KR20200121922A - Curable composition, cured film, color filter, light-blocking film, solid-state imaging element, image display device, method for producing cured film, and polyfunctional thiol compound - Google Patents

Abstract

Curable composition, cured film, color filter, light-shielding film, solid-state imaging device, image display device, method of producing cured film, and multifunctional thiol compound, which can obtain a cured film having excellent exposure sensitivity and excellent adhesion to a support Provides. The curable composition contains a polyfunctional thiol compound, a polymerizable compound, and a photoinitiator, and the polyfunctional thiol compound contains two or more thiol groups and an interactive group different from the thiol group.

Description

Curable composition, cured film, color filter, light-shielding film, solid-state imaging device, image display device, cured film manufacturing method, and multifunctional thiol compound {CURABLE COMPOSITION, CURED FILM, COLOR FILTER, LIGHT-BLOCKING FILM, SOLID-STATE IMAGING ELEMENT , IMAGE DISPLAY DEVICE, METHOD FOR PRODUCING 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 device, an image display device, a method for producing a cured film, and a polyfunctional thiol compound.

A color filter used in an image display device is provided with a light-shielding film called a black matrix for the purpose of shielding light between colored pixels and improving contrast.

Further, also in the solid-state imaging device, a light shielding film is provided for the purpose of preventing noise generation and improving image quality. At present, portable terminals of electronic devices such as cellular phones and PDAs (Personal Digital Assistant) are equipped with small and thin imaging units. Such an imaging unit is generally provided with a solid-state imaging device such as a charge coupled device (CCD) image sensor and a Complementary Metal-Oxide Semiconductor (CMOS) image sensor, and a lens for forming a subject image on the solid-state imaging device. have.

In Patent Document 1, "As a photosensitive resin composition for forming a partition wall separating pixels in an image display device, the photosensitive resin composition includes a binder polymer having a carboxyl group in the molecule as component (A), and component (B). A photosensitive resin composition containing a photopolymerizable compound as an example, a photopolymerization initiator as the component (C), a compound having a mercapto group as the component (D), and a black pigment as the component (E)." is described.

Patent Document 1: Japanese Laid-Open Patent Publication No. 2014-041188

The present inventors applied the photosensitive resin composition described in Patent Literature 1 on a support body, and exposed the obtained photosensitive resin composition layer to produce a cured film, and found that there is room for further improvement in exposure sensitivity. Specifically, when trying to obtain a finer pattern shape, the photosensitive resin composition described in Patent Document 1 has found that there is a problem that energy required for exposure increases.

Further, the inventor of the present invention examined the cured film obtained by the above method, and found that there is room for further improvement in adhesion to the support (hereinafter, also referred to as "substrate").

Therefore, the present invention makes it a subject to provide a curable composition capable of obtaining a cured film having excellent exposure sensitivity and excellent adhesion to a support.

Moreover, the present invention makes it a subject to provide a cured film, a color filter, a light-shielding film, a solid-state imaging device, an image display device, a method for producing a cured film, and a polyfunctional thiol compound.

The present inventors, as a result of earnestly examining in order to achieve the above object, found that a curable composition containing a predetermined polyfunctional thiol compound can solve the above object, and completed the present invention.

That is, it discovered that the said subject can be achieved by the following structure.

[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 an interactive group different from the thiol group. Composition.

[2] The curable composition according to [1], in which the polyfunctional thiol compound is a compound represented by formula (1).

[3] The curable composition according to [1] or [2], in which 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 to 14.

[5] Interaction groups other than thiol groups include hydroxyl, amino, pyridinyl, pyridinium, ammonium, phosphonium, carboxylic acid groups or salts thereof, phosphoric acid groups or salts thereof, sulfonic acid groups or salts thereof, aryl The curability according to any one of [1] to [4], which is at least one selected from the group consisting of a group, -Si(R ^X ) _p (R ^Y ) _3-p , and -(OR ^A ) _q -R ^Z Composition.

In addition, p represents an integer of 1 to 3, R ^X represents a hydrolyzable group, R ^Y represents a monovalent organic group excluding a hydrolyzable group, and p R ^X and 3-p R ^Y are each the same Yes, it can be different. Moreover, 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] Interaction groups other than thiol groups are hydroxyl, amino, pyridinyl, pyridinium, ammonium, phosphonium, carboxylic acid groups or salts thereof, phosphoric acid groups or salts thereof, and sulfonic acid groups or salts thereof. The curable composition according to any one of [1] to [5], which is at least one selected from the group consisting of.

[7] The interaction group different from the thiol group is at least one selected from the group consisting of a hydroxyl group, an amino group, a pyridinyl group, a carboxylic acid group or a salt thereof, a phosphoric acid group or a salt thereof, and a sulfonic acid group or a salt thereof, [ The curable composition according to any one of 1] to [6].

[8] The curable composition according to any one of [1] to [7], which further contains a colorant.

[9] The curable composition according to [8], in which the colorant contains a black pigment.

[10] The curable composition according to any one of [1] to [9], wherein the photoinitiator 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 containing the cured film according to [11].

[13] A light shielding film containing the cured film according to [11].

[14] A solid-state imaging device containing the cured film according to [11].

[15] An image display device containing the cured film according to [11].

[16] Curing including a curable composition layer forming step and an exposure step of exposing the curable composition layer, wherein a curable composition layer is formed on a support by using the curable composition according to any one of [1] to [10] Membrane manufacturing method.

[17] The method for producing a cured film according to [16], in which the curable composition layer forming step includes a step of directly applying a curable composition on a support to form a curable composition layer on the support.

[18] The method for producing a cured film according to [16] or [17], further comprising a developing step of developing the exposed curable composition layer, and a washing step of washing the developed curable composition layer.

[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 to 14.

[23] Interaction groups other than thiol groups are hydroxyl, amino, pyridinyl, pyridinium, ammonium, phosphonium, carboxylic acid groups or salts thereof, phosphoric acid groups or salts thereof, sulfonic acid groups or salts thereof, aryl It is described in any one of [19] to [22], which is at least one selected from the group consisting of a group, -Si(R ^X ) _p (R ^Y ) _3-p , and -(OR ^A ) _q -R ^Z Functional thiol compounds.

In addition, p represents an integer of 1 to 3, R ^X represents a hydrolyzable group, R ^Y represents a monovalent organic group excluding a hydrolyzable group, and p R ^X and 3-p R ^Y are each the same Yes, it can be different. Moreover, 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] Interfunctional groups other than thiol groups are hydroxyl groups, amino groups, pyridinyl groups, pyridinium groups, ammonium groups, phosphonium groups, carboxylic acid groups or salts thereof, phosphoric acid groups or salts thereof, and sulfonic acid groups or salts thereof. The polyfunctional thiol compound according to any one of [19] to [23], which is at least one selected from the group consisting of.

Advantageous Effects of Invention 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, the present invention can provide a cured film, a color filter, a light-shielding film, a solid-state imaging device, an image display device, a method for producing a cured film, and a polyfunctional thiol compound.

Hereinafter, the present invention will be described in detail.

Although the following description may be made based on a representative embodiment of the present invention, the present invention is not limited to such an embodiment.

In the present specification, the numerical range indicated by using "~" means a range including a numerical value described before and after "~" as a lower limit value and an upper limit value.

In the notation of the group (atomic group) in the present specification, the notation in which substituted and unsubstituted are not described includes not only not containing a substituent but also containing a substituent. For example, the "alkyl group" includes not only an alkyl group not containing a substituent (unsubstituted alkyl group) but also an alkyl group containing a substituent (substituted alkyl group).

"Active ray" or "radiation" in the present specification means, for example, a bright ray spectrum of a mercury lamp, and far ultraviolet rays, extreme ultraviolet lithography rays (EUV), X-rays, electron rays, etc. typified by excimer lasers. it means. In addition, in this specification, "light" means actinic rays and radiation. The term "exposure" in the present specification refers to a spectrum of a bright ray of a mercury lamp and exposure by far ultraviolet rays, X-rays, EUV rays, etc. typified by excimer lasers, as well as particle rays such as electron beams and ion beams, unless otherwise specified. Includes drawing.

In this specification, "(meth)acrylate" represents an acrylate and a methacrylate. In this specification, "(meth)acrylic" represents acrylic and methacrylic. In this specification, "(meth)acryloyl" represents acryloyl and methacryloyl. In this specification, "(meth)acrylamide" represents acrylamide and methacrylamide.

In the present specification, "monomer" and "monomer" are synonymous. A monomer is distinguished from an oligomer and a polymer, and refers to a compound having a weight average molecular weight of 2,000 or less. In the present specification, a polymerizable compound refers to a compound containing a polymerizable group, and may be a monomer or a polymer. The polymerizable group refers to a group involved in a polymerization reaction.

[Curable composition]

The curable composition is 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 an interactive group different from the thiol group. .

When the present inventor tries to produce a cured film having a fine pattern shape by forming a curable composition layer on a support by using the curable composition containing a thiol compound described in Patent Document 1, and exposing the curable composition layer, I discovered the problem of having to increase the exposure amount.

This is presumed to be because, when attempting to make the pattern shape finer, the opening of the photomask becomes narrow, and as a result, the amount of light irradiated to the curable composition layer further decreases. That is, since the amount of light reaching the bottom portion of the curable composition decreases, it is estimated that the bottom portion of the curable composition layer becomes difficult to cure.

In such a 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, if the exposure amount is increased, light diffracted at the mask opening, so-called "leakage light" tends to increase, and in the upper portion of the curable composition layer (ie, a portion closer to the photomask), the portion to be originally masked is exposed. As a result, there was a case where the pattern shape deteriorated.

In general, when a curable composition layer is formed on a support by using a curable composition containing a photopolymerization initiator, and the curable composition layer is exposed to light, a radical reaction is initiated by a photopolymerization initiator. At this time, radicals generated by the photopolymerization initiator and oxygen in the curable composition layer react, thereby generating peroxy radicals in some cases. Since the peroxy radical does not have an action of advancing the reaction, the polymerization reaction may stop.

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 a thiyl radical that is difficult to undergo polymerization deactivation by donating hydrogen to the peroxy radical, the polymerization reaction continues.

The polyfunctional thiol compound further contains an interactive group different from the thiol group. The interactive group interacts with the support (or, when the support has a top coating layer, with molecules constituting the top coating layer). Therefore, it is estimated that the polyfunctional thiol compound is likely to be unevenly distributed in a portion closer to the support (that is, the bottom portion) in the curable composition layer formed using the curable composition. In the curable composition layer, when the polyfunctional thiol compound is unevenly distributed at the bottom of the curable composition layer with a relatively small amount of light reaching during exposure, it is assumed that the action of the thiol group is more effectively exhibited.

That is, 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 is easily localized on the bottom, cyyl radicals are easily generated at the bottom of the curable composition layer, It is estimated that even with a small amount of light, it is sufficiently hardened to the bottom.

In addition, in the cured film, since the interactive group is unevenly distributed in a portion closer to the support (that is, the bottom portion), the interaction with the support becomes stronger, and it is estimated that it has excellent adhesion to the support.

Hereinafter, components contained in the curable composition according to an aspect of the present invention will be described.

[Multifunctional thiol compound]

The curable composition contains a predetermined polyfunctional thiol compound.

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

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 generally 30 or less are preferable, 20 or less are more preferable, and 14 or less are more preferable.

The number of the 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 interfunctional groups other than the thiol group contained in the polyfunctional thiol compound is not particularly limited, but generally 30 or less are preferable, 20 or less are more preferable, and 15 or less are more preferable.

In addition, in this specification, an interactive group means a group which can interact with another molecule. The interactive group includes a group capable of interacting in any mode 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 to be described later is preferable. Specific examples of the interactive group will be described in detail in the following paragraphs.

The content of the polyfunctional thiol compound is preferably 0.5 to 10 mass% with respect to the total solid content of the curable composition.

When the content of the polyfunctional thiol compound is 0.5 to 10% by mass, exposure sensitivity is more excellent.

The polyfunctional thiol compounds may be used singly or in combination of two or more. When two or more polyfunctional thiol compounds are used in combination, the total amount is preferably within the above range.

<Suitable aspect 1 of polyfunctional thiol compound>

As a polyfunctional thiol compound, a compound represented by the following formula (1) is preferable.

[Formula 1]

In formula (1), L ¹ and L ² each independently represent a divalent linking group. m represents the integer of 2-14, the integer of 3-14 is preferable, and 3-6 are more preferable. When m is an integer of 3 or more, the curable composition has better exposure sensitivity. n represents the 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 m pieces of L ¹ , n pieces of L ² , and n pieces of R ¹ may be the same or different.

Examples of the divalent linking group of L ¹ include a divalent aliphatic hydrocarbon group (preferably 1 to 8 carbon atoms), a divalent aromatic hydrocarbon group (preferably 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 group), or a combination thereof (e.g., alkyleneoxy group, alkyleneoxycarbonyl group, alkylenecarbonyloxy group, etc.) ), etc.

As the divalent linking group of L ² , it is the same as the aspect of L ¹ . In addition, L ¹ and L ² may be the same as or different from each other. In addition, m L ¹ and n L ² in one molecule of the polyfunctional thiol compound may be the same or different.

The m+n-valent linking group of L ³ is, for example, trimethylolpropane residue, -(CH ₂ ) _k- (k represents an integer of 2 to 6) isocyanure having three Trivalent linking groups such as rings, tetravalent linking groups such as pentaerythritol residues or pentavalent linking groups, hexavalent linking groups such as dipentaerythritol residues, and combinations thereof.

m+n is 3 or more, and 4 or more is preferable.

m+n is 29 or less, and 10 or less is preferable.

Examples of the m+n-valent linking group of L ³ include a group represented by any one of the following formulas (A) to (D), or a group in which these are combined.

[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 ³ may be the same or different from each other.

L ⁵ represents a tetravalent group. T ⁴ represents a single bond or a divalent linking group, and four T ⁴ may be the same or different from each other.

L ⁶ represents a pentavalent group. T ⁵ represents a single bond or a divalent linking group, and five T ^5s may be the same or different.

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.

In addition, the definition of the divalent linking group represented by T ³ , T ⁴ , T ⁵ and T ⁶ is synonymous with the definition of the divalent linking group represented by L ¹ described above.

As the m+n-valent linking group of L ³ , a group represented by the following formulas (E) to (J) or a group in which these are combined is preferable.

[Formula 3]

In formulas (E) to (J),

R represents a hydrogen atom or a monovalent organic group. As the monovalent organic group, an alkyl group is preferable. * Indicates a bonding position. t represents the integer of 2-11.

L ³ may be a group represented by the following formulas (K) to (O), or a combination thereof. In the formula, * represents a bonding position.

[Formula 4]

In Formula (1), R ¹ is the same as the aspect of the interactive group different from the thiol group already described.

Among them, since the cured film has more excellent adhesion to the support, examples of the interactive group different from the thiol group include a hydroxyl group, an amino group, a pyridinyl group, a pyridinium group, an ammonium group, a phosphonium group, a carboxylic acid group, or the like. Salt, phosphoric acid group or salt thereof, sulfonic acid group or salt thereof, aryl group, -Si(R ^X ) _p (R ^Y ) _3-p (hereinafter also referred to as “Si group” in the present specification), and -(OR ^A ) At least one selected from the group consisting of _q -R ^Z is preferred, and a hydroxyl group, an amino group, a pyridinyl group, a pyridinium group, an ammonium group, a phosphonium group, a carboxylic acid group or a salt thereof, a phosphoric acid group or a salt thereof, and a sulfonic acid group Or at least one selected from the group consisting of salts thereof is more preferred, and at least one selected from the group consisting of a hydroxyl group, an amino group, a pyridinyl group, a carboxylic acid group or a salt thereof, a phosphoric acid group or a salt thereof, and a sulfonic acid group or a salt thereof Paper is more preferred.

Since the functional group different from the thiol group is the functional group described above, the mechanism of the cured film having better adhesion to the support is not necessarily clear, but the inventors estimate as follows. In other words, interactions (non-bonding intermolecular forces) are largely classified into Van der Waals interactions, π-π stacking, hydrogen-π bonding, electrostatic interactions, or hydrogen bonding, and it is presumed that they are generally stronger in this order, " Hydrogen bonding" is the strongest, followed by "electrostatic interaction". Here, for example, the hydrogen-π bond, which is the bond between the pi electron of the phenyl group and the hydrogen of O-H, is considered to be weak compared to the above two, and it is assumed that the above effect is obtained. In addition, the mechanism by which the effect of the present invention is obtained is not limited to the above guess.

Further, the amino group includes a primary amino group (NH ₂ -), a secondary amino group (NR _a H-), and a tertiary amino 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 a hydrocarbon group (eg, an alkyl group).

In the above -Si(R ^X ) _p (R ^Y ) _3-p , R ^X represents a hydrolyzable group.

In the present specification, the hydrolyzable group is intended to be a group directly connected to a silicon atom (Si) and capable of undergoing a hydrolysis reaction, and, for example, an alkoxy group, a halogen atom, an acyloxy group, an alkenyloxy group, and an isocyloxy group. Anate group, etc. are mentioned.

R ^Y represents a monovalent organic group. However, from the organic group, the hydrolyzable group is excluded.

The monovalent organic group may be an organic group other than a hydrolyzable group, for example, an alkyl group, an alkenyl group, an aryl group, an alkylcarbonyl group, a cycloalkylcarbonyl group, an arylcarbonyl group, an alkyloxycarbonyl group, a cycloalkyloxy group. And a carbonyl group, an aryloxycarbonyl group, an alkylaminocarbonyl group, a cycloalkylaminocarbonyl group, an arylaminocarbonyl group, and a group obtained by combining them. Among them, an alkyl group, an aryl group, an alkenyl group, or a group combining these groups is preferable.

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

p is an integer of 1 to 3. Especially, since the cured film has more excellent adhesiveness with a support body, 3 is preferable for p.

Moreover, p number of R ^X and 3-p number of R ^Ys may be the same or different, respectively.

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 of the alkyl group in the alkyl group and the alkoxy group is preferably 1 to 6, and linear, branched, or It can be any of the illusions.

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

<Suitable aspect 2 of a polyfunctional thiol compound>

As the polyfunctional thiol compound, a compound represented by the following formula (2) is more preferable.

[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 for example, a divalent aliphatic hydrocarbon group (preferably 1 to 8 carbon atoms), a divalent aromatic hydrocarbon group (preferably 6 to 12 carbon atoms), -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 and the group described as L ¹ in the above formula (1), and the like.

In addition, R ² and R ³ may be the same or different from each other, and m R ² , n R ² , and n R ³ may be the same or different.

In formula (2), m represents the integer of 2-14, the integer of 3-14 is preferable, and 3-6 are more preferable. When m is an integer of 3 or more, the curable composition has better exposure sensitivity.

n represents the integer of 1-15, and 1-4 are preferable.

The value of m relative to n (m/n) is not particularly limited, but 0.13 to 14 are preferable, 1 to 5 are more preferable, and 2 to 5 are more preferable.

When m/n is in the range of 1 to 5, the adhesion between the cured film formed on the support body using the curable composition and the support body is more excellent.

When m+n is the same, the more a polyfunctional thiol compound having a smaller m/n, the better the pattern shape obtained by curing the curable composition, and the adhesion between the cured film formed on the support using the curable composition and the support. Better than this.

In the formula (2), M ¹ is each independently 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, m M ¹ and n M ¹ may be the same or different, respectively.

L ³ represents an m+n-valent linking group, and the aspect is as already described. In addition, R ¹ represents an interactive group different from a thiol group, and the aspect thereof is the same as that in the above-described formula (1).

In addition, each of n R ^1s may be the same or different.

The method for synthesizing the polyfunctional thiol compound is not particularly limited, and can be synthesized by combining known methods.

For example, a desired polyfunctional thiol compound can be synthesized by reacting a raw material compound having a plurality of thiol groups with a compound having a predetermined interactive group and a group capable of reacting with the thiol group. In addition, examples of the group capable of reacting with the thiol group include a carbon-carbon double bond group, a carbon-carbon triple bond group, an epoxy group, a carboxyl group, a halogen atom, an alkyl sulfonate group, an aryl sulfonate group, and the like.

More specifically, a desired polyfunctional thiol compound can be synthesized by reacting a (meth)acrylate compound having a predetermined interactive group with a raw material compound having a plurality of thiol groups by Michael addition.

Specific examples of the polyfunctional thiol compound are shown in Table 1 below. 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" means a methyl group (-CH ₃ ). "OTs" represents a tosyl group.

In Tables 1-1 to 1-6, R ¹ to R ³ , L ³ , and M ¹ are groups corresponding to each part in formula (2), and m and n are m in formula (2). And a number corresponding to n.

[Formula 6]

Symbols in Tables 1-1 to 1-6 intend the following contents.

*: The connection point of L ³ and M ¹ is shown.

●: In M ^1, and R ² of the column shows the connection point of the M ¹ and R ^2. Further, in the column R ³ represents a connection point of the R ³ and -S- group.

○: A thiol (-SH) group or a connection point with a -S- group is shown.

R ^3, R ¹ of the broken line (波線): indicates the connection point of the R ³ and R ^1.

Up arrow: indicates the same meaning as the column immediately above.

[Photopolymerization initiator]

The curable composition contains a photoinitiator.

The photopolymerization initiator is not particularly limited as long as it can initiate polymerization of the polymerizable compound, and a known photopolymerization initiator can be used. As a photoinitiator, it is preferable to have photosensitivity to a visible light range from an ultraviolet range, for example. The photoinitiator may be an activator that generates an action with a photoexcited sensitizer to generate an active radical, or may be an initiator that initiates cationic polymerization depending on the kind of the polymerizable compound.

The photopolymerization initiator preferably contains at least one compound having a molar extinction coefficient of at least about 50 in a wavelength range of about 300 nm to 800 nm (more preferably 330 nm to 500 nm).

The content of the photoinitiator is preferably 1 to 9% by mass with respect to the total solid content of the curable composition.

When the content of the photoinitiator is 1 to 9 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.

Photoinitiators may be used individually by 1 type, and may use 2 or more types together. When two or more types of photopolymerization initiators are used in combination, the total amount is preferably within the above range.

As a photoinitiator, for example, halogenated hydrocarbon derivatives (e.g., those containing a triazine skeleton, those containing an oxadiazole skeleton, etc.), acylphosphine compounds such as acylphosphine oxide, hexa Oxime compounds such as arylbiimidazole and oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, and hydroxyacetophenones.

As the halogenated hydrocarbon compound containing the triazine skeleton, for example, Wakabayashi et al., Bull. Chem. Soc. The compound described in Japan, 42, 2924 (1969), the compound described in British Patent Publication No. 1388492, the compound described in Japanese Patent Application Laid-Open No. 53-133428, the compound described in German Patent Publication No. 3337024, J. Org by FC Schaefer et al. . Chem.; 29, 1527 (1964), the compound described in Japanese Patent Laid-Open No. 62-058241, the compound described in Japanese Patent Laid-Open No. Hei 5-281728, the compound described in Japanese Patent Laid-Open No. Hei 5-034920, United States The compounds described in Patent Publication No. 4212976, etc. are mentioned.

From the viewpoint of exposure sensitivity, trihalomethyltriazine compound, benzyldimethylketal compound, α-hydroxyketone compound, α-aminoketone compound, acylphosphine compound, phosphine oxide compound, metallocene compound, oxime compound , Triallylimidazole dimer, onium compound, benzothiazole compound, benzophenone compound, acetophenone compound and its derivatives, cyclopentadiene-benzene-iron complex and its salt, halomethyloxadiazole compound, and 3- A compound selected from the group consisting of aryl substituted coumarin compounds is preferred.

Among them, trihalomethyltriazine compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, oxime compounds, triallylimidazole dimers, onium compounds, benzophenone compounds, or acetophenone compounds are more Preferably, at least one compound selected from the group consisting of a trihalomethyltriazine compound, an α-aminoketone compound, an oxime compound, a triallylimidazole dimer, and a benzophenone compound is more preferable.

