents a hydrolyzable group, R ^Y represents a monovalent organic group other than a hydrolyzable group, and p pieces of R ^X and 3-p pieces of R ^Y can be respectively The same or different, and R ^Z represents a hydrogen atom, an alkyl group or an alkoxy group, q represents an integer of 1 to 4, R ^A represents an alkylene group having 1 to 15 carbon atoms, and R _a represents a monovalent organic group ; R ³ represents a divalent unsubstituted aliphatic hydrocarbon group, -C(=O)-, -C(=O)-O-, -OC(=O)-O-, -C(=O)-NH- , -CH=N-, -N(R)-, or a group obtained by combining these with a group selected from the linking group group shown below, R represents an alkyl group; linking group group : Divalent unsubstituted aliphatic hydrocarbon group, -O-, -S-, -N(R ⁴ )-, -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- and groups obtained by combining these; R ⁴ in the aforementioned linking group group represents a monovalent organic group; in addition, R ² and R ³ They may be the same or different from each other, and n R ¹ , m R ² , n R ² , n R ³ , m M ¹ and n M ¹ may be respectively the same or different; where m is relative to The value of n (m/n) is 2 to 5. The curable composition according to claim 1, wherein m is an integer from 3 to 14. A curable composition comprising a polyfunctional thiol compound, a polymerizable compound and a photopolymerization initiator, wherein the polyfunctional thiol compound is a compound represented by formula (2),

In the formula, R ² represents a divalent linking group having 1 or more carbon atoms, m represents an integer of 3 to 14, n represents an integer of 1 to 15, and M ¹ independently represents a single bond, -O-, -S-, -N(R ⁴ )-, -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- or -CH=N-, R ⁴ represents a monovalent organic group, L ³ represents an m+n-valent linking group, and R ¹ represents a group selected from the group consisting of hydroxyl group, NR _a R _a -, pyridyl group, pyridinium group, ammonium group, phosphonium group, and carboxylic acid group or its salt, phosphoric acid group or its salt, sulfonic acid group or its salt, unsubstituted aryl group, -Si(R ^X ) _p (R ^Y ) _3-p and -(OR ^A ) _q -R ^Z of the group At least one; in addition, p represents an integer of 1 to 3, R ^X represents a hydrolyzable group, R ^Y represents a monovalent organic group other than a hydrolyzable group, and p pieces of R ^X and 3-p pieces of R ^Y can be respectively The same or different, and R ^Z represents a hydrogen atom, an alkyl group or an alkoxy group, q represents an integer of 1 to 4, R ^A represents an alkylene group having 1 to 15 carbon atoms, and R _a represents a monovalent organic group ; R ³ represents a divalent unsubstituted aliphatic hydrocarbon group, -C(=O)-, -C(=O)-O-, -OC(=O)-O-, -C(=O)-NH- , -CH=N-, -N(R)-, or a group obtained by combining these with a group selected from the linking group group shown below, R represents an alkyl group; the linking group group : Divalent unsubstituted aliphatic hydrocarbon group, -O-, -S-, -N(R ⁴ )-, -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- and groups obtained by combining these; R ⁴ in the aforementioned linking group group represents a monovalent organic group; in addition, R ² and R ³ They may be the same or different from each other, and the n R ^{1 s} , m R ² s, n R ² s, n R ³ s, m M ^{1 s} , and n M ^{1 s} may be the same or different, respectively. A curable composition comprising a polyfunctional thiol compound, a polymerizable compound and a photopolymerization initiator, wherein the polyfunctional thiol compound is a compound represented by formula (2),

In the formula, R ² represents a divalent linking group having 1 or more carbon atoms, m represents an integer of 2 to 14, n represents an integer of 1 to 15, and M ¹ independently represents a single bond, -O-, -S-, -N(R ⁴ )-, -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- or -CH=N-, R ⁴ represents a monovalent organic group, L ³ represents an m+n-valent linking group, and R ¹ represents a group selected from the group consisting of hydroxyl group, NR _a R _a -, pyridyl group, pyridinium group, ammonium group, phosphonium group, and carboxylic acid group or its salt, phosphoric acid group or its salt, sulfonic acid group or its salt, unsubstituted aryl group, -Si(R ^X ) _p (R ^Y ) _3-p and -(OR ^A ) _q -R ^Z of the group At least one; in addition, p represents an integer of 1 to 