In particular, in the case of using the curable composition for the production of a light-shielding film, it is necessary to form a fine pattern in a sharp shape, so it is important that the curable composition is developed without residue on the unexposed portion with curability. From such a viewpoint, it is particularly preferable to use an oxime compound as the photoinitiator. In particular, in the case of forming a fine pattern, stepper exposure is used for exposure for curing, but this exposure machine is sometimes damaged by halogen, and the amount of the photopolymerization initiator added is also required to be kept low. In view of these points, in order to form a fine pattern, it is particularly preferable to use an oxime compound as a photoinitiator.

As a specific example of a photoinitiator, paragraphs 0265 to 0268 of Japanese Unexamined Patent Application Publication No. 2013-029760 can be referred to, for example, and the contents are incorporated herein.

As a photoinitiator, a hydroxyacetophenone compound, an aminoacetophenone compound, and an acylphosphine compound can also be used suitably. More specifically, for example, the aminoacetophenone initiator described in JP-A-10-291969 A and the acylphosphine initiator described in JP-A-4225898 can also be used.

Examples of the hydroxyacetophenone compound include IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, and IRGACURE-127 (trade names, all manufactured by BASF).

Examples of the aminoacetophenone compound include commercially available products IRGACURE-907, IRGACURE-369, and IRGACURE-379EG (brand names, all manufactured by BASF). Examples of the aminoacetophenone compound include compounds described in Japanese Patent Application Laid-Open No. 2009-191179 in which the absorption wavelength is matched to a long-wave light source such as 365 nm or 405 nm.

Examples of the acylphosphine compound include commercially available IRGACURE-819 and DAROCUR-TPO (trade names, all manufactured by BASF).

<Oxime compound>

As a photoinitiator, more preferably, an oxime compound (oxime type initiator) is mentioned.

The curable composition, wherein the photopolymerization initiator is an oxime compound, has better exposure sensitivity. Further, the oxime compound is highly sensitive, has high polymerization efficiency, can cure the curable composition layer irrespective of the colorant concentration, and is preferable because it is easy to design with a high colorant concentration.

As a specific example of an oxime compound, the compound described in Unexamined-Japanese-Patent No. 2001-233842, the compound described in Unexamined-Japanese-Patent No. 2000-080068, and the compound described in Unexamined-Japanese-Patent No. 2006-342166 are mentioned.

As an oxime compound, 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, 2-acetoxyiminopentan-3-one, 2 -Acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3-(4-toluenesulfonyloxy)iminobutan-2-one, and 2- Ethoxycarbonyloxyimino-1-phenylpropan-1-one, etc. are mentioned.

In addition, J. C. S. Perkin II (1979) pp. 1653-1660, J. C. S. Perkin II (1979) pp. 156-162, Journal of Photopolymer Science and Technology (1995) pp. The compound described in 202-232, the compound described in JP 2000-066385 A, JP 2000-080068 A, JP 2004-534797 A, and JP 2006-342166 A. Compounds, etc. are also mentioned.

In a commercial item, IRGACURE-OXE01 (manufactured by BASF), IRGACURE-OXE02 (manufactured by BASF), IRGACURE-OXE03 (manufactured by BASF), or IRGACURE-OXE04 (manufactured by BASF) is also suitably used. In addition, TR-PBG-304 (made by Changzhou Tronly New Electronic Materials Co., Ltd.), Adeka Arcles NCI-831 and Adeka Arcles NCI-930 (manufactured by ADEKA) Or N-1919 (carbazole oxime ester skeleton-containing photoinitiator (made by ADEKA)) can also be used.

As oxime compounds other than those described above, compounds described in Japanese Laid-Open Patent Publication No. 2009-519904 in which an oxime is linked to carbazole N; The compound described in U.S. Patent Publication No. 7626957 in which a hetero substituent is introduced at the benzophenone moiety; The compounds described in Japanese Laid-Open Patent Publication No. 2010-015025 and US Patent Laid-Open Publication No. 2009-292039, in which a nitro group is introduced into a pigment region; Ketoxime compounds described in International Publication No. 2009-131189; Compounds described in US Patent Publication No. 7556910 containing a triazine skeleton and an oxime skeleton in the same molecule; A compound described in Japanese Patent Application Laid-Open No. 2009-221114, which has an absorption maximum at 405 nm and good sensitivity to a g-ray light source, may be used.

Preferably, for example, reference may be made to paragraphs 0274 to 0275 of Japanese Laid-Open Patent Publication No. 2013-029760, the contents of which are incorporated herein by reference.

Specifically, as an oxime compound, a compound represented by the following formula (OX-1) is preferable. Further, the N-O bond of the oxime compound may be an oxime compound of the (E) body, an oxime compound of the (Z) body, or a mixture of the (E) body and (Z) body.

[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 formula (OX-1), the monovalent substituent represented by R is preferably a monovalent nonmetallic group.

Examples of the monovalent nonmetallic group include an alkyl group, an aryl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a heterocyclic group, an alkylthiocarbonyl group, and an arylthiocarbonyl group. These groups may have one or more substituents. In addition, the above-described substituent may be substituted with another substituent.

Examples of the substituent include a halogen atom, an aryloxy group, an alkoxycarbonyl group or an aryloxycarbonyl group, an acyloxy group, an acyl group, an alkyl group, and an aryl group.

In formula (OX-1), as the monovalent substituent represented by B, an aryl group, heterocyclic group, arylcarbonyl group, or heterocyclic carbonyl group is preferable. These groups may have one or more substituents. As a substituent, the above-mentioned substituent is mentioned.

In formula (OX-1), the divalent organic group represented by A is preferably an alkylene group having 1 to 12 carbon atoms, a cycloalkylene group, or an alkynylene group. These groups may have one or more substituents. As a substituent, the above-mentioned substituent is mentioned.

As the photoinitiator, an oxime compound containing a fluorine atom can also be used. As specific examples of the oxime compound containing a fluorine atom, the compound described in JP 2010-262028 A; Compounds 24, 36 to 40 described in Japanese Patent Publication No. 2014-500852; The compound (C-3) described in JP 2013-164471 A, etc. are mentioned. This content is incorporated in this specification.

As a photoinitiator, a compound represented by the following general formulas (1) to (4) can also be used.

[Formula 8]

[Formula 9]

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

In the formula (2), R ^1, R ^2, R ³ and R ^4, and R ^1, R ^2, R ³ and R ⁴ with the consent of the formula (1), R ⁵ is -R ^6, -OR ⁶ , -SR ⁶ , -COR ⁶ , -CONR ⁶ R ⁶ , -NR ⁶ COR ⁶ , -OCOR ⁶ , -COOR ⁶ , -SCOR ⁶ , -OCSR ⁶ , -COSR ⁶ , -CSOR ⁶ , -CN , Represents a halogen atom or a hydroxy group, R ⁶ represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 4 to 20 carbon atoms, X is, It represents a direct bond or a carbonyl group, and a represents an integer of 0-4.

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 arylalkyl group having 7 to 30 carbon atoms, and R ³ And R ⁴ each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 4 to 20 carbon atoms, and X is a direct bond Or a carbonyl group.

In the formula ^{(4), R 1, R} 3 and R ^4, and R ^1, R ³ and R ⁴ with the consent of the formula (3), R ⁵ is -R ^6, -OR ^6, -SR ⁶ , -COR ⁶ , -CONR ⁶ R ⁶ , -NR ⁶ COR ⁶ , -OCOR ⁶ , -COOR ⁶ , -SCOR ⁶ , -OCSR ⁶ , -COSR ⁶ , -CSOR ⁶ , -CN, halogen atom or hydrogen Represents a oxy group, R ⁶ represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 4 to 20 carbon atoms, and X is a direct bond or a carbonyl group And a represents the integer of 0-4.

In the above formulas (1) and (2), R ¹ and R ² are each independently preferably a methyl group, an ethyl group, an n-propyl group, an i-propyl group, a cyclohexyl group, or a phenyl group. R ³ is preferably a methyl group, an ethyl group, a phenyl group, a tolyl group or a xylyl group. R ⁴ is preferably an alkyl group or a phenyl group having 1 to 6 carbon atoms. R ⁵ is preferably a methyl group, an ethyl group, a phenyl group, a tolyl group or a naphthyl group. X is preferably a direct bond.

In the formulas (3) and (4), R ¹ is each independently preferably a methyl group, an ethyl group, an n-propyl group, an i-propyl group, a cyclohexyl group, or a phenyl group. R ³ is preferably a methyl group, an ethyl group, a phenyl group, a tolyl group or a xylyl group. R ⁴ is preferably an alkyl group or a phenyl group having 1 to 6 carbon atoms. R ⁵ is preferably a methyl group, an ethyl group, a phenyl group, a tolyl group or a naphthyl group. X is preferably a direct bond.

As a specific example of the compound represented by Formula (1) and Formula (2), the compound of Paragraph No. 0076-0079 of JP 2014-137466 A is mentioned, for example. This content is assumed to be incorporated in the present specification.

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

[Formula 10]

The oxime compound preferably has a maximum absorption wavelength in a wavelength range of 350 nm to 500 nm, more preferably a maximum absorption wavelength in a wavelength range of 360 nm to 480 nm, and more preferably high absorbance at 365 nm and 405 nm.

The molar extinction 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 still more preferably 5,000 to 200,000 from the viewpoint of sensitivity.

Although a known method can be used for the molar extinction coefficient of the compound, for example, it is measured at a concentration of 0.01 g/L using an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian) using an ethyl acetate solvent. desirable.

Photoinitiators may be used in combination of two or more as needed.

[Polymerizable compound]

The curable composition contains a polymerizable compound.

The content of the polymerizable compound is preferably 1 to 40% by mass, and more preferably 10 to 40% by mass with respect 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. Moreover, a polymerizable compound may be used individually by 1 type, and may use 2 or more types together. When using two or more kinds of polymerizable compounds together, it is preferable that the total amount is within the above range.

The polymerizable compound is preferably a compound containing one or more groups containing ethylenically unsaturated bonds, more preferably a compound containing two or more, more preferably three or more, and more preferably five or more. It is particularly preferred. The upper limit is 15 or less, for example. 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 any of chemical forms such as a monomer, a prepolymer, an oligomer, and a mixture thereof, and a multimer thereof, and a monomer is preferable.

100-3,000 are preferable and, as for the molecular weight of a polymeric compound, 250-1,500 are more preferable.

It is preferable that it is a 3-15 functional (meth)acrylate compound, and, as for a polymeric compound, it is more preferable that it is a 3-6 functional (meth)acrylate compound.

Examples of monomers and prepolymers include unsaturated carboxylic acids (e.g., acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) or esters, amides, and multimers thereof. , Preferably, they are esters of an unsaturated carboxylic acid and an aliphatic polyhydric alcohol compound, and amides of an unsaturated carboxylic acid and an aliphatic polyhydric amine compound, and a multimer thereof. In addition, an addition reaction product of an unsaturated carboxylic acid ester or amide containing a nucleophilic substituent such as a hydroxy group, an amino group, or a mercapto group with a monofunctional or polyfunctional isocyanate or epoxy, and the unsaturated carboxylic acid ester or A dehydration condensation reaction product of amides and monofunctional or polyfunctional carboxylic acid is also preferably used. In addition, a reaction product of an unsaturated carboxylic acid ester or amide containing an electrophilic substituent such as an isocyanate group or an epoxy group, and a monofunctional or polyfunctional alcohol, amine, or thiol, a halogen group or tosyloxy A reaction product of an unsaturated carboxylic acid ester or amide containing a leaving substituent such as a group and a monofunctional or polyfunctional alcohol, amine, or thiol is also suitable. Further, in place of the above unsaturated carboxylic acid, it is also possible to use a group of compounds substituted with vinylbenzene derivatives such as unsaturated phosphonic acid and styrene, vinyl ether, allyl ether, or the like.

As these specific compounds, the compounds described in paragraphs 0095 to 0108 of JP 2009-288705 A can be suitably used also in the present invention.

The polymerizable compound is also preferably a compound containing at least one group containing an ethylenically unsaturated bond and having a boiling point of 100°C or higher under normal pressure. For example, reference can be made to the compounds described in paragraphs 0227 of JP 2013-029760 A and paragraphs 0254 to 0257 of JP 2008-292970 A, the contents of which are incorporated herein by reference.

The polymerizable compound is dipentaerythritol triacrylate (KAYARAD D-330, PET-30 as a commercial product, manufactured by Nippon Kayaku Corporation), dipentaerythritol tetraacrylate (KAYARAD D-320 as a commercial product, manufactured by Nippon Kayaku Corporation). , Dipentaerythritol penta (meth)acrylate (KAYARAD D-310 as a commercial product, manufactured by Nippon Kayaku Corporation), Dipentaerythritol hexa (meth)acrylate (KAYARAD DPHA as a commercial product, manufactured by Nippon Kayaku Corporation, A-DPH-) 12E, Shinnakamura Chemical Co., Ltd.), and a structure in which these (meth)acryloyl groups are interposed with an ethylene glycol residue or a propylene glycol residue (e.g., SR454, SR499 commercially available from Satomer Corporation) ) Is preferred. These oligomer types can also be used. Further, NK ester A-TMMT (pentaerythritol tetraacrylate, manufactured by Shin-Nakamura Chemical Corporation), KAYARAD RP-1040 (manufactured by Nippon Kayaku Corporation), and the like can also be used.

The mode of a preferable polymeric compound is shown below.

The polymerizable compound may have an acid group such as a carboxylic acid group, a sulfonic acid group, or a phosphoric acid group. As the polymerizable compound containing an acid group, an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid is preferable, and a non-aromatic carboxylic anhydride is reacted with an unreacted hydroxy group of the aliphatic polyhydroxy compound to give an acid group. A compound is more preferable, and in this ester, it is more preferable that the aliphatic polyhydroxy compound is pentaerythritol and/or dipentaerythritol. As a commercial item, Toa Kosei Co., Ltd. Aronix TO-2349, M-305, M-510, M-520, etc. are mentioned, for example.

The preferred acid value of the polymerizable compound containing an acid group is 0.1 to 40 mgKOH/g, more preferably 5 to 30 mgKOH/g. When the acid value of the polymerizable compound is 0.1 mgKOH/g or more, the developing dissolution property is good, and when it is 40 mgKOH/g or less, it is advantageous in terms of production and/or handling. Furthermore, photopolymerization performance is good and curability is excellent by being within the above range.

The polymerizable compound is also a preferred embodiment of a compound containing a caprolactone structure.

The compound containing a caprolactone structure is not particularly limited as long as it contains a caprolactone structure in the molecule, but examples include trimethylolethane, ditrimethylolethane, trimethylolpropane, and ditrimethylolpropane. Ε-caprolactone obtained by esterifying polyhydric alcohols such as paine, pentaerythritol, dipentaerythritol, tripentaerythritol, glycerin, diglycerol and trimethylolmelamine, and (meth)acrylic acid and ε-caprolactone Modified polyfunctional (meth)acrylates are mentioned. Among them, a compound containing a caprolactone structure represented by the following formula (Z-1) is preferable.

[Formula 11]

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

[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.

[Formula 13]

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

Polymeric compounds containing a caprolactone structure are commercially available from Nippon Kayaku as KAYARAD DPCA series, for example, in DPCA-20 (Formulas (Z-1) to (Z-3), m is 1, The number of groups represented by (Z-2) is 2, a compound in which R ¹ is all hydrogen atoms), DPCA-30 (in the same formula, m is 1, the number of groups represented by formula (Z-2) is 3, R ¹⁾ These are all hydrogen atoms), DPCA-60 (in the same formula, m is 1, the number of groups represented by formula (Z-2) is 6, R ¹ is all hydrogen atoms), DPCA-120 (same formula In which m is 2, the number of groups represented by formula (Z-2) is 6, and R ¹ is all hydrogen atoms).

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

[Formula 14]

In formulas (Z-4) and (Z-5), E is each independently -((CH ₂ ) _y CH ₂ O)-, or -((CH ₂ ) _y CH(CH ₃ ) O)- Represents, and y represents an integer of 0-10 each independently,

Each of X independently represents a (meth)acryloyl group, a hydrogen atom, or a carboxylic acid group.

In formula (Z-4), the total number of (meth)acryloyl groups is 3 or 4, m each independently represents an integer of 0-10, and the total of each m is an integer of 0-40.

In Formula (Z-5), the total number of (meth)acryloyl groups is 5 or 6, n each independently represents an integer of 0-10, and the sum of each n is an integer of 0-60.

In formula (Z-4), the integer of 0-6 is preferable and, as for m, the integer of 0-4 is more preferable.

The sum of each m is preferably an integer of 2 to 40, more preferably an integer of 2 to 16, and still more preferably an integer of 4 to 8.

In formula (Z-5), the integer of 0-6 is preferable and, as for n, the integer of 0-4 is more preferable.

The sum of each n is preferably an integer of 3 to 60, more preferably an integer of 3 to 24, and still more preferably an integer of 6 to 12.

In formula (Z-4) or formula (Z-5), -((CH ₂ ) _y CH ₂ O)- or -((CH ₂ ) _y CH(CH ₃ )O)- is the terminal on the oxygen atom side The form that binds to X is preferred.

The compounds represented by formula (Z-4) or formula (Z-5) may be used alone or in combination of two or more. In particular, in the formula (Z-5), in the form in which all of the six Xs are acryloyl groups, in the formula (Z-5), the compound in which all of the six Xs are acryloyl groups, and at least one of the six Xs The aspect in which is a mixture with a compound which is a hydrogen atom is preferred. By setting it as such a structure, developability can be improved more.

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

The compound represented by formula (Z-4) or formula (Z-5) is a process of bonding a ring-opening skeleton to pentaerythritol or dipentaerythritol by ring-opening addition reaction, which is a conventionally known process. And, it can be synthesized by a step of introducing a (meth)acryloyl group by reacting, for example, (meth)acryloyl chloride to the terminal hydroxy group of the ring-opening skeleton. Each step is a well-known step, and a person skilled in the art can easily synthesize a compound represented by the general formula (Z-4) or (Z-5).

Among the compounds represented by formula (Z-4) or formula (Z-5), pentaerythritol derivatives and/or dipentaerythritol derivatives are more preferred.

Specifically, compounds represented by the following formulas (a) to (f) (hereinafter also referred to as "exemplary compounds (a) to (f)") are exemplified, and among them, exemplary compounds (a) and (b) , (e), (f) are preferred.

[Formula 15]

[Formula 16]

Commercially available products of the polymerizable compounds represented by formulas (Z-4) and (Z-5) include, for example, SR-494, a tetrafunctional acrylate containing four ethyleneoxy chains manufactured by Sartomer Corporation, and manufactured by Nippon Kayaku Corporation. DPCA-60 which is a 6-functional acrylate containing 6 pentyleneoxy chains, and TPA-330 which is a trifunctional acrylate containing 3 isobutyleneoxy chains.

As the polymerizable compound, urethane acrylic described in Japanese Patent Publication No. 48-041708, Japanese Patent Publication No. 51-037193, Japanese Patent Publication No. Hei 2-032293, and Japanese Patent Publication No. Hei 2-016765. Rates; Oil containing an ethylene oxide skeleton described in Japanese Patent Publication No. 58-049860, Japanese Patent Publication No. 56-017654, Japanese Publication No. 62-039417, and Japanese Publication No. 62-039418. Letein compounds are also suitable. In addition, as described in JP-A-63-277653, JP-A-63-260909, and JP-A 1-105238, addition polymerizable containing an amino structure and/or a sulfide structure in a molecule By using compounds, it is possible to obtain a curable composition having very excellent photosensitive speed.

As commercially available products, urethane oligomer UAS-10, UAB-140 (manufactured by Sanyo Kokusaku Pulp Corporation), UA-7200 (manufactured by Shin-Nakamura Chemical Corporation), DPHA-40H (manufactured by Nippon Kayaku Corporation), UA-306H, UA-306T , UA-306I, AH-600, T-600, and AI-600 (manufactured by Kyoeisha), and the like.

As for the polymerizable compound, the SP (Solubility Parameter: dissolution parameter) value is preferably 9.50 or more, more preferably 10.40 or more, and still more preferably 10.60 or more.

In this specification, the SP value is obtained by the Hoy method unless otherwise specified (HL Hoy Journal of Painting, 1970, Vol. 42, 76-118). Although the unit is omitted for the SP value, the unit is cal ^1/2 cm ^-3/2 .

It is also preferable that the curable composition contains a polymerizable compound containing a cardo skeleton from the viewpoint of improving the development residue.

As the polymerizable compound containing a cardo skeleton, a polymerizable compound containing a 9,9-bisarylfluorene skeleton is preferable, and a compound represented by the following formula (Q3) is more preferable.

Equation (Q3)

[Formula 17]

In the formula (Q3), Ar ¹¹ to Ar ¹⁴ each independently represent an aryl group containing a benzene ring surrounded by a broken line. Each of X ¹ to X ⁴ independently represents a substituent containing a polymerizable group, and carbon atoms in the substituent may be substituted with a hetero atom. a and b each independently represent an integer of 1-5, and c and d each independently represent an integer of 0-5. R ¹ to R ⁴ each independently represent a substituent, e, f, g, and h each independently represent an integer greater than or equal to 0, and the upper limit values of e, f, g and h are each Ar ¹¹ to Ar ¹⁴ may contain It is a value obtained by subtracting a, b, c or d from the number of substituents present. However, in the case where Ar ¹¹ to Ar ¹⁴ are polycyclic aromatic hydrocarbon groups each independently containing a benzene ring surrounded by a broken line as one of the condensed rings, X ¹ to X ⁴ and R ¹ to R ⁴ are each independently benzene surrounded by a broken line. It may be substituted with a ring, or may be substituted with a ring other than the benzene ring surrounded by broken lines.

In formula (Q3), the aryl group containing a benzene ring surrounded by a broken line represented by Ar ¹¹ to Ar ¹⁴ is preferably an aryl group having 6 to 14 carbon atoms, and an aryl group having 6 to 10 carbon atoms (e.g., phenyl group, naphtha Tyl group) is more preferable, and it is more preferable that it is a phenyl group (only a benzene ring surrounded by broken lines).

In formula (Q3), X ¹ to X ⁴ each independently represent a substituent containing a polymerizable group, and carbon atoms in the substituent may be substituted with a hetero atom. Although there is no restriction|limiting in particular as a substituent containing a polymeric group represented by X ¹ to X ⁴ , It is preferable that it is an aliphatic group containing a polymerizable group.

The aliphatic group containing the polymerizable group represented by X ¹ to X ⁴ is not particularly limited, but it is preferably an alkylene group having 1 to 12 carbon atoms other than the polymerizable group, and more preferably an alkylene group having 2 to 10 carbon atoms. And, it is more preferable that it is a C2-C5 alkylene group.

In the aliphatic group containing a polymerizable group represented by X ¹ to X ⁴ , when the aliphatic group is substituted by a hetero atom, it is preferably substituted by -NR- (R is a substituent), an oxygen atom, or a sulfur atom, more preferably optionally substituted with an oxygen atom or a sulfur atom, -CH ₂ that do not neighbor each other in the aliphatic group - -, -CH ₂ that do not neighbor each other in the aliphatic group is more preferred that the optionally substituted oxygen atom. The aliphatic group containing the polymerizable group represented by X ¹ to X ⁴ is preferably substituted at 1 to 2 places by a hetero atom, more preferably at 1 to be substituted by a hetero atom, and Ar ¹¹ to Ar ¹⁴ are It is more preferable that one site adjacent to the aryl group containing a benzene ring surrounded by the indicated broken line is substituted by a hetero atom.

As the polymerizable group contained in the aliphatic group containing the polymerizable group represented by X ¹ to X ⁴ , a polymerizable group capable of radical polymerization or cationic polymerization (hereinafter, also referred to as a radical polymerizable group and a cationic polymerizable group, respectively) is preferable.

As the radical polymerizable group, a generally known radical polymerizable group can be used, and suitable examples include a polymerizable group containing an ethylenically unsaturated bond capable of radical polymerization, specifically a vinyl group, a (meth)acryloyloxy group, etc. Can be mentioned. Among them, a (meth)acryloyloxy group is preferable, and an acryloyloxy group is more preferable.

As the cationic polymerizable group, a generally known cationic polymerizable group can be used, and specifically, an alicyclic ether group, a cyclic acetal group, a cyclic lactone group, a cyclic thioether group, a spirothoester group, a vinyloxy group, etc. Can be lifted. Among them, an alicyclic ether group and a vinyloxy group are suitable, and an epoxy group, an oxetanyl group, and a vinyloxy group are particularly preferable.

It is preferable that the said polymerizable group contained by the substituent contained in Ar ¹¹ -Ar ¹⁴ is a radical polymerizable group.

Of Ar ¹¹ ~ Ar 2 or more of the ¹⁴ are preferably comprising a substituent containing a polymerizable group, and containing a substituent of the dog Ar ¹¹ ~ Ar 2 ~ 4 of ¹⁴ containing a polymerizable group, Ar ¹¹ ~ Ar ¹⁴ 2 Or it is more preferable that three contain a substituent containing a polymerizable group, and it is more preferable that two 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 broken line as one of the condensed rings, X ¹ to X ⁴ may each independently be substituted with a benzene ring surrounded by a broken line, and a broken line It may be substituted with a ring other than the benzene ring surrounded by.

In formula (Q3), a and b each independently represent the integer of 1-5, it is preferable that they are 1 or 2, and it is more preferable that both a and b are 1.

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 are 0.

In formula (Q3), R ¹ to R ⁴ each independently represent a substituent. The substituent represented by R ¹ to R ⁴ is not particularly limited, but for example, a halogen atom, a halogenated alkyl group, an alkyl group, an alkenyl group, an acyl group, a hydroxy group, a hydroxyalkyl group, an alkoxy group, an aryl group, a hetero And an aryl group and an alicyclic group. The substituent represented by R ¹ to R ⁴ is preferably an alkyl group, an alkoxy group or an aryl group, more preferably a C 1 to C 5 alkyl group, a C 1 to C 5 alkoxy group or a phenyl group, and a methyl group, a methoxy group or a phenyl group. More preferable.

In formula (Q3), when Ar ¹¹ to Ar ¹⁴ are each independently a polycyclic aromatic hydrocarbon group containing a benzene ring surrounded by a broken line as one of the condensed rings, R ¹ to R ⁴ are each independently a benzene ring surrounded by a broken line. It may be substituted, or may be substituted with a ring other than the benzene ring surrounded by broken lines.

In formula (Q3), e, f, g and h each independently represent an integer greater than or equal to 0, and the upper limit values of e, f, g and h are each from the number of substituents that Ar ¹¹ to Ar ¹⁴ may contain, a, These are the abbreviations of b, c or d, respectively.

e, f, g and h are each independently preferably 0 to 8, more preferably 0 to 2, and still more preferably 0.

When Ar ¹¹ to Ar ¹⁴ are each independently a polycyclic aromatic hydrocarbon group containing a benzene ring surrounded by a broken line as one of the condensed rings, e, f, g and h are preferably 0 or 1, and more preferably 0. .

As a compound represented by Formula (Q3), 9,9-bis[4-(2-acryloyloxyethoxy)phenyl]fluorene etc. are mentioned, for example. As the polymerizable compound containing a 9,9-bisarylfluorene skeleton, the compounds described in JP 2010-254732 A can also be suitably used.

Although it does not restrict|limit as a polymeric compound containing such a cardo skeleton, For example, Oncoat EX series (made by Nagase Sangyo), Ogsol (made by Osaka Gas Chemicals), etc. are mentioned.

[Optional ingredient]

<Coloring agent>

It is preferable that the curable composition contains a colorant. The colorant is at least one selected from the group consisting of a pigment and a dye, and may be a chromatic colorant or a black colorant, but 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 by the curable composition is used as a light-shielding film, from the viewpoint of obtaining more excellent light-shielding property, 50% by mass or more with respect to the total solid content of the curable composition desirable.

Although the upper limit of the content of the colorant is not particularly limited, in general, it is preferably 70% by mass or less with respect to the total solid content of the curable composition. When the content of the colorant is equal to or less than the upper limit, the curable composition has more excellent coatability.

(Pigment)

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

·Inorganic pigment

The inorganic pigment is not particularly limited, and a known inorganic pigment can be used.

As inorganic pigments, for example, zincation, lead white, lithopone, titanium oxide, chromium oxide, iron oxide, precipitated barium sulfate and barite powder, briquette, iron oxide red, sulfur lead, zinc sulfur (zinc sulfur one type , Zinc sulfur 2 types), ultramarine blue, Prussian blue (ferrocyanide iron potassium), zircon gray, praseodymium yellow, chromium titanium yellow, chromium green, peacock, victoria green, royal blue (no relation to Prussian blue) , Vanadium zirconium blue, chromium tin pink, manganese pink, and salmon pink. In addition, as a black inorganic pigment, a metal oxide, a metal nitride 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, And metal oxynitrides.

As the inorganic pigment, carbon black, titanium black, metal pigment, etc. (hereinafter, also referred to as "black pigment") are preferable from the viewpoint of obtaining a curable composition capable of forming a cured film having a high optical concentration at least in content. As a metal pigment, for example, a metal containing one or two or more metal elements selected from the group consisting of Nb, V, Co, Cr, Cu, Mn, Ru, Fe, Ni, Sn, Ti, and Ag Oxides and metal nitrides.

As the inorganic pigment, it contains at least one selected from the group consisting of a metal pigment containing titanium nitride, titanium oxynitride, niobium nitride, vanadium nitride, silver, or tin, and a metal pigment containing silver and tin. It is preferred, and it is more preferred that 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 be niobium oxynitride and vanadium oxynitride.

Moreover, carbon black can also be used as an inorganic pigment. Specific examples of the carbon black include commercially available organic pigments such as C. I. Pigment Black 1 and inorganic pigments such as C. I. Pigment Black 7, but are not limited thereto.

As the curable composition, in addition to the pigment described as a black pigment, a pigment having infrared absorption properties can also be used.

As a pigment having infrared absorption, a tungsten compound, a metal boride, and the like are preferable, and among them, a tungsten compound is preferable from the viewpoint of excellent light-shielding property at a wavelength in the infrared region. In particular, a tungsten compound is preferable from the viewpoint of excellent light-absorption wavelength range of the photopolymerization initiator related to the curing efficiency by exposure and the light transmittance in the visible light range.

These pigments may be used in combination of two or more, or may be used in combination with a dye described later. In order to adjust the color tone and increase the light-shielding property in the desired wavelength range, for example, a black pigment or a pigment having infrared light-shielding property, a chromatic color pigment such as red, green, yellow, orange, purple, and blue, or The aspect of mixing the dye mentioned later is mentioned. It is preferable to mix a red pigment or dye, or a purple pigment or dye with a black pigment or a pigment which has infrared light-shielding property, and it is more preferable to mix a red pigment with a black pigment or a pigment which has infrared light-shielding property.

Further, a near-infrared absorber and an infrared absorber described later may be added.

It is preferable that the black pigment contains titanium black and/or niobium oxynitride. Titanium black is a black particle containing a titanium atom. Preferably, they are lower order titanium oxide, titanium oxynitride or titanium nitride. The titanium black particles can modify the surface as necessary for the purpose of improving dispersibility and suppressing cohesion. It is possible to coat with silicon oxide, titanium oxide, germanium oxide, aluminum oxide, magnesium oxide, or zirconium oxide, and treatment with a water-repellent material as shown in JP 2007-302836 A is also possible.

Titanium black is typically titanium black particles, and it is preferable that both the primary particle diameter and the average primary particle diameter of the individual particles are small. The same goes for niobium oxynitride.

Specifically, the average primary particle diameter is preferably in the range of 10 nm to 45 nm.

In addition, the average primary particle diameter of the pigment can be measured using a transmission electron microscope (TEM). As the transmission electron microscope, for example, a transmission microscope HT7700 manufactured by Hitachi High Technologies can be used.

In the present specification, the average primary particle diameter of the pigment is the maximum length (Dmax: maximum length in two points on the outline of the particle image) of the particle image obtained using a transmission electron microscope, and the maximum length vertical length ( DV-max: When the image is interposed by two straight lines parallel to the maximum length, the shortest length connecting the two straight lines vertically) is measured and the average value of the rise (Dmax×DV-max) is measured. ) ^1/2 was taken as the particle diameter. As for the average primary particle diameter of the pigment, the particle diameter of 100 particles is measured by this method, and the arithmetic average value is intended.

The specific surface area of titanium black and niobium oxynitride is not particularly limited, but in order to obtain a predetermined performance after surface treatment of titanium black and niobium oxynitride with a water repellent, the BET (Brunauer, Emmett, Teller) method is used. It is preferable that the measured value is 5 m ² /g or more and 150 m ² /g or less, and more preferably 20 m ² /g or more and 120 m ² /g or less.

Examples of commercially available products of titanium black include titanium black 10S, 12S, 13R, 13M, 13M-C, 13R, 13R-N, 13M-T (brand name, Mitsubishi Material Co., Ltd.), Tilack D (brand name, Ako Kasei Co., Ltd. product), titanium nitride 50 nm (brand name, Wako Junyaku Co., Ltd. product), etc. are mentioned.

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

It is also preferable to further contain titanium black as a dispersion object containing titanium black and Si atoms.

In this aspect, titanium black is contained as a dispersion object in the curable composition, and the content ratio (Si/Ti) of Si atoms and Ti atoms in the dispersion object is preferably 0.05 or more in terms of mass, and 0.05 to 0.5 is It is more preferable, and 0.07 to 0.4 are more preferable.

Here, the said object to be dispersed includes both the titanium black in the state of the primary particle and the state of the aggregate (secondary particle).

In order to change the content ratio (Si/Ti) of the object to be dispersed (for example, to be 0.05 or more), the following means can be used.

First, titanium oxide and silica particles are dispersed using a disperser to obtain a dispersion, and the dispersion is reduced at a high temperature (for example, 850 to 1,000°C), whereby titanium black particles are used as main components, and Si and Ti It is possible to obtain a dispersion containing The reduction treatment may be performed in an atmosphere of a reducing gas such as ammonia.

Examples of titanium oxide include TTO-51N (brand name, manufactured by Ishihara Sangyo).

Commercially available products of silica particles include AEROSIL (registered trademark) 90, 130, 150, 200, 255, 300, 380 (brand name, manufactured by Evonik), and the like.

Dispersing agent may be used for the dispersion of titanium oxide and silica particles. As a dispersing agent, what will be described in the column of a dispersing agent mentioned later is mentioned.

The above dispersion may be performed in a solvent. As a solvent, water and an organic solvent are mentioned. What is described in the column of the organic solvent mentioned later is mentioned.

Titanium black whose content ratio (Si/Ti) is adjusted to, for example, 0.05 or more, is, for example, paragraph number [0005] and paragraph number [0016] to [0021] of JP 2008-266045. It can be produced by the method described in.

By adjusting the content ratio (Si/Ti) of Si atoms and Ti atoms in the object to be dispersed containing titanium black and Si atoms to a suitable range (for example, 0.05 or more), curing using a curable composition containing the object to be dispersed When the film is formed, residues derived from the curable composition outside the formation region of the cured film are reduced. In addition, the residue contains components derived from the curable composition such as titanium black particles and resin components.

The reason for the reduction of the residue is not yet clear, but the particle diameter of the above-described object to be dispersed tends to decrease (for example, the particle diameter of 30 nm or less), and the component containing the Si atom of the object to be dispersed increases. The adsorption property with the whole base is reduced. It is estimated that this contributes to improvement of the development removal property of an uncured curable composition (especially titanium black) in formation of a cured film.

Titanium black has excellent light-shielding properties for light in a wide wavelength range from ultraviolet light to infrared light, and therefore a dispersion object containing the above titanium black and Si atoms (preferably the content ratio (Si/Ti)) Is 0.05 or more in terms of mass) to exhibit excellent light-shielding properties.

In addition, the content ratio (Si/Ti) of the Si atom and the Ti atom in the object to be dispersed is, for example, the method (1-1) or method (1-2) described in paragraph 0033 of JP2013-249417A. It can be measured using.

For the object to be dispersed contained in the cured film obtained by curing the curable composition, in order to determine whether the content ratio (Si/Ti) of Si atoms and Ti atoms in the object to be dispersed is 0.05 or more, Japanese Laid-Open Patent Publication 2013-249417 Method (2) described in paragraph 0035 of the heading can be used.

In the dispersion object containing titanium black and Si atom, the titanium black can be used as described above.

In this dispersion, in addition to titanium black, black made of complex oxides such as Cu, Fe, Mn, V, Ni, cobalt oxide, iron oxide, carbon black, aniline black, etc. for the purpose of adjusting dispersibility and coloring properties, etc. You may use 1 type or in combination of 2 or more types of pigments. In this case, it is preferable that 50% by mass or more of the total object to be dispersed is occupied by the object to be dispersed made of titanium black.

In this dispersion, other colorants (organic pigments and/or dyes, etc.) may be used in combination with titanium black as long as the effect of the present invention is not impaired for the purpose of adjusting light-shielding properties, etc. do.

Hereinafter, the material used when introducing Si atoms into the object to be dispersed will be described. When introducing a Si atom into the object to be dispersed, a Si-containing material such as silica may be used.

Examples of silica that can be used include precipitated silica, fumed silica, colloidal silica, and synthetic silica, and these may be appropriately selected and used.

In addition, if the particle diameter of the silica particles is smaller than the film thickness when the cured film is formed, the light-shielding property is more excellent, and therefore it is preferable to use fine particle type silica. In addition, as an example of the fine particle type silica, the silica described in paragraph 0039 of Unexamined-Japanese-Patent No. 2013-249417 is mentioned, for example, 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 are infrared shielding materials that have high absorption for infrared (light with a wavelength of about 800 to 1,200 nm) (i.e., have high light-shielding property (shielding property) for infrared) and low absorption for visible light. . For this reason, when the curable composition contains a tungsten compound and/or a metal boride, it is possible to form a pattern having high light-shielding properties in the infrared region and high light transmittance in the visible region.

The tungsten compound and the metal boride have a smaller absorption even for light that is shorter than the visible range used for exposure such as high-pressure mercury lamps, KrF, ArF, etc. used for image formation. For this reason, by combining with the above-described polymerizable compound, a photoinitiator, and an alkali-soluble resin described later, an excellent pattern can be obtained, and development residues can be further suppressed in pattern formation.

Examples of the tungsten compound include a tungsten oxide compound, a tungsten boride compound, a tungsten sulfide compound, and the like, and a tungsten oxide compound represented by the following general formula (composition formula) (I) is preferable.

M _x W _y O _z … (I)

M represents a metal, W represents tungsten, and O represents oxygen.

0.001≤x/y≤1.1

2.2≤z/y≤3.0

As the metal of M, for example, alkali metal, alkaline earth metal, 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. are mentioned, but alkali metals are preferable. The number of metals for M may be one or two or more.

It is preferable that M is an alkali metal, Rb or Cs is more preferable, and Cs is more preferable.

When x/y is 0.001 or more, infrared rays can be sufficiently shielded, and when it is 1.1 or less, formation 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 it is 3.0 or less, infrared rays can be sufficiently shielded.

Specific examples of the tungsten oxide compound represented by the general formula (I) include Cs _0.33 WO ₃ , Rb _0.33 WO ₃ , K _0.33 WO ₃ , Ba _0.33 WO ₃ and the like, and Cs _0.33 WO ₃ or Rb _0.33 WO ₃ It is preferred, and Cs _0.33 WO ₃ is more preferred.

It is preferable that the tungsten compound is a fine particle. The average primary particle diameter of the tungsten fine particles is preferably 800 nm or less, more preferably 400 nm or less, and still more preferably 200 nm or less. When the average primary particle diameter is in such a range, since it becomes difficult for the tungsten fine particles to block visible light due to light scattering, the light transmittance in the visible light region can be made more reliably. From the viewpoint of avoiding light scattering, the smaller the average primary particle diameter is, the more preferable, but for reasons such as ease of handling at the time of manufacture, the average primary particle diameter of the tungsten fine particles is usually 1 nm or more.

It is possible to use two or more types of tungsten compounds.

The tungsten compound can be obtained 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 (refer to Japanese Patent Publication 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 Kinzoku Kozan Co., Ltd., for example.

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

It is preferable that the metal boride is a fine particle. The average primary particle size of the metal boride fine particles is preferably 800 nm or less, more preferably 300 nm or less, and further preferably 100 nm or less. When the average primary particle diameter is in such a range, since it becomes difficult for the metal boride fine particles to block visible light due to light scattering, the light transmittance in the visible light region can be made more reliably. From the viewpoint of avoiding light scattering, the smaller the average primary particle diameter is, the more preferable, but for reasons such as ease of handling at the time of manufacture, the average primary particle diameter of the metal boride fine particles is usually 1 nm or more.

Two or more types of metal borides may be used.

Metal boride can be obtained as a commercial item, and for example, it can be obtained as a dispersion of metal boride fine particles such as KHF-7 manufactured by Sumitomo Kinzoku Kozan Co., Ltd.

Particles containing titanium nitride

As the inorganic pigment, titanium nitride-containing particles containing Fe atoms can also be used. For the production of titanium nitride-containing particles, a gas phase reaction method is usually used, and specifically, an electric furnace method, a thermal plasma method, and the like are mentioned. Among these manufacturing methods, the thermal plasma method is preferred because of the fact that there is little mixing of impurities, the particle diameter is easy to be uniform, and the productivity is high.

As a method of generating the thermal plasma, a direct current arc discharge, a multiphase arc discharge, a high frequency (RF) plasma, a hybrid plasma, and the like can be exemplified, and a high frequency plasma with little mixing of impurities from the electrode is preferable. As a specific method for producing titanium nitride-containing fine particles by the thermal plasma method, for example, titanium powder is evaporated by high-frequency thermal plasma, nitrogen is introduced into the apparatus as a carrier gas, and the titanium powder is nitrided in the cooling process. And a method of synthesizing nitride-containing particles. In addition, the thermal plasma method is not limited to the above.

Although it does not specifically limit as a manufacturing method of titanium nitride-containing particles, The manufacturing method described in paragraphs <0037> to <0089> of International Publication No. 2010/147098 can be referred to. For example, instead of the Ag powder of International Publication No. 2010/147098, a component containing Fe and/or a component containing Si to be described later is used, and a mixture of this and a titanium powder material (titanium particles) is a raw material. Thus, titanium nitride-containing particles contained in the curable composition of the present invention can be produced.

It is preferable that the titanium powder material (titanium particle) used for the production of titanium nitride-containing particles is of high purity. The titanium powder material is not particularly limited, but the purity of the titanium element is preferably 99.99% or more, and more preferably 99.999% or more.

The titanium powder material (titanium particle) used for the production of titanium nitride-containing particles may contain atoms other than titanium atoms. Other atoms that can be included in the titanium powder material include, for example, Fe atoms and Si atoms.

When the titanium powder material contains Fe atoms, the content of Fe atoms is preferably more than 0.001% by mass relative to the total mass of the titanium powder material.

When the titanium powder material contains Si atoms, the content of Si atoms is preferably more than 0.002% by mass and less than 0.3% by mass, more preferably 0.01 to 0.15% by mass, and more preferably 0.02% by mass with respect to the total mass of the titanium powder material. It is more preferably -0.1% by mass. Since the Si atom content is more than 0.002 mass%, the patterning property of the cured film is further improved. Since the Si atom content is less than 0.3% by mass, the polarity of the outermost layer of the titanium nitride-containing particles obtained is more stabilized. Thereby, when dispersing the titanium nitride-containing particles, the adsorption property of the dispersant to the titanium nitride-containing particles is improved, the fine dispersion 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 titanium nitride-containing particles is preferably less than 1% by mass, more preferably less than 0.1% by mass, and substantially not included with respect to the total mass of the titanium powder material. It is more preferable not to.

The titanium nitride-containing particles are obtained using a thermal plasma method, and the diffraction angle 2θ of the peak originating from the (200) plane when CuKα rays are used as the X-ray source (detailed below) is greater than 42.6° and not more than 43.5°. It becomes easy to adjust to the range of.

The method of containing Fe atoms in the titanium nitride-containing particles is not particularly limited, for example, in the step of obtaining titanium particles (titanium powder) used as a raw material for the above-described titanium nitride-containing particles, introducing Fe atoms Method, etc. are mentioned. More specifically, when producing titanium by the Crawl method or the like, a reaction vessel made of a material containing Fe atoms such as stainless steel is used, or Fe atoms are used as a material of a press machine and a pulverizer when crushing titanium. Fe atoms can be attached to the surface of the titanium particles by using what they contain.

When the thermal plasma method is used for the production of titanium nitride-containing particles, in addition to the raw material titanium particles, components such as Fe particles and Fe oxide are added, and these are nitrided by thermal plasma method, thereby forming Fe atoms into the titanium nitride-containing particles. Can contain.

The Fe atom contained in the titanium nitride-containing particles may be contained in any form, such as ions, metal compounds (including complex compounds), intermetallic compounds, alloys, oxides, complex oxides, nitrides, oxynitrides, sulfides and oxysulfides. do. The Fe atom contained in the titanium nitride-containing particles may be present as an impurity at a position between the crystal lattice or may be present as an impurity at the grain boundary in an amorphous state.

The inventors of the present invention have found that the content of the Fe atom in the titanium nitride-containing particles is related to the patterning property and the corrosion resistance of the electrode as a result of intensive examination. It is considered that Fe atoms contained in the titanium nitride-containing particles are excellent in adhesion to the electrode and the substrate, and the titanium nitride in the titanium nitride-containing particles adheres to the electrode and the substrate through the Fe atom. It is considered that after patterning of the cured film such as development treatment, Fe atoms remain on the electrode and the substrate, and titanium nitride is easily removed. For this reason, it is estimated that patterning property of a cured film is improved by making content of the Fe atom in a titanium nitride containing particle into a predetermined amount or more. On the other hand, when the content of the Fe atom contained in the titanium nitride-containing particles is too large, the amount of Fe atoms remaining on the electrode and the substrate increases, and it is considered that it causes corrosion of the electrode. For this reason, it is estimated that the corrosion resistance of the electrode is improved by making the content of the Fe atom in the titanium nitride-containing particles less than or equal to a predetermined amount.

It is preferable that the content of the Fe atom in the titanium nitride-containing particles is more than 0.001% by mass and less than 0.4% by mass with respect to the total mass of the titanium nitride-containing particles. Especially, it is more preferable that it is 0.01 to 0.2 mass %, and it is still more preferable that it is 0.02 to 0.1 mass %. Since the content of the Fe atom is more than 0.001% by mass, the patterning property of the cured film is further improved. Since the content of the Fe atom is less than 0.4% by mass, the corrosion resistance of the electrode by the cured film is further improved (it can suppress that the cured film corrodes the electrode). That is, when the content of the Fe atom in the titanium nitride-containing particles is within the above range, excellent patterning property of a cured film and anticorrosive property of an electrode can be obtained.

The content of the Fe atom in the titanium nitride-containing particles can be measured by ICP (Inductively Coupled Plasma) emission spectroscopy.

It is preferable that the titanium nitride-containing particles further contain a Si atom (silicon atom). Thereby, the patterning property of a cured film is improved more. The reason why the patterning property is improved by containing the Si atom is considered to be the same as the Fe atom described above.