3, R ^X represents a hydrolyzable group, R ^Y represents a monovalent organic group other than a hydrolyzable group, and p pieces of R ^X and 3-p pieces of R ^Y can be respectively The same or different, and R ^Z represents a hydrogen atom, an alkyl group or an alkoxy group, q represents an integer of 1 to 4, R ^A represents an alkylene group having 1 to 15 carbon atoms, and R _a represents a monovalent organic group ; R ³ represents a divalent unsubstituted aliphatic hydrocarbon group, -C(=O)-, -C(=O)-O-, -OC(=O)-O-, -C(=O)-NH- , -CH=N-, -N(R)-, or a group obtained by combining these with a group selected from the linking group group shown below, R represents an alkyl group; the linking group group : Divalent unsubstituted aliphatic hydrocarbon group, -O-, -S-, -N(R ⁴ )-, -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- and groups obtained by combining these; R ⁴ in the aforementioned linking group group represents a monovalent organic group; in addition, R ² and R ³ They may be the same or different from each other, and the n R ^{1 s} , m R ² s, n R ² s, n R ³ s, m M ^{1 s} , and n M ^{1 s} may be the same or different, respectively. The curable composition as described in item 4 of the scope of the application, wherein The aforementioned m is an integer of 3 to 14. The curable composition according to any one of items 1 to 5 of the claimed scope, wherein the aforementioned R ¹ represents a group selected from the group consisting of NR _a R _a -, pyridyl, pyridinium, ammonium, phosphonium, at least one of the group of phosphoric acid group or its salt, sulfonic acid group or its salt, unsubstituted aryl group, -Si(R ^X ) _p (R ^Y ) _3-p and -(OR ^A ) _q -R ^Z , In addition, p represents an integer of 1 to 3, R ^X represents a hydrolyzable group, and R ^Y represents a monovalent organic group other than a hydrolyzable group, and p R ^X and 3-p R ^Y may be the same, respectively, or may be In addition, R ^Z represents a hydrogen atom, an alkyl group or an alkoxy group, q represents an integer of 1 to 4, R ^A represents an alkylene group having 1 to 15 carbon atoms, and R _a represents a monovalent organic group. The curable composition according to any one of items 1 to 5 of the claimed scope, wherein the aforementioned R ¹ is selected from the group consisting of hydroxyl, NR _a R _a -, pyridyl, pyridinium, ammonium, phosphonium at least one of a group, a carboxylic acid group or a salt thereof, a phosphoric acid group or a salt thereof, and a sulfonic acid group or a salt thereof, and R _a represents a monovalent organic group. The curable composition according to any one of items 1 to 5 of the claimed scope, wherein the aforementioned R ¹ is selected from the group consisting of hydroxyl, NR _a R _a -, pyridyl, carboxylate or its salt, phosphoric acid at least one of a group or a salt thereof and a sulfonic acid group or a salt thereof, and R _a represents a monovalent organic group. The curable composition according to any one of claims 1 to 5 of the claimed scope, further comprising a colorant. The curable composition according to claim 9, wherein the colorant contains a black pigment. The curable composition according to claim 10, wherein the black pigment contains at least one selected from the group consisting of titanium black and niobium oxynitride. The curable composition of claim 10, wherein the black pigment contains titanium black, and the titanium black is at least one selected from the group consisting of sub-titanium oxide, titanium oxynitride and titanium nitride. The curable composition of claim 9, wherein the coloring agent contains titanium oxynitride; niobium oxynitride; vanadium oxynitride; and contains Nb, V, Co, Cr, Cu, At least one of the group of metal oxides and metal nitrides of one or more metal elements from the group of Mn, Ru, Fe, Ni, Sn, Ti, and Ag. The curable composition according to any one of items 1 to 5 of the claimed scope, wherein the photopolymerization initiator is an oxime compound. The curable composition according to any one of items 1 to 5 of the scope of the application, further comprising a dispersant, the dispersant is a polymer compound, the polymer compound contains a structural unit including a graft chain, the aforementioned The graft chains contain polyester structures. A cured film obtained by curing the curable composition described in any one of Claims 1 to 15. A color filter comprising the cured