The content of the Si atom in the titanium nitride-containing particles is preferably more than 0.002% by mass and less than 0.3% by mass, more preferably 0.01 to 0.15% by mass, and more preferably 0.02 to 0.1% by mass with respect to the total mass of the titanium nitride-containing particles. It is more preferable to be. Since the Si atom content is more than 0.002 mass%, the patterning property of the cured film is further improved. Since the Si atom content is less than 0.3% by mass, the polarity of the outermost layer of the titanium nitride-containing particles is more stabilized. Thereby, when dispersing the titanium nitride-containing particles, the adsorption property of the dispersant to the titanium nitride-containing particles is improved, the fine dispersion of the titanium nitride-containing particles is reduced, and the generation of particles can be suppressed.

The content of the Si atom in the titanium nitride-containing particles can be measured by the same method as the Fe atom described above.

The method for containing Si atoms in the titanium nitride-containing particles is not particularly limited, and for example, in the step of obtaining titanium particles (titanium powder) used as a raw material for the above-described titanium nitride-containing particles, introducing Si atoms Method, etc. are mentioned. More specifically, when producing titanium by the Crawl method or the like, a reaction vessel made of a material containing Si atoms is used, or a press machine for crushing titanium and a material containing Si atoms is used. By doing so, the Si atom can be attached to the surface of the titanium particle.

When the thermal plasma method is used for the production of titanium nitride-containing particles, components such as Si particles and Si oxide are added in addition to the raw material titanium particles, and these are nitrided by the thermal plasma method, so that Si atoms are added to the titanium nitride-containing particles. Can contain.

Si atoms contained in the titanium nitride-containing particles may be contained in any form, such as ions, metal compounds (including complex compounds), intermetallic compounds, alloys, oxides, complex oxides, nitrides, oxynitrides, sulfides and oxysulfides. do. The Si atom contained in the titanium nitride-containing particles may be present as an impurity at an inter-crystal lattice position, or may exist as an impurity in an amorphous state at a grain boundary.

The content of titanium atoms (Ti atoms) in the titanium nitride-containing particles is preferably 10 to 85% by mass, more preferably 15 to 75% by mass, and more preferably 20 to 70% by mass with respect to the total mass of the titanium nitride-containing particles. It is more preferred that it is %. The content of the Ti atom in the titanium nitride-containing particles can be measured by ICP emission spectrometry.

The content of the nitrogen atom (N atom) in the titanium nitride-containing particles is preferably 3 to 60% by mass, more preferably 5 to 50% by mass, and more preferably 10 to 40% by mass with respect to the total mass of the titanium nitride-containing particles. It is more preferred that it is %. The nitrogen atom content can be analyzed by an inert gas fusion-thermal conductivity method.

Titanium nitride-containing particles contain titanium nitride (TiN) as a main component, and are usually remarkable when oxygen is mixed during the synthesis and when the particle diameter is small, but some oxygen atoms are removed due to oxidation of the particle surface. You may contain it.

The content of the oxygen atom in the titanium nitride-containing particles is preferably 1 to 40% by mass, more preferably 1 to 35% by mass, more preferably 5 to 30% by mass with respect to the total mass of the titanium nitride-containing particles. desirable. The content of the oxygen atom can be analyzed by an inert gas melting-infrared absorption method.

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

The titanium nitride-containing particles may be composite fine particles composed of titanium nitride particles and metal fine particles.

The composite fine particles refer to particles in which titanium nitride particles and metal fine particles are compounded or in a highly dispersed state. Here, "compounding" means that particles are composed of both titanium nitride and metal, and "highly dispersed state" means that titanium nitride particles and metal particles exist separately. In addition, it means that particles of a small amount of components do not aggregate and are uniformly and evenly dispersed.

The metal fine particles are not particularly limited, and examples include copper, silver, gold, platinum, palladium, nickel, tin, cobalt, rhodium, iridium, ruthenium, osmium, manganese, molybdenum, tungsten, niobium, and tantalum. , Calcium, titanium, bismuth, antimony, and lead, and at least one selected from alloys thereof. Among them, copper, silver, gold, platinum, palladium, nickel, tin, cobalt, rhodium and iridium, and at least one selected from alloys thereof are preferable, and copper, silver, gold, platinum and tin, and It is more preferable that it is at least 1 type selected from alloys. From the viewpoint of more excellent moisture resistance, it is preferable that it is silver.

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 with respect to the total mass of the titanium nitride-containing particles.

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

In the case of measuring the X-ray diffraction spectrum of the titanium compound using CuKα-ray as the X-ray source, TiN as the peak with the strongest intensity is near 2θ = 42.5°, and TiO is (200) The peak originating from the plane is seen in the vicinity of 2θ = 43.4°. On the other hand, although it is not the strongest peak, in the anatase type TiO ₂ , the peak originating from the (200) plane is near 2θ=48.1°, and in the rutile TiO ₂ the peak originating from the (200) plane is near 2θ=39.2°. Is observed. Therefore, as the crystal state containing more oxygen atoms, the peak position shifts toward a higher angle with respect to 42.5°.

The diffraction angle 2θ of the peak originating from the (200) plane of the titanium nitride-containing particles is preferably more than 42.6° and less than 43.5° from the viewpoint of the aging stability of the particles, and 42.7° from the viewpoint of excellent process margin during production. It is more preferably more than 43.5 degrees, and from the viewpoint of excellent reproducibility of particle performance, 42.7 degrees or more and less than 43.4 degrees are more preferable. In the case of containing titanium oxide TiO ₂ as a subcomponent, the peak derived from anatase-type TiO ₂ (101) as the strongest peak is in the vicinity of 2θ = 25.3°, and the peak derived from rutile-type TiO ₂ (110) is 2θ = It is seen around 27.4°. However, since TiO ₂ is white and serves as a factor for lowering the light-shielding property of the black matrix, it is preferably reduced to such an extent that it is not observed as a peak.

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

It is preferable that it is 20 nm or more, and, as for the crystallite size, it is more preferable that it is 20-50 nm. By forming a black matrix using titanium nitride-containing particles having a crystallite size of 20 nm or more, the transmitted light of the cured film exhibits blue to bluish violet with a peak wavelength of 475 nm or less, and a black matrix having high light blocking properties and ultraviolet sensitivity is obtained. I can. Since the crystallite size is 20 nm or more, the ratio of the active particle surface to the particle volume is reduced, resulting in a good balance, and the titanium nitride-containing particles are more excellent in heat resistance and/or durability.

··Particles containing metal nitride containing atom A

Further, as the inorganic pigment, as the metal nitride-containing particles, metal nitride-containing particles containing a predetermined atom A in the metal nitride-containing particles may be used.

Examples of the metal in the metal nitride-containing particles include Nb, V, Cr, Y, Zr, Nb, Hf, Ta, W, and Re, and Nb or V is more preferable.

Examples of the atom A include B, Al, Si, Mn, Fe, Ni, and Ag.

When the metal nitride-containing particles contain the atom A, the content is not particularly limited, but the content of the atom A in the metal nitride-containing particles is preferably 0.00005 to 10% by mass.

The method for producing the metal nitride-containing particles containing the atom A is not particularly limited, and a known method can be used.

For the production of metal nitride-containing particles, a gas phase reaction method is usually used, and specifically, an electric furnace method and a thermal plasma method are mentioned. Among these manufacturing methods, the thermal plasma method is preferred because of the fact that there is little mixing of impurities, the particle diameter is easy to be uniform, and the productivity is high.

As a specific method for producing metal nitride-containing particles by the thermal plasma method, for example, a metal fine particle manufacturing apparatus (a device similar to the "black composite fine particle manufacturing apparatus" described later) is used. The apparatus for producing metal fine particles includes, for example, a plasma torch for generating thermal plasma, a material supply apparatus for supplying metal raw material powder into the plasma torch, a chamber containing a cooling function, a cyclone for classifying the generated metal fine particles, and metal fine particles. It is configured by a recovery unit that recovers.

In the present specification, the metal fine particles mean particles having a primary particle diameter of 20 nm to 40 μm of particles containing a metal element.

The method for producing metal nitride-containing particles using the metal fine particle production apparatus is not particularly limited, and a known method can be used. Among them, since the yield of the metal nitride-containing particles having the following predetermined average primary particle diameter is increased, the method of producing the metal nitride-containing particles using the metal fine particle production apparatus preferably includes the following steps.

Step A: A step of supplying an inert gas that does not contain nitrogen gas into the plasma torch as a plasma gas to generate thermal plasma salt.

Step B: A step of supplying a metal raw material powder containing a transition metal to a thermal plasma salt in a plasma torch, and evaporating the metal raw material powder to obtain a gaseous raw material metal.

Step C: A step of cooling the gaseous raw material metal to obtain metal fine particles containing a transition metal.

Step D: A step of supplying an inert gas containing nitrogen gas into a plasma torch as plasma gas to generate thermal plasma salt.

Step E: A step of supplying metal fine particles containing a transition metal to a thermal plasma salt in a plasma torch, and evaporating the metal fine particles to obtain a gaseous raw material metal.

Step F: A step of cooling the gaseous raw material metal to obtain metal nitride-containing particles.

The method for producing metal nitride-containing particles may include the following step G depending on the purpose after the step C and/or the step F.

Step G: A step of classifying the obtained particles.

Before step A, between step A and step B, between step C and step D, or between step D and step E, the following step A2 may be further included.

Step A2: A step of mixing an atom A with a metal raw material powder containing a transition metal.

Before step A2, you may further include the following steps A3-1 to A3-3.

Step A3-1: A step of supplying an inert gas that does not contain nitrogen gas into the plasma torch as a plasma gas to generate thermal plasma salt.

Step A3-2: A step of supplying a raw material powder containing an atom A to a thermal plasma salt in a plasma torch, and evaporating the raw material powder to obtain an atom A in a gas phase.

Step A3-3: Step of cooling the gaseous atom A to obtain atomized atom A.

After step A3-3, you may further include step G.

In the present specification, the atom A that has been micronized refers to a particle having a primary particle diameter of 20 nm to 40 μm containing the atom A.

In addition, it is preferable that the manufacturing method of the said metal nitride-containing particle further includes the following process H after process F (when process G is included, after process G after process F).

Step H: A step of exposing the metal nitride-containing particles obtained in step F (or step G) to a mixed atmosphere of water vapor and nitrogen gas to perform nitriding treatment.

Depending on the purpose, the method for producing the metal nitride-containing particles may further include a step G after the step H. Hereinafter, suitable aspects of each step will be described in detail.

Process A

Step A is a step of supplying an inert gas that does not contain nitrogen gas into the plasma torch as a plasma gas to generate thermal plasma salt. The method of generating the thermal plasma salt is not particularly limited, but includes a direct current arc discharge method, a multi-phase arc discharge method, a high frequency plasma method, and a hybrid plasma method, and a high frequency plasma method in which impurities from the electrode are less mixed is preferred. .

The method of generating the thermal plasma salt by the high frequency plasma method is not particularly limited, and for example, a plasma gas is supplied into a plasma torch containing a high frequency oscillation coil and a quartz tube, and a high frequency current is applied to the high frequency oscillation coil. By doing this, the method of obtaining a thermal plasma salt is mentioned.

As the plasma gas in step A, an inert gas that does not contain nitrogen gas is exemplified. Argon gas, hydrogen gas, etc. are mentioned as an inert gas which does not contain nitrogen gas. The inert gas containing no nitrogen gas may be used alone or in combination of two or more.

Step A2

Step A2 is a step of mixing an atom A with a metal raw material powder containing a transition metal. The mixing method of the raw metal powder and the atom A is not particularly limited, and a known method can be used. For example, the material supply device for supplying metal raw material powder into the plasma torch may contain a mixing and dispersing function. Specifically, the material supply device described in paragraphs 0047 to 0058 of International Publication No. 2010/147098 can be used, and this content is incorporated in this specification. The method for producing metal nitride-containing particles may further include the following steps A3-1 to A3-3 before step A2.

Process B

Step B is a step of supplying a metal raw material powder containing a transition metal to a thermal plasma salt in a plasma torch, and evaporating the metal raw material powder to obtain a gaseous raw material metal. The method of supplying the metal raw material powder to the thermal plasma salt in the plasma torch is not particularly limited, but it is preferable that the resulting gaseous raw material metal is sprayed using a carrier gas from the viewpoint of becoming more uniform. It is preferable to use an inert gas that does not contain nitrogen gas as the carrier gas. The aspect of the inert gas containing no nitrogen gas is as described above.

When the method for producing metal nitride-containing particles includes the above step A2, it is preferable that the metal raw material powder is kept in a uniform dispersion state until the supply of the metal raw material powder into the plasma torch is reached. .

Process C

Step C is a step of cooling a gaseous raw material metal to obtain metal fine particles containing a transition metal. Although it does not specifically limit as a cooling method, It is preferable to use a chamber containing a cooling function. The gaseous raw material metal obtained in step B is introduced into a chamber containing the cooling function and rapidly cooled in the chamber, whereby metal fine particles having a desired particle diameter can be produced. The generated metal fine particles are recovered by, for example, a recovery unit. The atmosphere in the chamber is preferably an inert gas that does not contain nitrogen gas. The aspect of the inert gas containing no nitrogen gas is as described above.

Further, metal fine particles containing a transition metal are obtained by passing through the steps A to C. Metal fine particles containing a transition metal are likely to evaporate in step E. Even when the metal raw material powder contains impurities, the impurities can be removed by passing through the steps A to C.

Process D

Step D is a step of supplying an inert gas containing nitrogen gas into the plasma torch as a plasma gas to generate a thermal plasma salt. Examples of the inert gas containing nitrogen include nitrogen gas and nitrogen gas containing inert gas. Examples of the inert gas include argon gas and hydrogen gas. The nitrogen gas containing an inert gas is not particularly limited, but the content of the nitrogen gas is usually about 10 to 90 mol%, preferably about 30 to 60 mol%. Other aspects are the same as in step A.

Process E

Step E is a step of supplying metal fine particles containing a transition metal to the thermal plasma salt in a plasma torch, and evaporating the metal fine particles to obtain a gaseous raw material metal. The method of supplying the metal fine particles to the thermal plasma salt in the plasma torch is as described above, but the carrier gas is preferably an inert gas containing nitrogen. The aspect of the inert gas containing nitrogen is as described above.

In step E, since the raw metal, which has become metal fine particles in the steps A to C, is supplied to the thermal plasma salt, the raw material metal in the gas phase is easily obtained, and the state of the raw metal in the gas phase is also more uniform.

Process F

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

Process G

Step G is a step of classifying the obtained metal fine particles and/or metal nitride-containing particles. Although it does not specifically limit as a method of classification, For example, a cyclone can be used. The cyclone has a conical container, generates a swirling flow in the container, and has a function of classifying particles using centrifugal force. The classification is preferably performed in an atmosphere of an inert gas. The aspect of the inert gas is as described above.

Process H

Step H is a step of exposing the metal nitride-containing particles to a mixed atmosphere of water vapor and nitrogen gas to perform nitriding treatment. By passing through this process, the content of the metal nitride in the metal nitride-containing particles can be further increased. The method of exposing the metal nitride-containing particles to a mixed atmosphere of water vapor and nitrogen gas is not particularly limited, but for example, the metal nitride-containing particles are introduced into a thermostat filled with a gas mixture of water vapor and nitrogen gas, and allowed to stand for a predetermined time. Alternatively, a method of stirring may be mentioned, and it is more preferable to stand still because the surface and crystal boundary of the metal nitride-containing particles are more stabilized.

The mixing ratio of water vapor and nitrogen gas is preferably a condition in which the relative humidity is 25 to 95% in the air. The time to stand still or stir is preferably 0.5 to 72 hours, and the temperature at that time is preferably 10 to 40°C.

Step A3-1-A3-3

Steps A3-1 to A3-3 are a step of supplying an inert gas that does not contain nitrogen gas into the plasma torch as a plasma gas to generate a thermal plasma salt (A3-1), and to the thermal plasma salt in the plasma torch. A step of supplying a raw material powder containing A, evaporating the raw material powder to obtain an atom A in a gas phase (A3-2), and a step of cooling the atom A in the gas phase to obtain fine particles composed of an atom A (A3 -3). Aspects in each step are the above-described steps A, B (instead of the metal raw material powder containing the transition metal, the raw material powder containing the atom A is used), and the step C (instead of the metal fine particles containing the transition metal) E, obtaining atomized atom A).

By passing through the said process, atom A becomes microparticles|fine-particles, and it becomes easy to evaporate in process E. Moreover, impurities (metal components other than atom A, etc.) contained in the raw material powder containing the atom A can be removed by passing through the above process.

Suitable aspects of the method for producing metal nitride-containing particles containing atom A

As a preferred aspect of the method for producing metal nitride-containing particles containing an atom A, a method having the following steps in order is exemplified.

Step A: A step of supplying an inert gas that does not contain nitrogen gas into the plasma torch as plasma gas to generate thermal plasma salt.

Step B: A step of supplying a metal raw material powder containing a transition metal to a thermal plasma salt in a plasma torch, and evaporating the metal raw material powder to obtain a gaseous raw material metal.

Step C: A step of cooling the gaseous raw material metal to obtain metal fine particles containing a transition metal.

Step G: A step of classifying the obtained particles.

Step A3-1: A step of supplying an inert gas that does not contain nitrogen gas into the plasma torch as a plasma gas to generate thermal plasma salt.

Step A3-2: A step of supplying a raw material powder containing an atom A to a thermal plasma salt in a plasma torch, and evaporating the raw material powder to obtain an atom A in a gas phase.

Step A3-3: Step of cooling the gaseous atom A to obtain atomized atom A.

Step G: A step of classifying the obtained particles.

Step A2: A step of mixing an atom A (a micronized atom A in this case) with a metal raw material powder containing a transition metal (in this case, metal fine particles).

Step D: A step of supplying an inert gas containing nitrogen gas into a plasma torch as plasma gas to generate thermal plasma salt.

Step E: A step of supplying metal fine particles containing a transition metal to a thermal plasma salt in a plasma torch, and evaporating the metal fine particles to obtain a gaseous raw material metal.

Step F: A step of cooling the gaseous raw material metal to obtain metal nitride-containing particles.

Step G: A step of classifying the obtained particles.

Step H: A step of exposing the metal nitride-containing particles obtained in step G to a mixed atmosphere of steam and nitrogen gas to perform nitriding treatment.

In the series of steps described above, the order of steps A to C and steps A3-1 to A3-3 may be replaced. That is, after steps A3-1 to A3-3, steps A to C may be performed.

According to a preferred aspect of the method for producing the metal nitride-containing particles containing the atom A, the metal raw material powder and the impurities contained in the raw material particles can be removed, and the metal nitride-containing particles having a desired average primary particle diameter can do. As the reason, it is assumed that the transition metal and/or atom A is ionized by plasma treatment, and when the ions are cooled, the transition metal, atom A and impurities are made into fine particles by reflecting their respective melting points. At this time, atoms with a low melting point are rapidly granulated, and atoms with a high melting point are slowed down. For this reason, it is assumed that the fine particles (Steps B and C, and Steps A3-2 and A3-3) once plasma-treated as described above tend to become a single component (single crystal). When the particles of a single component obtained as described above are classified, particles of impurities can be removed by the difference between the particles of the transition metal and/or the particles of the atom A and the density and/or the diameter of the particles of the impurities. The classification can be performed by appropriately setting classification conditions using, for example, a cyclone or the like.

Purification of metal raw powder and raw powder

As a metal raw material powder containing a transition metal that can be used in the step B (hereinafter, simply referred to as "metal raw material powder") and a raw material powder containing the atom A (hereinafter simply referred to as "raw material powder"), , Although not particularly limited, a high purity one is preferable. Although the content of the transition metal in the metal raw material powder is not particularly limited, 99.99% or more is preferable and 99.999% or more is more preferable. The same is true for the content of the atom A in the raw material powder.

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

The method for producing metal nitride-containing particles may further include the following step A0 before step B (in the case of including step A2, before step A2).

Step A0: A step of removing impurities from the metal raw material powder and/or the raw material powder.

Process A0

In step A0, the method of removing impurities from the metal raw material powder and/or the raw material powder (separation and purification method) is not particularly limited, for example, paragraphs 0013 to 0030 of Japanese Laid-Open Patent Publication No. 2012-211048 for niobium. The method described in can be used, and a method similar to this can be used for other metal raw material powders and/or raw material powders.

Coating of metal nitride-containing particles

The metal nitride-containing particles may be metal nitride-containing particles coated with an inorganic compound. That is, it may be a coated metal nitride-containing particle having a metal nitride-containing particle and a coating layer formed using an inorganic compound that coats the metal nitride-containing particle. 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 oxides such as SiO ₂ , ZrO ₂ , TiO ₂ , GeO ₂ , Al ₂ O ₃ , Y ₂ O ₃ , and P ₂ O ₅ , and hydroxides such as aluminum hydroxide and zirconium hydroxide are used. Can be lifted. Among them, aluminum hydroxide is preferable because it is easy to form a thinner film and a film having a higher coverage ratio is easily formed.

When it is intended to control the refractive index of the metal nitride-containing particles, silicon oxide is preferable as the low refractive index coating, and zirconium hydroxide is preferable as the high refractive index coating.

The method of coating the metal nitride-containing particles with an inorganic compound is not particularly limited, but it is preferable that the production method of the metal nitride-containing particles includes the following inorganic compound coating step.

Inorganic compound coating process

The inorganic compound coating process is a process of coating the metal nitride-containing particles with an oxide and/or hydroxide. Although it does not specifically limit as a coating method, For example, the following wet coating method etc. are mentioned.

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

In the second wet coating method, first, the metal nitride-containing particles are mixed with an organic solvent such as alcohol to prepare a slurry. Next, in the slurry, 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, and the slurry is fired at high temperature. When the slurry is fired at a high temperature, a sol gel reaction proceeds to obtain metal nitride-containing particles coated with oxide.

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

·Organic pigment

As an organic pigment, for example, color index (CI) pigment yellow 1, 2, 3, 4, 5, 6, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35:1, 36, 36:1, 37, 37:1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 193, 194, 199, 213, 214, etc.;

CI Pigment Orange 2, 5, 13, 16, 17:1, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 71, 73, etc.;

CI Pigment Red 1, 2, 3, 4, 5, 6, 7, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48:1, 48:2, 48:3, 48: 4, 49, 49:1, 49:2, 52:1, 52:2, 53:1, 57:1, 60:1, 63:1, 66, 67, 81:1, 81:2, 81: 3, 83, 88, 90, 105, 112, 119, 122, 123, 144, 146, 149, 150, 155, 166, 168, 169, 170, 171, 172, 175, 176, 177, 178, 179, 184, 185, 187, 188, 190, 200, 202, 206, 207, 208, 209, 210, 216, 220, 224, 226, 242, 246, 254, 255, 264, 270, 272, 279, etc.;

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.

Can be mentioned. In addition, pigments may be used alone or in combination of two or more.

(dyes)

As a dye, for example, JP-A-64-090403, JP-A-64-091102, JP-A-1-094301, JP-A-6-011614, JP 2592207 , U.S. Patent Publication No.4808501, U.S. Patent Publication No.5667920, U.S. Patent Publication No.505950, JP-A No. 5-333207, JP-A-6-035183, JP-A6-051115 A dye disclosed in Japanese Patent Application Laid-Open No. Hei 6-194828 and the like can be used. In terms of chemical structure, pyrazole azo compound, pyromethane compound, anilinoazo compound, triphenylmethane compound, anthraquinone compound, benzylidene compound, oxonol compound, pyrazolo triazol azo compound, pyridonazo compound, Cyanine compounds, phenothiazine compounds, pyrrolopyrazole azomethine compounds, and the like can be used. You may use a dye multimer as a dye. Examples of the dye multimer include compounds described in JP2011-213925A and JP2013-041097A. A polymerizable dye having polymerizable properties in the molecule may be used, and as a commercial item, the RDW series manufactured by Wako Junyaku Co., Ltd. is mentioned, for example.

(Infrared absorber)

The coloring agent may further contain an infrared absorber.

The infrared absorber means a compound having absorption in the infrared region (preferably, the wavelength of 650 to 1,300 nm). The infrared absorber is preferably a compound having a maximum absorption wavelength in a wavelength range of 675 to 900 nm.

As a colorant having such spectral properties, for example, pyrrolopyrrole compounds, copper compounds, cyanine compounds, phthalocyanine compounds, iminium compounds, thiol complex compounds, transition metal oxide compounds, squarylium A compound, a naphthalocyanine compound, a quaterylene compound, a dithiol metal complex system compound, a chromonium compound, etc. are mentioned.

As the phthalocyanine compound, naphthalocyanine compound, iminium compound, cyanine compound, squarylium compound, and chromonium compound, the compounds disclosed in paragraphs 0010 to 0081 of JP 2010-111750 A may be used, This content is incorporated in this specification. As for the cyanine compound, "functional pigment, Makoto Ogawara / Masaru Matsuoka / Daiiro Kitao / Tsuneaki Hirashima, work, Kodansha Scientific" can be referred to, the contents of which are incorporated herein by reference. .

As a colorant having the above spectroscopic properties, a compound disclosed in paragraphs 0004 to 0016 of JP-A-07-164729 A and/or a compound disclosed in paragraphs 0027 to 062 of JP 2002-146254, Japanese Laid-Open Patent Publication 2011-164583 It is also possible to use near-infrared absorbing particles having a number average agglomerated particle diameter of 5 to 200 nm and consisting of crystallites of an oxide containing Cu and/or P disclosed in paragraphs 0034 to 0067 of the heading.

As the compound having a maximum absorption wavelength in the wavelength range of 675 to 900 nm, at least one selected from the group consisting of a cyanine compound, a pyrrolopyrrole compound, a squarylium compound, a phthalocyanine compound, and a naphthalocyanine compound Paper is preferred.

The infrared absorber is preferably a compound that dissolves at least 1% by mass in water at 25°C, and more preferably a compound dissolves at least 10% by mass in water at 25°C. By using such a compound, the solvent resistance becomes good.

As for the pyrrolopyrrole compound, paragraphs 0049 to 062 of JP 2010-222557 A can be referred to, and the contents are incorporated herein by reference. The cyanine compound and the squarylium compound are Paragraph Nos. 0022 to 0063 of International Publication No. 2014/088063, Paragraph Nos. 0053 to 0118 of International Publication No. 2014/030628, Paragraph Nos. 0028 to 0704 of Japanese Unexamined Patent Application Publication No. 2014-059550, Paragraph Nos. 0013 to 0091 of International Publication No. 2012/169447, Paragraph Nos. 0019 to 0033 of Japanese Unexamined Patent Application Publication No. 2015-176046, Paragraph Nos. 0053 to 0099 of Japanese Unexamined Patent Application Publication No. 2014-063144, and Paragraphs of Japanese Unexamined Patent Publication No. 2014-052431 Nos. 0085 to 0150, paragraph numbers 0076 to 0124 of JP 2014-044301 A, paragraph numbers 0045 to 0078 of JP 2012-008532 A, paragraph numbers 0027 to 0067 of JP 2015-172102 A, Japanese Patent Application Publication Paragraph numbers 0029 to 0067 of JP 2015-172004 A, paragraph numbers 0029 to 0085 of JP 2015-040895 A, paragraph numbers 0022 to 0036 of JP 2014-126642 A, paragraph number 0011 of JP 2014-148567 A ~0017, paragraph numbers 0010 to 0025 of Japanese Unexamined Patent Application Publication No. 2015-157893, paragraph numbers 0013 to 0026 of Japanese Unexamined Patent Application Publication No. 2014-095007, paragraph numbers 0013 to 0047 of Japanese Unexamined Patent Publication 2014-080487, and Japanese Unexamined Patent Application Publication Reference may be made to paragraph numbers 0007 to 0028 of 2013-227403, the contents of which are incorporated herein by reference.

At least one type of infrared absorber selected from the group consisting of compounds represented by the following general formulas 1 to 3 is preferable.

General Formula 1

[Formula 18]

In 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.

Formula 1-A

[Formula 19]

In General Formula 1-A, Z ^1A represents a group of non-metal atoms forming a nitrogen-containing heterocycle, R ^2A represents an alkyl group, an alkenyl group, or an aralkyl group, d represents 0 or 1, and the broken line is connected Show hand

Formula 2

[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, and R ² and R ³ , R ⁴ and R ⁵ may be bonded to each other to form a ring,

R ⁶ and R ⁷ each independently represent a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group, -BR ^A R ^B , or a metal atom, and R ^A and R ^B are each independently a hydrogen atom, or Represents a substituent,

R ⁶ may have a covalent bond or a coordination bond with R ^1a or R ^3, and R ⁷ may be a covalent bond or a coordination bond with R ^1b or R ⁵ .

Formula 3

[Formula 21]

In General Formula 3, Z ¹ and Z ² are each independently a non-metal atom group forming a 5- or 6-membered nitrogen-containing heterocycle which may be condensed,

R ¹⁰¹ and R ¹⁰² each independently represent an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group, or an aryl group,

L ¹ represents a metaprint consisting of an odd number of metains,

a and b are each independently 0 or 1,

When a is 0, a carbon atom and a nitrogen atom are bonded by a double bond, and when b is 0, a carbon atom and a nitrogen atom are bonded by a single bond,

When the moiety represented by Cy in the formula is a cation moiety, X ¹ represents an anion, c represents the number necessary to balance the charge, and when the moiety represented by Cy in the formula is an anion moiety, X ¹ represents a cation, c Represents the number necessary to balance the charge, and c is 0 when the charge at the site represented by Cy in the formula is neutralized in the molecule.

(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 an organic pigment is substituted with an acidic group, a basic group, or a phthalimidemethyl group. As the pigment derivative, from the viewpoint of dispersibility and dispersion stability of the colorant A, a pigment derivative having an acidic group or a basic group is preferable. It is particularly preferable that the pigment derivative has a basic group. The combination of the above-described resin (dispersant) and the pigment derivative is preferably a combination in which the dispersant is an acidic dispersant and the pigment derivative has a basic group.

As organic pigments for constituting pigment derivatives, diketopyrrolopyrrole pigments, azo pigments, phthalocyanine pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, perinone pigments, perylene pigments , Thioindigo pigments, isoindolin pigments, isoindolinone pigments, quinophthalone pigments, tren pigments, metal complex pigments, and the like.

As the acidic group which the pigment derivative has, 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 more preferable. As a basic group which the pigment derivative has, an amino group is preferable and a tertiary amino group is more preferable.

When the curable composition contains a pigment derivative, the content of the pigment derivative is preferably 1 to 30% by mass, more preferably 3 to 20% by mass, based on the mass of the pigment. As for the pigment derivative, only 1 type may be used and 2 or more types may be used together.

<Polymerization inhibitor>

The curable composition may contain a polymerization inhibitor. By containing a polymerization inhibitor, the curable composition has more excellent aging stability. In addition, in the present specification, the term stability over time means that a cured film having an excellent pattern shape can be obtained even when the curable composition is prepared and stored for a predetermined period of time.

In the curable composition during storage, the polymerization inhibitor has an action of suppressing the progress of the reaction between the polyfunctional thiol compound and the polymerizable compound, and it is assumed that the above effect is obtained.

The content of the polymerization inhibitor is preferably 0.001 to 1% by mass, more preferably 0.005 to 1% by mass, and still more preferably 0.05 to 1% by mass with respect 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 aging stability.

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

As a phenolic compound, for example, phenol, 4-methoxyphenol, hydroquinone, 2-tert-butylhydroquinone, catechol, 4-tert-butyl-catechol, 2,6-di-tert-butylphenol , 2,6-di-tert-butyl-4-methylphenol, 2,6-di-tert-butyl-4-ethylphenol, 4-hydroxymethyl-2,6-di-tert-butylphenol, pentaeryth Lithol tetrakis (3,5-di-tert-butyl-4-hydroxyhydrocinnamate), 4-methoxy-1-naphthol, and 1,4-dihydroxynaphthalene.

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

[Formula 22]

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

Examples of R ₁ to R ₅ in formula (IH-1) include a hydrogen atom, an alkyl group having 1 to 5 carbon atoms (eg, a methyl group and an ethyl group, etc.), and an alkoxy group having 1 to 5 carbon atoms (eg, a methoxy group and an ethoxy group. Period, etc.), a C2-C4 alkenyl group (for example, a vinyl group, etc.), or a phenyl group is preferable.

Among them, R ₁ and R ₅ are each independently a hydrogen atom or a tert-butyl group more preferably, R ₂ and R ₄ are more preferably a hydrogen atom, and R ₃ is a hydrogen atom, a C 1 to C 5 alkyl group or a C 1-5 alkoxy groups are more preferable.

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

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

[Formula 23]

R ₆ in formula (IH-2) represents a hydrogen atom, a hydroxy group, an amino group, an alkoxy group, an alkoxycarbonyl group, or an acyl group. Among them, a hydrogen atom or a hydroxy group is preferable, and a hydroxy group is more preferable.

R ₇ to R ₁₀ in formula (IH-2) each independently represent a hydrogen atom or an alkyl group. 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 a polymerization inhibitor, each of the above compounds may be used singly, two may be used in combination, or three or more may be used in combination.

It is preferable that the polymerization inhibitor contains a phenolic compound. Among them, it is more preferable that the polymerization inhibitor contains two or more phenolic compounds. The curable composition containing another phenolic compound has a more excellent effect of the present invention.

It is preferable that the polymerization inhibitor contains a phenolic compound and a hindered amine compound. A curable composition containing a phenolic compound and a hindered amine compound has a more excellent effect 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. It is preferable that the curable composition contains an organic solvent.

When the curable composition contains a solvent, the solid content of the curable composition is preferably 10 to 30% by mass. When the solid content of the curable composition is more than the lower limit, the viscosity is low and the coatability becomes good. Further, since the concentration of the highly reactive compound is lowered, stability over time becomes good. When the solid content of the curable composition is less than or equal to the upper limit, the viscosity is maintained at a low degree and the coatability becomes good. Further, the coloring agent having a heavy specific gravity becomes difficult to settle, and the stability with time becomes good.

(Organic solvent)

When the curable composition contains an organic solvent, the content of the organic solvent is preferably 70 to 90% by mass with respect to the total mass of the curable composition.

In addition, an organic solvent may be used individually by 1 type, and may use 2 or more types together. When using two or more types of organic solvents together, it is preferable that the total amount falls within the above range.

Although it does not specifically limit as an organic solvent, For example, acetone, methyl ethyl ketone, cyclohexane, ethylene dichloride, tetrahydrofuran, toluene, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether , Ethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, acetylacetone, cyclohexanone, cyclopentanone, diacetone alcohol, ethylene glycol monomethyl ether Teracetate, ethylene glycol ethyl ether acetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether acetate, 3-methoxypropanol, methoxymethoxyethanol, diethylene glycol mono Methyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl Etheracetate, 3-methoxypropylacetate, N,N-dimethylformamide, dimethyl sulfoxide, γ-butyrolactone, 3-ethoxymethylpropionate, 3-ethoxypropionate ethyl, ethylcellosolve acetate , Methyl 3-methoxypropionate, 2-heptanone, ethyl carbitol acetate, butyl carbitol acetate, ethyl acetate, butyl acetate, methyl lactate, and ethyl lactate.

In the case of containing two or more kinds of organic solvents, the above methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycoldimethyl ether, butyl acetate, 3 -Methyl methoxypropionate, 2-heptanone, cyclohexanone, cyclopentanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether, and propylene glycol monomethyl ether acetate It is preferably composed of two or more selected from the group.

(water)

The curable composition may contain water. Water may be added intentionally, or may be contained in the curable composition inevitably 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 the water content is within the above range, the occurrence of pinholes is suppressed when the cured film is produced, and the moisture resistance of the cured film is improved.

<Dispersant>

It is preferable that the curable composition contains a dispersant. The dispersant contributes to improving the dispersibility of the colorant. In this specification, the dispersant and the binder resin described later are different components.

When the curable composition contains a dispersant, the content of the dispersant is preferably 0.05 to 50% by mass, and more preferably 0.05 to 30% by mass with respect to the total solid content of the curable composition.

When the content of the dispersant is 0.05 to 30 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.

Dispersants may be used alone or in combination of two or more. When using two or more kinds of dispersants in combination, it is preferable that the total amount is within the above range.

As the dispersant, for example, a known pigment dispersant can be appropriately selected and used. Among them, a high molecular compound is preferable.

As a dispersant, a polymer dispersant (e.g., polyamidoamine 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, naphthalene sulfonic acid formalin condensate], polyoxyethylene alkyl phosphate ester, polyoxyethylene alkyl amine, and pigment derivatives.

Polymer compounds can be further classified into linear polymers, terminal modified polymers, graft polymers, and block polymers from their structure.

(Polymer compound)

The polymer compound acts to prevent re-aggregation of the object to be dispersed by adsorbing on the surface of the object to be dispersed of the colorant (eg, inorganic pigment). For this reason, terminal-modified polymers, graft-type polymers, and block-type polymers containing anchor sites on the pigment surface are preferred.

It is preferable that the high molecular compound contains a structural unit containing a graft chain. In this specification, "structural unit" is synonymous with "repeating unit".

Since the polymer compound containing the structural unit containing such a graft chain has affinity with a solvent due to the graft chain, it is excellent in dispersibility of colorants such as black pigments and dispersion stability after aging (stability with time). . The polymer compound containing a structural unit containing a graft chain has affinity with a polymerizable compound or other resins that can be used in combination due to the presence of the graft chain. As a result, it becomes difficult to generate a residue due to alkali development.

When the graft chain is long, the steric repulsion effect increases, and the dispersibility of a black pigment or the like is improved. On the other hand, if the graft chain is too long, the adsorption power to colored pigments such as black pigments decreases, and the dispersibility of the black pigments tends to decrease. For this reason, the number of atoms excluding hydrogen atoms in the graft chain is preferably 40 to 10,000, more preferably 50 to 2,000 excluding hydrogen atoms, and more preferably 60 to 500 atoms excluding hydrogen atoms .

Here, the graft chain represents from the origin of the main chain of the copolymer (an atom bonded to the main chain in a group branched from the main chain) to the terminal of the group branched from the main chain.

It is preferable that the graft chain contains a polymer structure, and as such a polymer structure, for example, a poly(meth)acrylate structure (for example, a poly(meth)acrylic structure), a polyester structure, a polyurethane Phosphorus structure, polyurea structure, polyamide structure, and polyether structure.

In order to improve the interaction between the graft chain and the solvent and thereby increase the dispersibility of the black pigment, the graft chain is at least one selected from the group consisting of a polyester structure, a polyether structure, and a poly(meth)acrylate structure. It is preferable that it is a graft chain containing a species, and it is more preferable that it is a graft chain containing at least either a polyester structure or a polyether structure.

Although it does not specifically limit as a macromonomer containing such a graft chain, A macromonomer containing a reactive double bond group can be used suitably.

Corresponding to the structural unit containing the graft chain contained in the polymer compound, commercially available macromonomers suitably used for the synthesis of polymer compounds include AA-6 (trade name, manufactured by Toa Kosei), AA-10 (trade name, Toa Kosei). Co., Ltd.), AB-6 (brand name, Toa Kosei Co., Ltd.), AS-6 (brand name, Toa Kosei Co., Ltd.), AN-6 (brand name, Toa Kosei Co., Ltd.), AW-6 (brand name, Toa Kosei Co., Ltd.), AA-714 (Brand name, manufactured by Toa Kosei), AY-707 (brand name, manufactured by Toa Kosei), AY-714 (brand name, manufactured by Toa Kosei), AK-5 (brand name, manufactured by Toa Kosei), AK-30 (brand name, by Toa Kosei) ), AK-32 (brand name, manufactured by Doa Kosei), Blammer PP-100 (brand name, manufactured by Nichiyu), Blammer PP-500 (brand name, manufactured by Nichiyu), Blammer PP-800 (brand name, manufactured by Nichiyu Corporation) ), Blammer PP-1000 (brand name, manufactured by Nichiyu Corporation), Blammer 55-PET-800 (brand name, manufactured by Nichiyu Corporation), Blammer PME-4000 (brand name, manufactured by Nichiyu Corporation), Blammer PSE-400 (brand name) , Nichiyu Corporation), Blammer PSE-1300 (brand name, Nichiyu Corporation make), Blammer 43PAPE-600B (brand name, Nichiyu Corporation make), etc. are mentioned. Among them, AA-6 (brand name, manufactured by Toa Kosei), AA-10 (brand name, manufactured by Toa Kosei), AB-6 (brand name, manufactured by Toa Kosei), AS-6 (brand name, manufactured by Toa Kosei), AN-6 (Brand name, manufactured by Toa Kosei), and Blemmer PME-4000 (brand name, manufactured by Nichiyu), and the like are preferable.

It is preferable that the dispersant contains at least one structure selected from the group consisting of methyl polyacrylate, methyl polymethacrylate, and cyclic or chain polyester. It is more preferable that the dispersant contains at least one structure selected from the group consisting of methyl polyacrylate, polymethyl methacrylate, and chain polyester. It is more preferable that the dispersant contains at least one structure selected from the group consisting of a methyl polyacrylate structure, a polymethyl methacrylate structure, a polycaprolactone structure, and a polyvalerolactone structure. The dispersant may contain the above structure alone in one dispersant, or may contain a plurality of these structures in one dispersant.

Here, the polycaprolactone structure means containing a structure obtained by ring-opening ε-caprolactone as a repeating unit. The polyvalerolactone structure refers to containing a structure obtained by ring-opening δ-valerolactone as a repeating unit.

As a specific example of the dispersant containing a polycaprolactone structure, j and k in the following formula (1) and the following formula (2) are 5, and are mentioned. Moreover, as a specific example of the dispersing agent containing a polyvalerolactone structure, what j and k in following formula (1) and following formula (2) are 4 are mentioned.

As a specific example of the dispersing agent containing a methyl polyacrylate structure, what X ⁵ in the following formula (4) is a hydrogen atom, and R ⁴ is a methyl group is mentioned. Moreover, as a specific example of the dispersing agent containing a polymethyl methacrylate structure, the thing which X ⁵ in following formula (4) is a methyl group, and R ⁴ is a methyl group is mentioned.

Structural unit containing a graft chain

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

[Formula 24]

In formulas (1) to (4), W ¹ , W ² , W ³ , and W ⁴ each independently represent an oxygen atom or NH. W ¹ , W ² , W ³ , and W ⁴ are preferably oxygen atoms.

In formulas (1) to (4), X ¹ , X ² , X ³ , X ⁴ , and X ⁵ each independently represent a hydrogen atom or a monovalent organic group. 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 (carbon atom number), each independently, from the viewpoint of synthetic constraints, A hydrogen atom or a methyl group is more preferable, and a methyl group is more preferable.

In formulas (1) to (4), Y ¹ , Y ² , Y ³ , and Y ⁴ each independently represent a divalent linking group, and the linking group is not particularly limited in terms of structure. As the divalent linking group represented by Y ¹ , Y ² , Y ³ , and Y ⁴ , specifically, the following linking groups (Y-1) to (Y-21), etc. are exemplified. In the structures shown below, A and B each mean a binding site. Among the structures shown below, (Y-2) or (Y-13) is more preferable from the simplicity of synthesis.

[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, but specifically, an alkyl group, a hydroxy group, an alkoxy group, an aryloxy group, a heteroaryloxy group, an alkylthioether group, an arylthioether group, a heteroarylthioether group, and And amino groups. Among these, as the organic group represented by Z ¹ , Z ² , Z ³ , and Z ⁴ , in particular, from the viewpoint of improving dispersibility, it is preferable to contain a steric repulsion effect, and each independently an alkyl group or alkoxy having 5 to 24 carbon atoms A group is more preferable, and among them, each independently a branched alkyl group having 5 to 24 carbon atoms, a cyclic alkyl group having 5 to 24 carbon atoms, or an alkoxy group having 5 to 24 carbon atoms is more preferable. The alkyl group contained in the alkoxy group may be linear, branched, or cyclic.

In formulas (1) to (4), n, m, p, and q are each independently an integer of 1 to 500.

In formula (1) and formula (2), j and k each independently represent the integer of 2-8. In formulas (1) and (2), j and k are preferably an integer of 4 to 6, and most preferably 5 from the viewpoint of stability over time and developability of the curable composition.

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, a plurality of R ³ may be the same or different.

In formula (4), R ⁴ represents a hydrogen atom or a monovalent organic group, and the monovalent organic group is not particularly limited in terms of structure. R ⁴ is preferably a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group, and more preferably a hydrogen atom or an alkyl group. When R ⁴ is an alkyl group, a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, or a cyclic alkyl group having 5 to 20 carbon atoms is preferable, and a linear alkyl group having 1 to 20 carbon atoms is more preferable, A linear alkyl group having 1 to 6 carbon atoms is more preferable. In formula (4), when q is 2 to 500, a plurality of X ⁵ and R ⁴ present in the graft copolymer may be the same or different from each other.

The high molecular compound may contain structural units containing graft chains having two or more different structures. That is, structural units represented by formulas (1) to (4) having different structures may be included in the molecule of the polymer compound, and n, m, p, and q in formulas (1) to (4) When each represents an integer of 2 or more, in formulas (1) and (2), j and k may contain different structures in the side chain, and in formulas (3) and (4), in the molecule A plurality of R ³ , R ^4, and X ⁵ may be the same or different.

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

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

[Formula 26]

Formula (1A) of the, X ^1, Y ^1, Z ¹ and n is ¹ and X, Y ^1, Z ¹ and n and the consent of the formula (1), are also the same preferable range. In the formula ^{(2A), X 2, Y} 2, Z 2 and m is ^2, and X, Y ^2, Z ² and m and consent of the formula (2) are also the same preferable range.

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

[Formula 27]

In the formula (3A) or ^{(3B), X 3, Y} 3, Z 3 , and p is ^3, and X, Y ^3, Z ^3, and p and consent of the formula (3) are also the same preferable range.

It is more preferable that a high molecular compound contains a structural unit represented by Formula (1A) as a structural unit containing a graft chain.

In the polymer compound, the structural unit containing the graft chain (for example, the structural unit represented by the above formulas (1) to (4)) is 2 to 90% of the total mass of the polymer compound in terms of mass. It is preferably included in the range, and more preferably included in the range of 5 to 30%. When the structural unit containing the graft chain is contained within this range, the dispersibility of the black pigment is high, and the developability when forming a cured film is good.

·Hydrophobic structural unit

It is preferable that the polymer compound contains 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 (eg, 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 expressed more reliably.

The ClogP value is a value calculated with the program "CLOGP" available from Daylight Chemical Information System, Inc. This program provides the value of "calculated logP" calculated by the fragment approach of Hansch, Leo (see document below). The fragment approach is based on the chemical structure of the compound, and the logP value of the compound is estimated by dividing the chemical structure into partial structures (fragments) and summing the logP contributions assigned to the fragments. The details are described in the following documents. In this specification, the ClogP value is intended as a 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 log Poct from structure. Chem. Rev., 93, 1281-1306, 1993.

logP means the common logarithm of the partition coefficient P (Partition Coefficient), and is a physical property value indicating how an organic compound is distributed in a two-phase equilibrium of oil (usually 1-octanol) and water, as a quantitative value. It is represented by the following equation.

logP=log(Coil/Cwater)

In the formula, Coil represents the molar concentration of the compound in the oil phase, and Cwater represents the molar concentration of the compound in the aqueous phase.

If the value of logP increases positively based on 0, the solubility increases, and if the absolute value increases as negative, it means that the water solubility increases.There is a correlation between the water solubility of organic compounds and the negative. It is widely used as a parameter for evaluating hydrophilicity.

It is preferable that the high molecular compound contains as a hydrophobic structural unit at least one structural unit selected from structural units derived from monomers represented by the following formulas (i) to (iii).