film described in claim 16 of the scope of application. A light-shielding film comprising the cured film described in claim 16 of the patent application. A solid-state imaging element comprising the cured film described in claim 16 of the patent application. An image display device comprising the cured film described in claim 16 of the patent application scope. A method for producing a cured film, comprising: a process for forming a layer of a curable composition, using the curable composition described in any one of the first to 15th claims in the scope of application, and forming the curable composition on a support layer; and an exposure process, exposing the aforementioned curable composition layer. The method for manufacturing a cured film according to claim 21, wherein the curable composition layer forming process comprises coating the curable composition on the support to form the curable composition on the support Material layer process. The method for producing a cured film according to the 21st or 22nd claim, further comprising: a development process, for developing the exposed curable composition layer; and a cleaning process for developing the developed hardening layer The composition layer is cleaned. A polyfunctional thiol compound, which is a compound represented by formula (2),

In the formula, R ² represents a divalent linking group having 1 or more carbon atoms, m represents an integer of 2 to 14, n represents an integer of 1 to 15, and M ¹ independently represents a single bond, -O-, -S-, -N(R ⁴ )-, -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- or -CH=N-, R ⁴ represents a monovalent organic group, L ³ represents an m+n-valent linking group, and R ¹ represents a group selected from the group consisting of hydroxyl group, NR _a R _a -, pyridyl group, pyridinium group, ammonium group, phosphonium group, and carboxylic acid group or its salt, phosphoric acid group or its salt, sulfonic acid group or its salt, unsubstituted aryl group, -Si(R ^X ) _p (R ^Y ) _3-p and -(OR ^A ) _q -R ^Z of the group At least one; in addition, p represents an integer of 1 to 3, R ^X represents a hydrolyzable group, R ^Y represents a monovalent organic group other than a hydrolyzable group, and p pieces of R ^X and 3-p pieces of R ^Y can be respectively The same or different, and R ^Z represents a hydrogen atom, an alkyl group or an alkoxy group, q represents an integer of 1 to 4, R ^A represents an alkylene group having 1 to 15 carbon atoms, and R _a represents a monovalent organic group ; R ³ represents a divalent unsubstituted aliphatic hydrocarbon group, -C(=O)-, -C(=O)-O-, -OC(=O)-O-, -C(=O)-NH- , -CH=N-, -N(R)-, or a group obtained by combining these with a group selected from the linking group group shown below, R represents an alkyl group; the linking group group : Divalent unsubstituted aliphatic hydrocarbon group, -O-, -S-, -N(R ⁴ )-, -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- and groups obtained by combining these; R ⁴ in the aforementioned linking group group represents a monovalent organic group; in addition, R ² and R ³ They may be the same or different from each other, and n R ¹ , m R ² , n R ² , n R ³ , m M ¹ and n M ¹ may be respectively the same or different; where m is relative to The value of n (m/n) is 2 to 5. The polyfunctional thiol compound according to claim 24, wherein m is an integer from 3 to 14. A polyfunctional thiol compound, which is a compound represented by formula (2),

In the formula, R ² represents a divalent linking group having 1 or more carbon atoms, m represents an integer of 3 to 14, n represents an integer of 1 to 15, and M ¹ independently represents a single bond, -O-, -S-, -N(R ⁴ )-, -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- or -CH=N-, R ⁴ represents a monovalent organic group, L ³ represents an m+n-valent linking group, and R ¹ represents a group selected from the group consisting of hydroxyl group, NR _a R _a -, pyridyl group, pyridinium group, ammonium group, phosphonium group, and carboxylic acid group or its salt, phosphoric acid group or its salt, sulfonic acid group or its salt, unsubstituted aryl group, -Si(R ^X ) _p (R ^Y ) _3-p and -(OR ^A ) _q -R ^Z of the group At least one; in addition, p represents an integer of 1 to 3, R ^X represents a hydrolyzable group, R ^Y represents a monovalent organic group other than a hydrolyzable group, and p pieces of R ^X and 3-p pieces of R ^Y can be respectively The same or different, and R ^Z represents a hydrogen atom, an alkyl group or an alkoxy group, q represents an integer of 1 to 4, R ^A represents an alkylene group having 1 to 15 carbon atoms, and R _a represents a monovalent organic group ; R ³ represents a divalent unsubstituted aliphatic hydrocarbon group, -C(=O)-, -C(=O)-O-, -OC(=O)-O-, -C(=O)-NH- , -CH=N-, -N(R)-, or a group obtained by combining these with a group selected from the linking group group shown below, R represents an alkyl group; the linking group group : Divalent unsubstituted aliphatic hydrocarbon group, -O-, -S-, -N(R ⁴ )-, -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- and groups obtained by combining these; R ⁴ in the aforementioned linking group group represents a monovalent organic group; In addition, R ² and R ³ They may be the same or different from each other, and the n R ^{1 s} , m R ² s, n R ² s, n R ³ s, m M ^{1 s} , and n M ^{1 s} may be the same or different, respectively. A polyfunctional thiol compound, which is a compound represented by formula (2),

In the formula, R ² represents a divalent linking group having 1 or more carbon atoms, m represents an integer of 2 to 14, n represents an integer of 1 to 15, and M ¹ independently represents a single bond, -O-, -S-, -N(R ⁴ )-, -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- or -CH=N-, R ⁴ represents a monovalent organic group, L ³ represents an m+n-valent linking group, and R ¹ represents a group selected from the group consisting of hydroxyl group, NR _a R _a -, pyridyl group, pyridinium group, ammonium group, phosphonium group, and carboxylic acid group or its salt, phosphoric acid group or its salt, sulfonic acid group or its salt, unsubstituted aryl group, -Si(R ^X ) _p (R ^Y ) _3-p and -(OR ^A ) _q -R ^Z of the group At least one; in addition, p represents an integer of 1 to 3, R ^X represents a hydrolyzable group, R ^Y represents a monovalent organic group other than a hydrolyzable group, and p pieces of R ^X and 3-p pieces of R ^Y can be respectively The same or different, and R ^Z represents a hydrogen atom, an alkyl group or an alkoxy group, q represents an integer of 1 to 4, R ^A represents an alkylene group having 1 to 15 carbon atoms, and R _a represents a monovalent organic group ; R ³ represents a divalent unsubstituted aliphatic hydrocarbon group, -C(=O)-, -C(=O)-O-, -OC(=O)-O-, -C(=O)-NH- , -CH=N-, -N(R)-, or a group obtained by combining these with a group selected from the linking group group shown below, R represents an alkyl group; the linking group group : Divalent unsubstituted aliphatic hydrocarbon group, -O-, -S-, -N(R ⁴ )-, -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- and groups obtained by combining these; R ⁴ in the aforementioned linking group group represents a monovalent organic group; in addition, R ² and R ³ They may be the same or different from each other, and the n R ^{1 s} , m R ² s, n R ² s, n R ³ s, m M ^{1 s} , and n M ^{1 s} may be the same or different, respectively. The polyfunctional thiol compound according to claim 27, wherein m is an integer from 3 to 14. The polyfunctional thiol compound according to any one of items 24 to 28 of the claimed scope, wherein the aforementioned R ¹ represents a group selected from the group consisting of NR _a R _a -, pyridyl, pyridinium, ammonium, phosphonium , phosphoric acid group or its salt, sulfonic acid group or its salt, unsubstituted aryl group, -Si(R ^X ) _p (R ^Y ) _3-p and -(OR ^A ) _q -R ^Z at least one kind of the group , in addition, p represents an integer of 1 to 3, R ^X represents a hydrolyzable group, R ^Y represents a monovalent organic group other than the hydrolyzable group, p R ^X and 3-p R ^Y may be the same, respectively, In addition, R ^Z represents a hydrogen atom, an alkyl group or an alkoxy group, q represents an integer of 1 to 4, R ^A represents an alkylene group having 1 to 15 carbon atoms, and R _a represents a monovalent organic group. The polyfunctional thiol compound as described in any one of items 24 to 28 of the claimed scope, wherein the aforementioned R ¹ is selected from the group consisting of hydroxyl, NR _a R _a -, pyridyl, pyridinium, ammonium, At least one of a phosphonium group, a carboxylic acid group or a salt thereof, a phosphoric acid group or a salt thereof, and a sulfonic acid group or a salt thereof, and R _a represents a monovalent organic group.