[Formula 28]

In formulas (i) to (iii), R ¹ , R ² and R ³ are each independently a hydrogen atom, a halogen atom (e.g., a fluorine atom, a chlorine atom, a bromine atom, etc.), or a carbon number 1-6 alkyl group (for example, a methyl group, an ethyl group, a propyl group, etc.) is shown.

R ¹ , R ² and R ³ are preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and more preferably a hydrogen atom or a methyl group. 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 is preferably an oxygen atom.

L is a single bond or a divalent linking group. As a divalent linking group, a divalent aliphatic group (e.g., 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 (e.g. , Arylene group, substituted arylene group), divalent heterocyclic group, oxygen atom (-O-), sulfur atom (-S-), imino group (-NH-), substituted imino group (-NR ³¹ -, where R ³¹ is an aliphatic group, an aromatic group or a heterocyclic group), a carbonyl group (-CO-), and combinations thereof.

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

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

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

It is preferable that L is a single bond, an alkylene group, or a divalent linking group containing an oxyalkylene structure. It is more preferable that the oxyalkylene structure is an oxyethylene structure or an oxypropylene structure. L may contain a polyoxyalkylene structure containing two or more oxyalkylene structures repeatedly. 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 is an aliphatic group (e.g., an alkyl group, a substituted alkyl group, an unsaturated alkyl group, a substituted unsaturated alkyl group), an aromatic group (e.g., an aryl group, a substituted aryl group, an arylene group, a substituted arylene group), a heterocyclic group, or these A combination of is mentioned. In these groups, an oxygen atom (-O-), a sulfur atom (-S-), an imino group (-NH-), a substituted imino group (-NR ³¹ -, wherein R ³¹ is an aliphatic group, an aromatic group or a heterocyclic group. ), or a carbonyl group (-CO-) may be contained.

The aliphatic group may have a cyclic structure or a branched structure. The number of carbon atoms of the aliphatic group is preferably 1 to 20, more preferably 1 to 15, and still more preferably 1 to 10. The aliphatic group further includes a cyclic group hydrocarbon group and a interchangeable hydrocarbon group, and examples of the cyclic group hydrocarbon group include a bicyclohexyl group, a perhydronaphthalenyl group, a biphenyl group, and a 4-cyclohexylphenyl group. . As the interchangeable hydrocarbon ring, for example, pineine, boneine, nopineine, noboneine, bicyclooctane ring (bicyclo[2.2.2]octane ring, and bicyclo[3.2.1] Octane ring, etc.), such as bicyclic hydrocarbon rings, homobledine, adamantane, tricyclo[5.2.1.0 ^2,6 ]decane, and tricyclo[4.3.1.1 ^2,5 ]undecaine ring, etc. Tricyclic hydrocarbon rings, tetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ]dodecane, and tetracyclic hydrocarbons such as perhydro-1,4-methano-5,8-methanonaphthalene rings And summoning. In the interchangeable hydrocarbon ring, a condensed cyclic hydrocarbon ring such as perhydronaphthalene (decalin), perhydroanthracene, pahydrophenanthrene, perhydroacenaphthene, perhydrofluorene, perhydroindene, and perhydro Condensed rings obtained by condensing a plurality of 5- to 8-membered cycloalkane rings such as phenalene rings are also included.

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, the aliphatic group does not have an acid group as a substituent.

The number of carbon atoms in the aromatic group is preferably 6 to 20, more preferably 6 to 15, and still 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, and a heterocyclic group. However, the aromatic group does not have an acid group as a substituent.

It is preferable that the heterocyclic group contains a 5-membered ring or a 6-membered ring as a heterocycle. Other heterocycles, aliphatic rings or aromatic rings may be condensed with the heterocycle. The heterocyclic group may have a substituent. Examples of the substituent include a halogen atom, a hydroxy group, an oxo group (=O), a thioxo group (=S), an imino group (=NH), a substituted imino group (=NR ³² , wherein R ³² is an 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 are each independently a hydrogen atom, a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom, etc.), and having 1 to 6 carbon atoms. It represents an alkyl group (for example, a methyl group, an ethyl group, a propyl group, etc.), Z, or LZ. Here, L and Z have the same meaning as above. As R ⁴ , R ⁵ , and R ⁶ , a hydrogen atom or an alkyl group having 1 to 3 carbon atoms is preferable, and a hydrogen atom is more preferable.

As a monomer represented by formula (i), R ¹ , R ² and R ³ are a hydrogen atom or a methyl group, L is a single bond or a divalent linking group containing an alkylene group or an oxyalkylene structure, and X is an oxygen atom or already A compound wherein Z is an aliphatic group, a heterocyclic group or an aromatic group is preferable.

As the monomer represented by formula (ii), a compound in which R ¹ is a hydrogen atom or a methyl group, L is an alkylene group, and Z is an aliphatic group, a heterocyclic group or an aromatic group is preferable.

As the monomer represented by formula (iii), a compound in which R ⁴ , R ⁵ , and R ⁶ is a hydrogen atom or a methyl group, and Z is an aliphatic group, a heterocyclic group, or an aromatic group is preferable.

Examples of typical compounds represented by formulas (i) to (iii) include radical polymerizable compounds selected from acrylic acid esters, methacrylic acid esters, and styrenes.

As an example of a typical compound represented by formulas (i) to (iii), the compounds described in paragraphs 0089 to 0093 of JP 2013-249417 A can be referred to, and these contents are incorporated herein by reference.

In the polymer compound, the hydrophobic structural unit is preferably contained in a range of 10 to 90%, more preferably in a range of 20 to 80%, based on the total mass of the polymer compound in terms of mass. When the content is in the above range, good pattern formation is obtained.

Functional groups that can interact with colorants such as black pigments

The polymer compound can introduce a functional group capable of forming an interaction with a colorant such as a black pigment. Here, it is preferable that the polymer compound further contains a structural unit containing a functional group capable of forming an interaction with a colorant such as a black pigment.

Examples of functional groups capable of forming an interaction with a colorant such as a black pigment include an acid group, a basic group, a coordination group, and a functional group having reactivity.

When the polymeric compound contains an acid group, a basic group, a coordinating group, or a reactive functional group, each structural unit containing an acid group, a structural unit containing a basic group, a structural unit containing a coordinating group, or a structure having reactivity It is preferred to contain units.

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 to the polymer compound, the curable composition contains alkali-soluble polymer compounds as a dispersant that contributes to the dispersion of colorants such as black pigments. The curable composition containing such a high molecular compound has excellent light-shielding properties in the exposed portion, and the alkali developability in the unexposed portion is improved.

When the polymer compound contains a structural unit containing an acid group, the polymer compound is easily compatible with the solvent, and the coating property tends to be improved.

This is a polymer compound in which the acid group in the structural unit containing the acid group easily interacts with a colorant such as a black pigment, and the polymer compound stably disperses a colorant such as a black pigment while dispersing a colorant such as a black pigment It is estimated that this is because the viscosity of the polymer is lowered and the polymer compound itself is also easily stably dispersed.

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

As an acid group that is a functional group capable of forming an interaction with a colorant such as a black pigment, for example, a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, or a phenolic hydroxy group, etc., and at least a carboxylic acid group, a sulfonic acid group, and a phosphoric acid group One type is preferable, and a carboxylic acid group is more preferable since the adsorption power to a colorant such as a black pigment is good, and the dispersibility of the colorant is high.

That is, it is preferable that the high molecular compound further contains a structural unit containing at least one of a carboxylic acid group, a sulfonic acid group, and a phosphoric acid group.

The high molecular compound may have one or two or more structural units containing an acid group.

The polymer compound may or may not contain a structural unit containing an acid group, but when it contains, the content of the structural unit containing an acid group is, in terms of mass, preferably 5 to the total mass of the polymer compound. It is 80%, and more preferably, it is 10-60% from a viewpoint of damage suppression of the image intensity by alkali development.

As a basic group that is a functional group capable of forming an interaction with a colorant such as a black pigment, for example, a primary amino group, a secondary amino group, a tertiary amino group, a heterocycle containing an N atom, and an amide group, etc. And preferred is a tertiary amino group from the viewpoint of having good adsorption power to colorants such as black pigments and high dispersibility of the colorant. The polymer compound may contain one or two or more of these basic groups.

The polymer compound may or may not contain a structural unit containing a basic group, but when it is contained, the content of the structural unit containing a basic group is, in terms of mass, 0.01% or more and 50% of the total mass of the polymer compound. The following are preferable, and from the viewpoint of suppressing developability inhibition, 0.01% or more and 30% or less are more preferable.

As a functional group which is a functional group capable of forming an interaction with a colorant such as a black pigment, and a functional group having reactivity, for example, an acetylacetoxy group, a trialkoxysilyl group, an isocyanate group, an acid anhydride, and an acid chloride And the like. Preferred is an acetylacetoxy group from the viewpoint of good adsorption power to colorants such as black pigments and high dispersibility of the colorant. The polymer compound may have one or two or more of these groups.

The polymer compound may or may not contain a structural unit containing a coordinating group or a structural unit containing a reactive functional group, but if it is contained, the content of these structural units is the total amount of the polymer compound in terms of mass. The mass is preferably 10% or more and 80% or less, and more preferably 20% or more and 60% or less from the viewpoint of suppressing developability inhibition.

When the polymer compound contains a functional group capable of forming an interaction with a colorant such as a black pigment in addition to the graft chain, it is sufficient to contain a functional group capable of forming an interaction with a colorant such as the above various black pigments, There is no particular limitation on how these functional groups are introduced, but it is preferable that the polymer compound contains at least one structural unit selected from structural units derived from monomers represented by the following general formulas (iv) to (vi).

[Chemical Formula 29]

In formulas (iv) to (vi), R ¹¹ , R ¹² , and R ¹³ are each independently a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, etc.), or Represents an alkyl group having 1 to 6 carbon atoms (eg, a methyl group, an ethyl group, a propyl group, etc.).

In formulas (iv) to (vi), R ¹¹ , R ¹² , and R ¹³ are preferably each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably, each independently It is a hydrogen atom or a methyl group. In general formula (iv), it is particularly preferable that R ¹² and R ¹³ are each a hydrogen atom.

X ₁ in formula (iv) represents an oxygen atom (-O-) or an imino group (-NH-), and is preferably an oxygen atom.

Y in formula (v) represents a metaphosphorus group or a nitrogen atom.

L ₁ in formulas (iv) to (v) represents a single bond or a divalent linking group. Examples of the divalent linking group include a divalent aliphatic group (e.g., an alkylene group, a substituted alkylene group, an alkenylene group, a substituted alkenylene group, an alkynylene group, and a substituted alkynylene group), and a divalent aromatic group (e.g. For example, an arylene group and a substituted arylene group), a divalent heterocyclic group, an oxygen atom (-O-), a sulfur atom (-S-), an imino group (-NH-), a substituted imino bond (-NR ³¹ ′ -Herein, R ³¹ ′ includes an aliphatic group, an aromatic group or a heterocyclic group), a carbonyl bond (-CO-), and combinations thereof.

The divalent aliphatic group may have a cyclic structure or a branched structure. The number of carbon atoms of the aliphatic group is preferably 1 to 20, more preferably 1 to 15, and still 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. Examples of the substituent include a halogen atom, a hydroxy group, an aromatic group, and a heterocyclic group.

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

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

It is preferable that L ₁ is a single bond, an alkylene group, or a divalent linking group containing an oxyalkylene structure. It is more preferable that the oxyalkylene structure is an oxyethylene structure or an oxypropylene structure. L ₁ may contain a polyoxyalkylene structure containing two or more oxyalkylene structures repeatedly. 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 capable of forming an interaction with a colorant such as a black pigment other than the graft chain, and is preferably a carboxylic acid group and a tertiary amino group, and is a carboxylic acid group. It is more preferable.

In formula (vi), R ¹⁴ , R ¹⁵ , and R ¹⁶ are each independently a hydrogen atom, a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom, etc.), and having 1 to 6 carbon atoms. An alkyl group (eg, methyl group, ethyl group, propyl group, etc.), -Z ₁ , or L ₁ -Z ₁ is represented. Here, L ₁ and Z ₁ is, and L ₁ and Z ₁ and copper in the above, preferred examples are the same. As R ¹⁴ , R ¹⁵ , and R ¹⁶ , each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms is preferable, and a hydrogen atom is more preferable.

As a monomer represented by 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, and X ₁ is oxygen A compound in which it is an atom or an imino group and Z ₁ is a carboxylic acid group is preferable.

As the monomer represented by formula (v), 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 metaphosphorus group is preferable.

Further, as the monomer represented by formula (vi), a compound in which 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 preferable.

Below, a typical example of a monomer (compound) represented by Formula (iv)-Formula (vi) is shown.

Examples of monomers include methacrylic acid, crotonic acid, isocrotonic acid, a reaction product of a compound containing an addition polymerizable double bond and a hydroxyl group in the molecule (e.g., 2-hydroxyethyl methacrylic acid) and succinic anhydride , A reaction product of a compound containing an addition polymerizable double bond and a hydroxy group in a molecule and a phthalic anhydride, a reaction product of a compound containing an addition polymerizable double bond and a hydroxy group in a molecule and a tetrahydroxyphthalic anhydride, an addition polymerization in a molecule Reaction product of compound containing double bond and hydroxy group with trimellitic anhydride, reaction product of compound containing addition polymerizable double bond and hydroxy group in molecule with pyromellitic anhydride, acrylic acid, acrylic acid dimer, acrylic acid oligomer , Maleic acid, itaconic acid, fumaric acid, 4-vinylbenzoic acid, vinylphenol, and 4-hydroxyphenylmethacrylamide.

The content of the structural unit containing a functional group capable of forming an interaction with a colorant such as a black pigment is the total mass of the polymer compound from the viewpoint of interaction with a colorant such as a black pigment, stability over time, and permeability to a developer. Relatively, 0.05% by mass to 90% by mass is preferable, 1.0% by mass to 80% by mass is more preferable, and 10% by mass to 70% by mass is still more preferable.

·Other structural units

Further, for the purpose of improving all performances such as image intensity, the polymeric compound is mutually interrelated with a structural unit containing a graft chain, a hydrophobic structural unit, and a coloring agent such as a black pigment, as long as the effect of the present invention is not impaired. Different from the structural unit containing a functional group capable of forming an action, other structural units having various functions (e.g., structural units containing a functional group having affinity with the dispersion medium used in the dispersion) are further added. You may have it.

Examples of such other structural units include structural units derived from radically polymerizable compounds selected from acrylonitrile and methacrylonitrile.

In the polymer compound, one or two or more of these different structural units can be used, and the content thereof, in terms of mass, is preferably 0% or more and 80% or less, and 10% or more and 60% with respect to the total mass of the polymer compound. The following are more preferable. When the content is in the above range, sufficient pattern formation is maintained.

·Physical properties of polymer compounds

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 10 mgKOH/g or more and 200 mgKOH/g or less, and more preferably 20 mgKOH/g or more and 120 mgKOH/g or less.

When the acid value of the polymer compound is 160 mgKOH/g or less, pattern peeling during development when 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 becomes more favorable. In addition, when the acid value of the polymer compound is 20 mgKOH/g or more, sedimentation of colorants such as black pigments can be more suppressed, the number of coarse particles can be further reduced, and the aging stability of the curable composition can be further improved.

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

The weight average molecular weight of the polymer compound is 4,000 or more and 300,000 or less as a polystyrene conversion value by GPC (Gel Permeation Chromatography: Gel Permeation Chromatography) method from the viewpoint of pattern peeling inhibition and developability during development when forming a cured film. It is preferable, it is 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 uses HLC-8020GPC (manufactured by Toso), and uses TSKgel SuperHZM-H, TSKgel SuperHZ4000, TSKgel SuperHZ2000 (tosogen, 4.6mmID×15cm) as columns, and THF (tetrahydrofuran) as an eluent. It is based.

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

As a specific example of a high molecular compound, "DA-7301" by Kusumoto Kasei, "Disperbyk-101 (polyamidoamine phosphate), 107 (carboxylic acid ester), 110 (copolymer containing an acid group), 111 (phosphoric acid) by BYK Chemie System dispersant), 130 (polyamide), 161, 162, 163, 164, 165, 166, 170, 190 (polymer copolymer)", "BYK-P104, P105 (high molecular weight unsaturated polycarboxylic acid)", manufactured by EFKA " EFKA4047, 4050 to 4010 to 4165 (polyuretein), EFKA4330 to 4340 (block copolymer), 4400 to 4402 (modified polyacrylate), 5010 (polyesteramide), 5765 (high molecular weight polycarboxylic acid salt), 6220 (Fatty acid polyester), 6745 (phthalocyanine derivative), 6750 (azo pigment derivative)", "Azisper PB821, PB822, PB880, PB881" manufactured by Ajinomoto Fine Techno, "Florene TG-" manufactured by Kyoeisha Chemical Co., Ltd. 710 (uretain oligomer)", "Polyflo No. 50E, No.300 (acrylic copolymer)", "Disparon KS-860, 873SN, 874, #2150 (aliphatic polyhydric carboxylic acid) manufactured by Kusumoto Kasei Corporation" , #7004 (polyetherester), DA-703-50, DA-705, DA-725", "Demol RN, N (naphthalenesulfonic acid formalin polycondensate), MS, C, SN-B ( Aromatic sulfonic acid formalin polycondensate)", "Homogenol L-18 (polymer polycarboxylic acid)", "Emulgen 920, 930, 935, 985 (polyoxyethylene nonylphenyl ether)", "Acetamine 86 (Ste Arylamine acetate)", "Solspurs 5000 (phthalocyanine derivative), 22000 (azo pigment derivative), 13240 (polyesteramine), 3000, 12000, 17000, 20000, 27000 (functional part at the end), manufactured by Nippon Lubrizol Polymer), 24000, 28000, 32000, 38500 (graft copolymer)", Nikko Chemicals' "Nikko T106 (polyoxyethylene sorbitan monooleate), MYS-IEX (poly Oxyethylene monostearate)", Kawaken Fine Chemical "Hinoact T-8000E", etc., Shin-Etsu Chemical Co., Ltd. "Organosiloxane Polymer KP341", Yusho "W001: Cationic Surfactant", Polyoxyethylene Lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol die Nonionic surfactants such as stearate and sorbitan fatty acid ester, anionic surfactants such as "W004, W005, W017", Morishita Sangyo's "EFKA-46, EFKA-47, EFKA-47EA, EFKA Polymer 100, EFKA" Polymer 400, EFKA Polymer 401, EFKA Polymer 450", Sannovco's "Disperse Aid 6, Disperse Aid 8, Disperse Aid 15, Disperse Aid 9100" and other polymer dispersants, ADEKA's "Adeka Pluronic L31" , F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, P-123", and "Ionet (brand name) S- made by Sanyo Kasei 20" and the like. In addition, acrybase FFS-6752, acrybase FFS-187, acrycure RD-F8, and cyclomer P can also be used.

Commercially available products of benign resins include, for example, DISPERBYK-130, DISPERBYK-140, DISPERBYK-142, DISPERBYK-145, DISPERBYK-180, DISPERBYK-187, DISPERBYK-191, DISPERBYK-2001, DISPERBYK manufactured by Vicchemy. -2010, DISPERBYK-2012, DISPERBYK-2025, BYK-9076, Azisper PB821 by Ajinomoto Fine Techno, Azisper PB822, and Azisper PB881.

These polymer compounds may be used alone or in combination of two or more.

As a specific example of the polymer compound, the polymer compound described in paragraphs 0127 to 0129 of JP2013-249417A can be referred to, and these contents are incorporated in the present specification.

As the dispersing agent, in addition to the above-described polymeric compound, a graft copolymer of paragraphs 0037 to 0115 of Japanese Laid-Open Patent Publication No. 2010-106268 (paragraphs 0075 to 0133 of the corresponding US2011/0124824) can be used, and these contents can be used. , Incorporated herein.

In addition to the above, a polymer compound containing a constituent component containing a side chain structure formed by bonding an acidic group of paragraphs 0028 to 0084 of Japanese Laid-Open Patent Publication No. 2011-153283 (paragraphs 0075 to 0133 of the corresponding US2011/0279759) is bonded through a linking group. Can be used, these contents can be used, and are incorporated herein.

<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 with respect 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.

Binder resin may be used individually by 1 type, and may use 2 or more types together. When two or more types of binder resins are used in combination, the total amount is preferably within the above range.

As the binder resin, it is preferable to use a linear organic polymer. As such a linear organic polymer, a well-known thing can be used arbitrarily. Preferably, a linear organic polymer soluble or swellable in water or weak alkaline water is selected in order to enable the development of water or weakly alkaline water. Among them, as the binder resin, an alkali-soluble resin (a resin containing a group promoting alkali solubility) is particularly preferred.

As the binder resin, it is a linear organic polymer, from among alkali-soluble resins containing at least one group promoting alkali solubility in a molecule (preferably, a molecule having a (meth)acrylic copolymer or a styrene-based copolymer as a main chain). You can choose appropriately. From the viewpoint of heat resistance, polyhydroxystyrene resin, polysiloxane resin, (meth)acrylic resin, (meth)acrylamide resin, (meth)acrylic/(meth)acrylamide copolymer resin, epoxy resin and polyether resin A mid-based resin is preferable, and a (meth)acrylic resin, a (meth)acrylamide-based resin, a (meth)acrylic/(meth)acrylamide copolymer resin, or a polyimide-based resin is more preferable from the viewpoint of controlling developability. .

As a group (hereinafter, also referred to as an acid group) that promotes alkali solubility, a carboxylic acid group, a phosphoric acid group, a sulfonic acid group, and a phenolic hydroxy group may be mentioned. Among them, those soluble in an organic solvent and capable of developing with a weakly alkaline aqueous solution are preferred, and alkali-soluble resins containing structural units derived from (meth)acrylic acid are more preferred. These acid groups may be one type or two or more types.

As a binder resin, a 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 the side chain, for example, Japanese Laid-Open Patent Publication No. 59-044615, Japanese Laid-Open Patent Publication No. 54-034327, Japanese Laid-open Patent Publication No. 58-012577, and Japanese Laid-Open Patent Publication No. 54 Those described in JP-025957, JP-A-54-092723, JP-A-59-053836, and JP-A-59-071048 are mentioned. As a radical polymer containing a carboxylic acid group in the side chain, a resin obtained by single or copolymerizing a monomer containing a carboxylic acid group, or an acid anhydride unit obtained by copolymerizing a monomer containing an acid anhydride alone or by copolymerization is hydrolyzed, half esterified, or half amideized. Resins, and epoxy acrylates obtained by modifying an epoxy resin with an unsaturated monocarboxylic acid and an acid anhydride.

Examples of the monomer containing a carboxylic acid group include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, and 4-carboxylstyrene. An acidic cellulose derivative containing a carboxylic acid group in the side chain is also exemplified.

As a monomer containing an acid anhydride, maleic anhydride etc. are mentioned. In addition, those obtained by adding a cyclic acid anhydride to a polymer containing a hydroxy group are useful.

Acetal-modified polyvinyl alcohol-based binder resins containing an acidic group are described in respective publications such as European Patent Publication No. 993966, European Patent Publication No. 1204000, and Japanese Patent Laid-Open No. 2001-318463. The acetal-modified polyvinyl alcohol-based binder resin containing an acid group is suitable because it has excellent balance of film strength and developability.

Further, as the water-soluble linear organic polymer, polyvinylpyrrolidone or polyethylene oxide is useful. Further, in order to increase the strength of the 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 monomer as needed] copolymer, and [allyl(meth)acrylate/(meth)acrylic acid/other additions as needed Polymerizable vinyl monomer] The copolymer is suitable because it has excellent balance of film strength, sensitivity, and developability.

As a commercial item, for example, Acrybase FF-187, FF-426 (manufactured by Fujikura Kasei), Aclique RD-F8 (manufactured by Nippon Shokubai), Cyclomer P(ACA) 230AA manufactured by DaicelAllnex, etc. Can be lifted.

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

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) as the binder resin.

The definition of the structural unit containing the graft chain is the same as the structural unit containing the graft chain contained in the dispersant, and the suitable range is also the same.

Examples of the acid group include a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, or a phenolic hydroxy group, and at least one of a carboxylic acid group, a sulfonic acid group, and a phosphoric acid group is preferable, and a carboxylic acid group is more preferable.

(Structural unit containing an acid group)

As the structural unit containing an acidic group, it is preferable to contain at least one structural unit selected from structural units derived from monomers represented by the following formulas (vii) to (ix).

[Formula 30]

In formulas (vii) to (ix), R ²¹ , R ²² , and R ²³ are each independently a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, etc.), or Represents an alkyl group having 1 to 6 carbon atoms (eg, a methyl group, an ethyl group, a propyl group, etc.).

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

X ₂ in formula (vii) represents an oxygen atom (-O-) or an imino group (-NH-), and is preferably an oxygen atom.

In addition, Y in formula (viii) represents a metaphosphorus 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 a divalent aliphatic group (e.g., an alkylene group, a substituted alkylene group, an alkenylene group, a substituted alkenylene group, an alkynylene group, and a substituted alkynylene group), and a divalent aromatic group (e.g. For example, an arylene group and a substituted arylene group), a divalent heterocyclic group, an oxygen atom (-O-), a sulfur atom (-S-), an imino group (-NH-), a substituted imino bond (-NR ⁴¹ ′ -Herein, R ⁴¹ ′ includes an aliphatic group, an aromatic group or a heterocyclic group), a carbonyl bond (-CO-), and combinations thereof.

The divalent aliphatic group may have a cyclic structure or a branched structure. The number of carbon atoms of the aliphatic group is preferably 1 to 20, more preferably 1 to 15, and still 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. Examples of the substituent include a halogen atom, a hydroxy group, an aromatic group, and a heterocyclic group.

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

It is preferable that the divalent heterocyclic group contains a 5-membered ring or a 6-membered ring as a heterocycle. One or more of other heterocycles, aliphatic rings, or aromatic rings may be condensed with the heterocycle. The heterocyclic group may have a substituent. As an example of a substituent, a halogen atom, a hydroxyl group, an oxo group (=O), a thioxo group (=S), an imino group (=NH), a substituted imino group (=NR ⁴² , wherein R ⁴² is an aliphatic group, Aromatic group or heterocyclic group), aliphatic group, aromatic group and heterocyclic group.

It is preferable that L ₂ is a single bond, an alkylene group, or a divalent linking group containing an oxyalkylene structure. It is more preferable that the oxyalkylene structure is an oxyethylene structure or an oxypropylene structure. L ₂ may contain a polyoxyalkylene structure containing two or more oxyalkylene structures repeatedly. 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 (vii) to (ix), Z ₂ is an acid group, and it is preferable that it is a carboxylic acid group.

In formula (ix), R ²⁴ , R ²⁵ , and R ²⁶ are each independently a hydrogen atom, a halogen atom (e.g., fluorine, chlorine, bromine, etc.), and an alkyl group having 1 to 6 carbon atoms (e.g. For example, a methyl group, an ethyl group, a propyl group, etc.), -Z ₂ , or L ₂ -Z ₂ is represented. Here, L ₂ and Z ₂ are, and L ₂ and Z ₂ as agreed in the above, preferred examples are the same. As R ²⁴ , R ²⁵ , and R ²⁶ , each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms is preferable, and a hydrogen atom is more preferable.

As a monomer represented by 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, and X ₂ is oxygen A compound in which it is an atom or an imino group and Z ₂ is a carboxylic acid group is preferable.

As the monomer represented by formula (vii), 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 metaphosphorus group is preferable.

Further, as the monomer represented by formula (ix), a compound in which R ²⁴ , R ²⁵ , and R ²⁶ are each independently a hydrogen atom or a methyl group, and Z ₂ is a carboxylic acid group is preferable.

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

The binder resin may have one type or two or more types of structural units containing an acid group.

The content of the structural unit containing an acidic group is, in terms of mass, preferably 5 to 95% with respect to the total mass of the binder resin, and more 10 to 90% from the viewpoint of suppressing damage to the image intensity due to alkali development. desirable.

<Surfactant>

It is preferable that the curable composition contains a surfactant. The surfactant contributes to the improvement of the coating properties of the curable composition.

When the curable composition contains a surfactant, the content of the surfactant is preferably 0.001 to 2.0% by mass with respect to the total solid content of the curable composition.

Surfactant may be used individually by 1 type, and may use 2 or more types together. When two or more surfactants are used in combination, the total amount is preferably within the above range.

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

For example, when the curable composition contains a fluorine-based surfactant, liquid properties (especially, fluidity) of the curable composition are further improved. That is, in the case of forming a film using a curable composition containing a fluorine-based surfactant, 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 coating property to the surface to be coated is improved. . For this reason, even in the case of forming a thin film of about several μm with a small amount of liquid, it is effective in that a film having a uniform thickness with a small thickness variation can be more suitably performed.

The fluorine content rate in the fluorine-based surfactant is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and still more preferably 7 to 25% by mass. The fluorine-based surfactant having a fluorine content within this range is effective in terms of uniformity of the thickness of the coating film and/or liquid-forming properties, and has good solubility in the curable composition.

As a fluorine-based surfactant, for example, Megapak F171, Copper F172, Copper F173, Copper F176, Copper F177, Copper F141, Copper F142, Copper F143, Copper F144, Copper R30, Copper F437, Copper F475, Copper F479, Copper F482, copper F554, copper F780 (above, manufactured by DIC Corporation), Fluorad FC430, copper FC431, copper FC171 (above, Sumitomo 3M Corporation), Surfron S-382, Dong SC-101, Dong SC -103, East SC-104, East SC-105, East SC-1068, East SC-381, East SC-383, East S-393, East KH-40 (above, manufactured by Asahi Glass), PF636, PF656, PF6320, PF6520, PF7002 (manufactured by OMNOVA), etc. are mentioned.

A block polymer can also be used as a fluorine-based surfactant, and as a specific example, the compound of Unexamined-Japanese-Patent No. 2011-089090 is mentioned, for example. Compound (F-1) represented by the following formula is also mentioned as a fluorine-type surfactant. In compound (F-1), the structural units represented by (A) and (B) in the formula are 62 mol% and 38 mol%, respectively. Among the structural units 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 15,311, for example.

[Formula 31]

Specific examples of nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane, their ethoxylates and propoxylates (for example, glycerol propoxylate, glycerin ethoxylate, etc.), poly Oxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol Choledistearate, sorbitan fatty acid ester (BASF Pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2, Tetronic 304, 701, 704, 901, 904, 150R1), Solspurs 20000 (Nihon Lubrizol Co., Ltd.), etc. are mentioned. In addition, Pionine D-6112-W manufactured by Takemoto Yushi Co., Ltd., NCW-101, NCW-1001, and NCW-1002 manufactured by Wako Junyaku High School can also be used.

Specific examples of cationic surfactants include phthalocyanine derivatives (trade name, EFKA-745, manufactured by Morishita Sangyo Co., Ltd.), organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (Met). Acrylic acid-based (co)polymer polyflo No. 75, No. 90, No. 95 (Kyoeisha Chemical Co., Ltd. product), W001 (Yusho Co., Ltd.), etc. are mentioned.

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

As a silicone surfactant, for example, "Toray Silicon DC3PA", "Toray Silicon SH7PA", "Toray Silicon DC11PA", "Toray Silicon SH21PA", "Toray Silicon SH28PA", "Toray Silicon" manufactured by Toray Dow Corning Co., Ltd. SH29PA", "Toray Silicon SH30PA", "Toray Silicon SH8400", "TSF-4440", "TSF-4300", "TSF-4445", "TSF-4460", "TSF-" manufactured by Momentive Performance Materials, Inc. 4452", "KP341", "KF6001", "KF6002" manufactured by Shin-Etsu Silicon Co., Ltd., "BYK307", "BYK323", "BYK330" manufactured by Big Chemical Corporation, and the like.

<Silane coupling agent>

A silane coupling agent is a compound containing a hydrolyzable group and other functional groups in a molecule. Moreover, hydrolyzable groups, such as an alkoxy group, are bonded to a silicon atom.

The hydrolyzable group refers to a substituent that is directly connected to a silicon atom and capable of generating a siloxane bond by a hydrolysis reaction and/or a condensation reaction. As a hydrolyzable group, a halogen atom, an alkoxy group, an acyloxy group, and an alkenyloxy group are mentioned, for example. When the hydrolyzable group contains a carbon atom, the carbon number is preferably 6 or less, and more preferably 4 or less. In particular, an alkoxy group having 4 or less carbon atoms or an alkenyloxy group having 4 or less carbon atoms is preferable.

When forming a cured film on a substrate, it is preferable that the silane coupling agent does not contain a fluorine atom and a silicon atom (except for a silicon atom to which a hydrolyzable group is bonded) in order to improve the adhesion between the substrate and the cured film. , A fluorine atom, a silicon atom (however, excluding a silicon atom to which a hydrolyzable group is bonded), an alkylene group substituted with a silicon atom, a linear alkyl group having 8 or more carbon atoms, and a branched chain alkyl group having 3 or more carbon atoms are not preferably included.

It is preferable that the silane coupling agent contains a group represented by the following formula (Z). * Indicates a bonding position.

Formula (Z) *-Si-(R _Z1 ) ₃

In formula (Z), R _Z1 represents a hydrolyzable group, and the definition is as described above.

It is preferable that the silane coupling agent contains at least one type of curable functional group selected from the group consisting of a (meth)acryloyloxy group, an epoxy group, and an oxetanyl group. The curable functional group may be directly bonded to a silicon atom, or may be bonded to a silicon atom through a linking group.

Further, as a preferred embodiment of the curable functional group contained in the silane coupling agent, a radical polymerizable group is also mentioned.

The molecular weight of the silane coupling agent is not particularly limited, and 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 preferred embodiments of the silane coupling agent, a silane coupling agent X represented by formula (W) is mentioned.

Formula (W) R _Z2 -Lz-Si-(R _Z1 ) ₃

R _z1 represents a hydrolyzable group, and the definition is as described above.

R _z2 represents a curable functional group, the definition is as described above, and the suitable range is also the same as above.

Lz represents a single bond or a divalent connecting group. When Lz represents a divalent linking group, examples of the divalent linking group include an alkylene group optionally substituted by a halogen atom, an arylene group optionally substituted by a halogen atom, -NR ¹² -, -CONR ¹² -, -CO-, -CO ₂ -, -SO ₂ NR ¹² -, -O-, -S-, -SO ₂ -, or a combination thereof. Among them, at least one selected from the group consisting of an alkylene group which may be substituted with a halogen atom having 2 to 10 carbon atoms and an arylene group which may be substituted with a halogen atom having 6 to 12 carbon atoms, or these groups and -NR ¹² -, A group consisting of a combination of at least one group selected from the group consisting of -CONR ¹² -, -CO-, -CO ₂ -, -SO ₂ NR ¹² -, -O-, -S-, and -SO _2- It is preferable, and the alkylene group which may be substituted with a C2-C10 halogen atom, -CO ₂ -, -O-, -CO-, -CONR ¹² -, or a group consisting of a combination of these groups is more preferable. Here, R ¹² represents a hydrogen atom or a methyl group.

As the silane coupling agent X, N-β-aminoethyl-γ-aminopropyl-methyldimethoxysilane (Shin-Etsu Chemical Co., Ltd. make, brand name KBM-602), N-β-aminoethyl-γ-aminopropyl -Trimethoxysilane (Shin-Etsu Chemical Industries make, brand name KBM-603), N-β-aminoethyl-γ-aminopropyl-triethoxysilane (Shin-Etsu Chemical Industries make, brand name KBE-602) , γ-aminopropyl-trimethoxysilane (Shin-Etsu Chemical Co., Ltd. make, brand name KBM-903), γ-aminopropyl-triethoxysilane (Shin-Etsu Chemical Co., Ltd. make, trade name KBE-903), 3 -Methacryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., brand name KBM-503), and glycidoxyoctyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., brand name KBM-4803), etc. Can be lifted.

As another suitable aspect of the silane coupling agent, a silane coupling agent Y which has at least a silicon atom, a nitrogen atom, and a curable functional group in the molecule and contains a hydrolyzable group bonded to a silicon atom is mentioned.

This silane coupling agent Y just needs to have at least one silicon atom in a molecule|numerator, and the silicon atom can couple|bond with the following atoms and substituents. They may be the same atom, substituent or different. Atoms and substituents that can be bonded include a hydrogen atom, a halogen atom, a hydroxy group, an alkyl group having 1 to 20 carbon atoms, an alkenyl group, an alkynyl group, an aryl group, an amino group substituted with an alkyl group and/or an aryl group, a silyl group, An alkoxy group having 1 to 20 carbon atoms, an aryloxy group, and the like. These substituents are also silyl group, alkenyl group, alkynyl group, aryl group, alkoxy group, aryloxy group, thioalkoxy group, alkyl group and/or aryl group substituted amino group, halogen atom, sulfonamide group, alkoxycarbo It may be substituted with a nil group, an amide group, a urea group, an ammonium group, an alkyl ammonium group, a carboxylic acid group, or a salt thereof, a sulfo group, or a salt thereof.

In addition, at least one hydrolyzable group is bonded to the silicon atom. The definition of the hydrolyzable group is as described above.

The group represented by formula (Z) may be contained in the silane coupling agent Y.

The silane coupling agent Y has at least one nitrogen atom in its molecule, and the nitrogen atom is preferably present in the form of a secondary amino group or a tertiary amino group, that is, the nitrogen atom contains at least one organic group as a substituent. It is desirable to do. In addition, as the structure of the amino group, it may exist in the molecule in the form of a partial structure of a nitrogen-containing heterocycle, or may exist as a substituted amino group such as aniline.

Here, examples of the organic group include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a combination thereof. These may further have a substituent, and examples of the substituent that 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, a sulfonamide group, an alkoxycarbo A nil group, a carbonyloxy group, an amide group, a urea group, an alkyleneoxy group, an ammonium group, an alkyl ammonium group, a carboxylic acid group, or a salt thereof, a sulfo group, and the like.

It is preferable that the nitrogen atom is bonded to a curable functional group through an arbitrary organic linking group. As a preferable organic linking group, the nitrogen atom mentioned above and the substituent which can be introduced into the organic group bonded to it are mentioned.

The definition of the curable functional group contained in the silane coupling agent Y is as above, and the suitable range is also the same as above.

The silane coupling agent Y needs to have at least one or more curable functional groups per molecule, but it is also possible to contain two or more curable functional groups. From the viewpoint of sensitivity and stability, it is preferable to contain 2 to 20 curable functional groups in the molecule, more preferably 4 to 15, and still more preferably 6 to 10.

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

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

The curable composition may contain a silane coupling agent individually by 1 type, and may contain 2 or more types. When the curable composition contains two or more types of silane coupling agents, the total may be within the above range.

<Ultraviolet absorber>

The curable composition may contain an ultraviolet absorber. Thereby, the shape of the pattern of the cured film can be made more excellent (precise).

As the ultraviolet absorber, salicylate-based, benzophenone-based, benzotriazole-based, substituted acrylonitrile-based, and triazine-based ultraviolet absorbers can be used. As specific examples of these, the compounds of paragraphs 0137 to 0142 of JP 2012-068418 A (corresponding paragraphs 0251 to 0254 of US2012/0068292) can be used, the contents of which can be used, and are incorporated herein.

In addition, a diethylamino-phenylsulfonyl-based ultraviolet absorber (manufactured by Daito Chemical Co., Ltd., brand name: UV-503) is also suitably used.

Examples of the ultraviolet absorber include compounds exemplified in paragraphs 0134 to 0148 of JP 2012-032556 A.

The content of the ultraviolet absorber is preferably 0.001 to 15% by mass, more preferably 0.01 to 10% by mass, and still more preferably 0.1 to 5% by mass with respect to the total solid content of the curable composition.

<Thermal polymerization initiator>

The curable composition may contain a thermal polymerization initiator.

The 1 minute half-life temperature of the thermal polymerization initiator is preferably 120 to 300°C, more preferably 150 to 250°C, more preferably 150 to 230°C, and 170 to 200 from the viewpoint of stability and curability of the photosensitive resin composition. C is particularly preferred. When the half-life temperature of the thermal polymerization initiator for 1 minute is equal to or greater than the lower limit, it is not excessively cured during drying of the coating film, and developability is good. When the half-life temperature of the thermal polymerization initiator for 1 minute is equal to or less than the lower limit, the curability is good.

From the viewpoint of volatility, the molecular weight of the thermal polymerization initiator is preferably 100 or more, more preferably 150 or more, even more preferably 200 or more, and particularly preferably 250 or more. As for the upper limit, 1,000 or less are preferable, and 500 or less are more preferable, for example. When the molecular weight of the thermal polymerization initiator is equal to or greater than the above lower limit, volatilization of the thermal polymerization initiator during drying of the coating film can be effectively suppressed, and the curability is good.

As the thermal polymerization initiator, a compound that generates a radical by heat (hereinafter, simply referred to as a thermal radical generator) or a compound that generates an acid by heat (hereinafter, also referred to as a thermal acid generator) may be used. In particular, a thermal radical generator is preferred. Since the thermal radical generator can accelerate radical polymerization of ethylenically unsaturated groups, in the case of using a compound containing a group having an ethylenically unsaturated bond as a crosslinking agent, the polymerization reaction of the crosslinking agent can be more effectively promoted. It can be cured in a short time. In addition, the reaction by which the polymerization reaction is initiated and promoted by the thermal acid generator is ring-opening polymerization of epoxy. Since the polymerization rate of epoxy ring-opening polymerization is slower than that of radical polymerization, the curability cannot be sufficiently promoted in some cases.

(Thermal Radical Generator)

As the thermal radical generator, a known thermal radical generator can be used. The thermal radical generator is a compound that generates a radical by the energy of heat and initiates or accelerates the polymerization reaction of the crosslinking agent.

Examples of the thermal radical generator include aromatic ketones, onium salt compounds, organic peroxides, thio compounds, hexaarylbiimidazole compounds, ketoxime ester compounds, borate compounds, azinium compounds, metallocene compounds, active ester compounds, and carbon dioxide. A compound having a rosen bond, an azo compound, etc. are mentioned. Among them, an azo compound is more preferable.

[Method for preparing curable composition]

The method for producing the curable composition includes the following mixing and dispersing steps. It is preferable to include a stationary process and/or a filtration process. Hereinafter, suitable aspects will be described in detail for each step.

[Mixing and dispersing process]

The mixing and dispersion step is a step of mixing the above components by a known mixing method (for example, a stirrer, a homogenizer, a high pressure emulsifying device, a wet pulverizer, and a wet disperser) to obtain a curable composition. In the mixing and dispersing step, each component constituting the curable composition may be blended together, or may be sequentially blended after dissolving or dispersing each component in an organic solvent. The order of addition and working conditions at the time of compounding are not particularly limited. The mixing and dispersion step may include a step of preparing a dispersion.

(Process to produce dispersion)

The process of preparing a dispersion is a process of mixing a colorant, a dispersant, and a solvent, and dispersing the colorant by the above method to prepare a dispersion. A curable composition can be produced by mixing other components with the prepared dispersion.

In the process of preparing the dispersion, the mechanical force used for dispersing the pigment may include compression, compression, impact, shear, and cavitation. Specific examples of these processes include a bead mill, a sand mill, a roll mill, a high-speed impeller, a sand grinder, a flow jet mixer, a high-pressure wet atomization, and ultrasonic dispersion. In addition, "Distributed Technology Exhibition, published by Joho Kiko Co., Ltd., July 15, 2005" and "Real comprehensive data collection of dispersion technology and industrial application focusing on suspension (high/liquid dispersion system), Keii Kaihatsu The process and disperser described in "Center Press Publication, October 10, 1978" can be used suitably.

In the step of preparing the dispersion, the pigment may be refined by a salt milling step. Materials, equipment, processing conditions, and the like used in the salt milling process can be those described in JP 2015-194521 A and JP 2012-046629 A, for example.

It is preferable that the manufacturing method of a curable composition includes a process of obtaining the said coloring agent by thermal plasma method. The process of obtaining the colorant is performed before mixing the above components. The aspect of the specific manufacturing process of the colorant by the thermal plasma method is the same as above.

<Political process>

Before the colorant is provided to the mixing and dispersing step or the step of preparing a dispersion, the colorant may pass through the following stationary steps.

The stationary process means that the colorant obtained by the thermal plasma method is not exposed to the atmosphere after its production, and in a sealed container in which the oxygen concentration is controlled, for a predetermined time (preferably 12 to 72 hours, more preferably 12 to 48 hours). Time, more preferably 12 to 24 hours) is a step to stand still. At this time, it is more preferable if the moisture content in the sealed container is controlled.

At this time, 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 still 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. Among them, it is more preferable to use nitrogen gas.

After passing through the said stationary process, the surface of the colorant and crystal grain boundaries become stable. Thereby, the occurrence of pinholes in the cured film obtained by curing the curable composition can be suppressed.

In addition, since the said stationary process can be replaced with the process H demonstrated in the manufacturing method of a coloring agent, and the curable composition has a more excellent effect of this invention, it is preferable to replace with a process H.

<Filtration process>

The filtration step is a step of filtering the curable composition prepared by the mixing and dispersing step with a filter. In the filtration step, foreign matters can be removed from the curable composition and/or defects can be reduced.

The filter can be used without any particular limitation as long as it has been conventionally used for filtration applications or the like. For example, filters made of fluororesins such as PTFE (polytetrafluoroethylene), polyamide resins such as nylon, and polyolefin resins such as polyethylene and polypropylene (PP) (containing high density and ultra-high molecular weight), etc. Can be mentioned. Among these materials, polypropylene (containing high-density polypropylene) and nylon are preferable.

The pore diameter of the filter is preferably 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 more preferably about 0.3 to 0.7 μm. By setting it as this range, it becomes possible to reliably remove fine foreign matters, such as impurities and aggregates contained in a pigment, suppressing filtration clogging of a pigment.

When using a filter, other filters may be combined. In that case, filtering by the 1st filter may be performed only once, and may be performed twice or more. When filtering is performed twice or more by combining other filters, it is preferable that the pore diameter of the second and subsequent pores is the same or larger than that of the first filtering. You may combine the first filters of different pore diameters within the above range. The pore diameter here can refer to the nominal value of the filter manufacturer. As a commercially available filter, for example, among various filters provided by Nippon Paul Corporation, Advantech Toyo Corporation, Nihon Integras Corporation (formerly Nippon Microlith Corporation) or Kitz Micro Filter, etc. You can choose.

The second filter may be formed of the same material as the first filter. The pore diameter of the second filter is preferably about 0.2 to 10.0 μm, preferably about 0.2 to 7.0 μm, and more preferably about 0.3 to 6.0 μm.

[Cured film (light shielding film)]

A cured film is obtained by curing the curable composition. A colorant is contained in the cured film. The cured film is suitably used as a light-shielding film, and specifically, it is suitably used for light-shielding of the peripheral part of a light receiving part of an image sensor.

Hereinafter, a case where the cured film is used as a light-shielding film in the peripheral portion of the light receiving portion of the image sensor will be described as an example.

The film thickness of the light-shielding film is not particularly limited, but since the light-shielding film has a more excellent effect of the present invention, the film thickness after drying is preferably 0.2 μm or more and 50 μm or less, more preferably 0.3 μm or more and 10 μm or less, and 0.3 μm It is more preferably 5 μm or less. Since the above-described curable composition has a high optical density per unit volume (because of high light-shielding property), it is also possible to reduce the film thickness compared to a curable composition using a conventional black pigment.

As the size of the light-shielding film (length of one side of the light-shielding film provided around the sensor light-receiving portion), from the viewpoint of the light-shielding film having a more excellent effect of the present invention, 0.001 mm or more and 10 mm or less are preferable, and 0.05 mm or more and 7 mm or less are more preferable, and 0.1 More preferably mm or more and 3.5 mm or less.

[Method for producing a cured film]

Next, a method of manufacturing a cured film (light shielding film) will be described.

Hereinafter, the manufacturing method will be described in detail for each process.

The manufacturing method of a cured film includes the following curable composition layer formation process and an exposure process. It is preferable that the manufacturing method of a cured film further includes a developing process.

Curable composition layer formation process: A process of forming a curable composition layer on a support body.

Exposure process: A process of exposing the curable composition layer.

Developing step: A step of developing a curable composition layer after exposure to form a pattern-shaped cured film (light shielding film).

Specifically, the curable composition is applied directly or via another layer on a substrate, a curable composition layer is formed (curable composition layer forming process), exposed through a predetermined mask pattern, and a light-irradiated coating film By curing only a part (exposure process) and developing with a developer (development process), the cured film can be manufactured.

Hereinafter, each step will be described.

<Curable composition layer formation process>

The curable composition layer forming step is a step of forming a curable composition layer on a support (hereinafter also referred to as "substrate"). Among them, it is preferable to include a coating step of applying a curable composition on a support to form a curable composition layer, and a coating step of directly applying the curable composition on a support to form a curable composition layer on the support It is more preferable to include.

As the substrate, for example, alkali-free glass, soda glass, Pyrex (registered trademark) glass, quartz glass used for liquid crystal display devices, and a transparent conductive film attached thereto, photoelectric conversion element substrate used for solid-state imaging devices, etc. (For example, a silicon substrate), a CCD (Charge Coupled Device) substrate, a CMOS (Complementary Metal-Oxide Semiconductor) substrate, and the like.

The support may be provided with an undercoat layer in order to improve adhesion to the upper layer, prevent diffusion of substances, or planarize the surface of the substrate (hereinafter, also referred to as "support with an undercoat layer").

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

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

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

<Exposure process>

The exposure step is a step of exposing the curable composition layer (coating film) formed in the curable composition layer forming step through a mask to cure only the portion of the coated film irradiated with light.

The exposure is preferably performed by irradiation with actinic rays or radiation, particularly, ultraviolet rays such as g-rays, h-rays, and i-rays are preferable, and high-pressure mercury lamps are more preferable. Although the exposure amount is not particularly limited, it can be appropriately selected depending on the type of pigment to be used and/or the shape of the mask pattern. For example, the embodiment of the lower limit value for the example of forming a film by curing a composition containing the black pigment according to the exposure value is more preferably 50mJ / cm ² or more are preferred, 80mJ / cm ² or more. The upper limit of the exposure dose, 1,500mJ / cm ² or less is preferred, and more preferred is 500mJ / cm ² under. When the exposure amount is 80 mJ/cm ² or more and less than 500 mJ/cm ² , the method for producing a cured film (light shielding film) has more excellent stability and productivity.

Further, as to a coating film formed by curing a composition containing a chromatic color pigment described in the Examples, it is the lower limit of the exposure dose is more preferred 50mJ / cm ² or more are preferred, 80mJ / cm ² or more. The upper limit of the exposure dose, 1,500mJ / cm ² or less is preferred, and particularly preferred 500mJ / cm ² less than the more preferred, and less than 400mJ / cm ² is more preferred, and less than 300mJ / cm ^2. When the exposure amount is 80 mJ/cm ² or more and 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, in forming the light-shielding film for a solid-state image sensor, exposure with an i-line stepper is preferable.

<Development process>

The developing process is a process of developing the exposed curable composition layer. By the developing process, a pattern-shaped cured film can be obtained.

It is preferable that the manufacturing method of the said cured film includes a developing process and the following washing process. In the developing step, an alkali developing treatment (development step) is performed, and the non-light irradiated portion in the exposure step is eluted into an aqueous alkali solution. Thereby, only the photocured part (the light-irradiated coating film part) remains.

As the developer, when producing a light-shielding color filter containing a black matrix for a solid-state image sensor, an organic alkali developer that does not cause damage to the underlying circuit or the like is preferable. The developing temperature is usually preferably 20 to 30°C, and the developing time is preferably 20 to 90 seconds.

As an alkaline aqueous solution, an inorganic developer and an organic developer can be mentioned, for example. Examples of the inorganic developer include an alkaline aqueous solution in which sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, sodium silicate, or sodium metasilicate is dissolved in a concentration of 0.001 to 10% by mass, preferably 0.01 to 1% by mass. have. As an organic developer, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, or 1,8-diazabicyclo-[ 5.4.0] An alkaline aqueous solution obtained by dissolving an alkaline compound such as -7-undecene so that the concentration is 0.001 to 10% by mass, preferably 0.01 to 1% by mass. An appropriate amount of a water-soluble organic solvent such as methanol and ethanol and/or a surfactant may be added to the alkaline aqueous solution, for example. Moreover, as a developing method, a puddle developing method, a shower developing method, etc. can be used, for example.

<Cleaning process>

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

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

A color filter containing a cured film (black matrix) is suitable for a solid-state image pickup device such as a CCD image sensor and/or a CMOS image sensor. In particular, it is suitable for high resolution CCD image sensors and/or CMOS image sensors exceeding 1 million pixels. That is, the color filter containing the cured film is suitable for a solid-state imaging device. The color filter may contain a structure in which a cured film for forming each color pixel is embedded in a space partitioned by, for example, a lattice shape by a partition wall.

The cured film (black matrix) is disposed between, for example, a light receiving portion of each pixel constituting a CCD image sensor and/or a CMOS image sensor, and a microlens for condensing light.

[Solid image sensor]

The solid-state imaging device contains the cured film (black matrix). It is preferable that the solid-state image sensor further contains a color filter containing a black matrix and, if necessary, a patterned film composed of pixels of different colors (three or four colors).

The solid-state imaging device is not particularly limited as long as it contains the black matrix and functions as a solid-state imaging device, and, for example, constitutes a light-receiving area of a solid-state imaging device (CCD image sensor, CMOS image sensor, etc.) on a substrate. A solid-state image pickup device containing a light-receiving element made of a plurality of photodiodes and polysilicon and the like, and containing the black matrix on a surface opposite to the light-receiving element formation surface of the substrate.

The color filter may have a structure in which a cured film forming each color pixel is buried in a space partitioned by, for example, a lattice shape by a partition wall. It is preferable that the partition wall in this case has a low refractive index for each color pixel. As an example of a solid-state image pickup device containing such a structure, the solid-state image pickup device described in JP 2012-227478 A and JP 2014-179577 A can be mentioned.

[Image display device]

The cured film can be suitably used for an image display device (eg, a liquid crystal display device and an organic electroluminescent display device).

For the definition of the image display device and the details of each image display device, for example, "Electronic Display Device (Akio Sasaki, published in Chosakai Kogyo Co., Ltd.)", and "Display Device (Sumiaki Ibuki, Sankyo Corporation)" Tosho Co., Ltd. published in the first year of Heisei)" About the liquid crystal display device, it describes in "Next-generation liquid crystal display technology (edited by Tatsuo Uchida, published in 1994, Chosakai Kogyo)", for example. The cured film is suitable for, for example, a liquid crystal display device of the system described in "Next-generation liquid crystal display technology".

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

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

The color filter containing the cured film is suitable for a color TFT (Thin Film Transistor) type liquid crystal display device. About the liquid crystal display device of the color TFT system, it is described in "color TFT liquid crystal display (Kyoritsu Shopan Co., Ltd. published in 1996)", for example. In addition, the color filter may include a horizontal electric field driving method such as IPS (In Plane Switching); Liquid crystal display with enlarged viewing angles such as pixel division methods such as MVA (Multi-domain Vertical Alignment), Super-Twist Nematic (STN), Twisted Nematic (TN), Vertical Alignment (VA), on-chip spacer (OCS) , Fringe field switching (FFS), and Reflective Optically Compensated Bend (R-OCB).

The color filter is suitable for a bright, high-definition color-filter on array (COA) liquid crystal display device. In the liquid crystal display of the COA system, in addition to the usual required properties, properties required for an interlayer insulating film, that is, low dielectric constant and resistance to stripping solutions, are sometimes required in addition to the properties required for a color filter. A COA liquid crystal display device containing the color filter has a better resolution or more excellent durability. Further, in order to satisfy the required characteristics of a low dielectric constant, a resin film may be further contained on the color filter layer.

These image display systems are described, for example, on page 43 of "EL, PDP, LCD Display-Latest Trends in Technology and Market-(Toray Research Center Research and Research Section 2001)". In addition, in the above, EL stands for Electroluminescence, PDP stands for Plasma Display Panel, and LCD stands for liquid crystal display.

In addition to the color filter, the liquid crystal display includes various members such as an electrode substrate, a polarizing film, a retardation film, a backlight, a spacer, and a viewing angle compensation film. The color filter can be applied to a liquid crystal display device composed of these known members. Regarding these members, for example, "The market of materials and chemicals around the '94 liquid crystal display (Kentaro Shima Co., Ltd., published in CMC 1994)", and "The current status and future prospects of the liquid crystal-related market in 2003 (bottom volume) (Omote Ryokichi Fuji Chimera Soken, published in 2003)".

Regarding the backlight, SID meeting Digest 1380 (2005) (A. Konno et al.), and/or monthly display pages 18 to 24 (Yasuhiro Shima) of December 2005 issue, pages 25 to 30 (Yagi Takaaki), etc. It is described.

The cured film may include portable devices such as personal computers, tablets, mobile phones, smart phones, and digital cameras; Office Automation (OA) equipment such as printer multifunction printers and scanners; Industrial devices such as surveillance cameras, barcode readers, and automated teller machines (ATMs), high speed cameras, and personal authentication using facial image authentication; Vehicle-mounted camera devices; Medical camera devices such as endoscopes, capsule endoscopes, and catheters; Optical filters and modules used in space devices such as biometric sensors, biosensors, military reconnaissance cameras, three-dimensional map cameras, meteorological and marine observation cameras, land resource exploration cameras, and exploration cameras for space astronomy and deep space targets. It is suitable for a light-shielding member and a light-shielding layer, furthermore an antireflection member and an antireflection layer.

The cured film can also be used for applications such as micro LED (Light Emitting Diode) and micro OLED (Organic Light Emitting Diode). The cured film is suitable for a member that imparts a light-shielding function or an anti-reflection function in addition to the optical filter and optical film used for micro LEDs and micro OLEDs.

Examples of micro LEDs and micro OLEDs include those described in Japanese Unexamined Patent Publication No. 2015-500562 and Japanese Unexamined Patent Publication 2014-533890.

The cured film is suitable as an optical filter and an optical film used for a quantum dot display. Moreover, the said cured film is suitable as a member which imparts a light-shielding function and an antireflection function.

Examples of quantum dot displays include U.S. Patent Application Publication No. 2013/0335677, U.S. Patent Application Publication No. 2014/0036536, U.S. Patent Application Publication No. 2014/0036203, and U.S. Patent Application Publication No. 2014/0035960 The thing described in is mentioned.

Example

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

[Synthesis of polyfunctional thiol compound S-15]

The polyfunctional thiol compound S-15 represented by the following formula was synthesized by the following method.

[Formula 32]

In addition, in the above formula, "Et" represents an ethyl group (-CH ₂ CH ₃ ), and is the same as follows.

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

(Chloroform in ¹ H-NMR 300MHz): 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.

[Formula 33]

In a nitrogen atmosphere, pentaerythritol tetra (3-mercaptopropionate) (manufactured by TCI) (2.00 g) and 2-hydroxyethyl acrylate (0.475 g) were dissolved in tetrahydrofuran (10.0 g) to react I got the liquid. Next, the internal temperature of the reaction solution was cooled to 5°C or less. To the reaction solution after cooling, triethylamine (0.450 g) was added. After that, the temperature of the liquid of the reaction solution was raised to 50°C. After heating up, the reaction solution was stirred for 3 hours. Thereafter, hexane (50 g) was added to the reaction solution, and the supernatant component of the reaction solution after the addition of hexane was removed. To the reaction solution after removal of the supernatant component, hexane (50 g) was added again, and the supernatant component of the reaction solution after the re-addition of hexane was removed. After that, the solvent remaining in the reaction solution 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 deuterium 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).

[Synthesis of polyfunctional thiol compound S-17]

The polyfunctional thiol compound S-17 represented by the following formula was synthesized by the following method.

[Formula 34]

In addition, in the above formula, "Me" intends a methyl group (-CH ₃ ), and is the same as follows.

In a nitrogen atmosphere, pentaerythritol tetra(3-mercaptopropionate) (manufactured by TCI) (2.00 g) and acrylic acid 2-(dimethylamino) ethyl (0.586 g) were dissolved in tetrahydrofuran (10.0 g). To obtain a reaction solution. Next, the internal temperature of the reaction solution was cooled to 5°C or less. To the reaction solution after cooling, triethylamine (0.450 g) was added. After that, the temperature of the liquid of the reaction solution was raised to 50°C. After heating up, the reaction solution was stirred for 3 hours. Thereafter, hexane (50 g) was added to the reaction solution, and the supernatant component of the reaction solution after the addition of hexane was removed. To the reaction solution after removal of the supernatant component, hexane (50 g) was added again, and the supernatant component of the reaction solution after the re-addition of hexane was removed. After that, the solvent remaining in the reaction solution 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.

(Chloroform in ¹ H-NMR 300MHz): 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.

[Formula 35]

In a nitrogen atmosphere, pentaerythritol tetra (3-mercaptopropionate) (manufactured by TCI) (2.00 g) and acrylic acid 3- (trimethoxysilyl) propyl (1.92 g) were added to tetrahydrofuran (10.0 g). It was dissolved and a reaction solution was obtained. Next, the internal temperature of the reaction solution was cooled to 5°C or less. To the reaction solution after cooling, triethylamine (0.450 g) was added. After that, the temperature of the liquid of the reaction solution was raised to 50°C. After heating up, the reaction solution was stirred for 3 hours. Thereafter, hexane (50 g) was added to the reaction solution, and the supernatant component of the reaction solution after the addition of hexane was removed. To the reaction solution after removal of the supernatant component, hexane (50 g) was added again, and the supernatant component of the reaction solution after the re-addition of hexane was removed. Thereafter, the solvent remaining in the reaction solution 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.

(Chloroform in ¹ H-NMR 300MHz): 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, 64~66, 69, 71, 73~75, 88~90, and 112~114]

Polyfunctional thiol compounds S-8, 20, 22, 24, 25, 64 to 66, 69, 71, 73 to 75, 88 to 90, and 112 to by the same method as above except that the raw material has been appropriately changed. 114 was synthesized.

In addition, the structure of each polyfunctional thiol compound identified by ¹ H-NMR is as shown in Tables 1-1 to 1-6.

[Preparation of the curable compositions of Examples 1 to 23 and Comparative Examples 2 and 3]

The polyfunctional thiol compound shown in each column of Table 2 and the following components were mixed, and the curable compositions of Examples 1 to 23 and Comparative Examples 2 and 3 were prepared.

<Composition>

Organic solvent 1 (cyclohexanone)... 17.12 parts by mass

Alkali-soluble resin 1 (benzyl methacrylate/methacrylic acid (47/53 [mass ratio]), 30 mass% propylene glycol monomethyl ether solution, Mw=11,000)... 1.23 parts by mass

Alkali-soluble resin 2 (Accurure RD-F8 (made by Nippon Shokubai))... 0.23 parts by mass

Polymerizable compound (radical polymerizable compound, Shin-Nakamura Chemical Industry Co., Ltd. product, NK ester A-DPH-12E)... 1.96 parts by mass

Polymerization inhibitor (paramethoxyphenol)... 0.0007 parts by mass

Photopolymerization initiator (IRGACURE OXE02)... 0.975 parts by mass

Polyfunctional thiol compound (polyfunctional thiol compound shown in Table 2 below)... 0.35 parts by mass

Fluorine-based surfactant (manufactured by DIC, brand name: Megapak F-475, 1% by mass propylene glycol monomethyl ether acetate solution)... 2.50 parts by mass

Chromatic colorant 1: Dye solution 1 (dye solution prepared by the following method)... 24.57 parts by mass

Chromatic colorant 2: Pigment dispersion P1 (C. I. Pigment Blue 15:6 dispersion prepared by the following method, solid content concentration 11.8 mass%)... 51.40 parts by mass

In addition, in Table 2, T-1 and T-2 represent the following polyfunctional thiol compounds (polyfunctional thiol compounds having no mutual functional groups).

[Formula 36]

[Preparation of dye solution 1]

Dye solution 1 was prepared by mixing each of the following components.

Organic solvent (cyclohexanone)... 21.55 parts by mass

Dye (A-1 of the following structure)... 3.02 parts by mass

[Formula 37]

[Preparation of Pigment Dispersion P1]

Pigment dispersion liquid P1 was prepared in the following procedure.

CI Pigment Blue 15:6 (blue pigment, hereinafter also referred to as "PB 15:6") 19.4 parts by mass (average primary particle diameter 55 nm), pigment dispersant DISPERBYK-161 (solid content concentration 30% by mass, BYK) 2.95 parts by mass Parts, alkali-soluble resin 1 (benzyl methacrylate / methacrylic acid (47/53 [mass ratio]), 30 mass% propylene glycol monomethyl ether solution, Mw = 11,000) in terms of solid content 2.95 parts by mass (solution 9.93 parts by mass) and 165.3 parts by mass of propylene glycol monomethyl ether were mixed and dispersed for 3 hours by a beads mill (zirconia beads 0.3 mm in diameter). Then, further, dispersion treatment was performed under a pressure of 2000 kg/cm ^{3 and} a flow rate of 500 g/min using a high-pressure disperser NANO-3000-10 (manufactured by Nippon BEI) equipped with a decompression mechanism. This dispersion treatment was repeated 10 times to obtain a CI Pigment Blue 15:6 dispersion liquid, which is a pigment dispersion liquid P1. With respect to the obtained pigment dispersion P1, the average primary particle diameter of the pigment was measured by the dynamic light scattering method (Microtrac Nanotrac UPA-EX150 (manufactured by Nikkiso Co., ltd.) and found to be 24 nm.

[Preparation of the 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]

About the curable composition of each Example and the comparative example, exposure sensitivity was evaluated by the following method. Moreover, using the said curable composition, the adhesiveness to the glass base material of the pattern formed by the following method on a glass base material was evaluated by the following method. The evaluation results were put together and shown in Table 2 below.

[Exposure sensitivity]

The curable compositions of each of Examples and Comparative Examples were spin-coated on a glass substrate, and then dried to form a coating film (curable composition layer) having a thickness of 1.0 μm on the glass substrate. Spin coat conditions were set at 300 rpm for 5 seconds, 800 rpm for 20 seconds, and drying conditions at 100°C for 80 seconds. Next, the obtained coating film (curable composition layer) is 10 mJ/cm ² to 10 mJ/cm ² using a proximity-type exposure machine (manufactured by Hitachi Hi-Tech Denshi Engineering Co., Ltd.) using a test photomask having a line width of 2.0 μm and having an ultra-high pressure mercury lamp. The curable composition layer was cured in a pattern shape by exposure at various exposure amounts of 2,000 mJ/cm ² . 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 pattern-shaped cured film. Then, after rinsing the obtained pattern-shaped cured film with running water for 20 seconds, it air-dried.

The exposure sensitivity was evaluated by the minimum exposure amount at which the pattern line width after development of the region irradiated with light in the exposure step was 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 for} practical use under the above test conditions. The results were put together in Table 2 and shown.

〔Adhesion〕

In the pattern-shaped cured film produced in the above exposure sensitivity test, whether or not pattern defects occurred was observed with a SEM (Scanning Electron Microscope), and evaluated based on the following criteria. The results were put together in Table 2 and shown.

-Evaluation standard-

A: No pattern defect was observed.

B: There were 1-3 defects per pattern square 1.0 μm.

C: Pattern defects were 4 or more and 10 or less per 1.0 μm square pattern.

D: Pattern defects were 11 or more per 1.0 μm square pattern.

In addition, evaluation "B" or more is a practical range.

[Table 2]

From the results shown in Table 2, the curable compositions (curable compositions containing colored colorants) of Examples 1 to 23 containing a predetermined polyfunctional thiol compound had excellent exposure sensitivity and excellent adhesion to a support. there was.

On the other hand, in the curable composition of Comparative Example 1 that does not contain a polyfunctional thiol compound, the above effect was not obtained. In the polyfunctional thiol compounds of Comparative Examples 2 and 3 containing the polyfunctional thiol compound having no interactive group, the above effect was not obtained.

The curable compositions of Examples 2, 10, 18, and 21 in which m of the polyfunctional thiol compound represented by formula (2) was 3 or more had better exposure sensitivity compared to the curable composition of Example 1.

In the curable composition of Example 10, compared with the curable composition of Example 18 in which m+n was the same and m/n was larger, the obtained cured film had better adhesion to the support.

A carboxylic acid group or a salt thereof, a hydroxyl group, an amino group, a pyridinyl group, a phosphoric acid group or a salt thereof, a sulfonic acid group or a salt thereof, or -Si(R ^X ) _p (R ^Y ) _3-p Phosphorus, the curable composition of Examples 2 to 6, 8 and 9, compared with Example 7 in which the interactive group was a phenyl group, the resulting cured film had more excellent adhesion to the support.

[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. As a result, the same results as in Example 1 were obtained.

[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), and evaluated in the same manner as above. , The same result as in Example 1 was obtained.

[Preparation of curable compositions of Examples 24 to 54 and 59, and Comparative Examples 4 to 6]

The polyfunctional thiol compound shown in each column of Table 4 and each component were mixed in the composition shown in Table 3 to prepare the curable compositions of Examples 24 to 54 and 59, and Comparative Examples 5 and 6. A curable composition of Comparative Example 4 was prepared in the same manner as in Example 24 except that the polyfunctional thiol compound was not added.

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

[Table 3]

<Coloring agent>

Each colorant was produced by the following method.

(Titanium nitride-containing particles TiN-1)

First, Ti particles (TC-200, manufactured by Toho Tech) were plasma-treated in Ar gas to form Ti nanoparticles. The Ti nanoparticles after plasma treatment were allowed to stand for 24 hours under conditions of 50 ppm or less of O ₂ concentration and 30° C. in an Ar gas atmosphere. Thereafter, it was allowed to stand at 30° C. for 24 hours in a state where O ₂ gas was introduced into an Ar atmosphere so that the O ₂ concentration became 100 ppm (pretreatment of Ti particles).

Thereafter, the obtained Ti nanoparticles were classified using a TTSP separator manufactured by Hosokawa Micron under the condition of a yield of 10%, to obtain a powder of Ti particles. The primary particle diameter of the obtained powder was 120 nm when the average particle diameter of 100 particles was determined by the arithmetic average by TEM observation.

The titanium nitride-containing particles TiN-1 were manufactured using an apparatus similar to the black composite fine particle production apparatus described in Fig. 1 of International Publication No. 2010/147098.

Specifically, in the black composite fine particle manufacturing apparatus, a high frequency voltage of about 4 MHz and about 80 kVA is applied to a high frequency oscillation coil of a plasma torch, and argon gas 50 L/min and nitrogen 50 L/min as plasma gas from a plasma gas supply source. By supplying a mixed gas of, argon-nitrogen thermal plasma salt was generated 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 Co., Ltd.) and Si powder (Silicon powder SI006031) were mixed so that the respective mass ratios were Ti/Fe/Si=residue/0.05/0.05. This mixture was supplied together with argon gas as a carrier gas into a thermal plasma salt in a plasma torch, evaporated in the thermal plasma salt, and 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 rate in the chamber at this time was 5 m/sec, and the supply amount was 1,000 L/min. Further, the pressure in the cyclone was 50 kPa, and the feed rate of each raw material from the chamber to the cyclone was 10 m/s (average value).

In this way, titanium nitride-containing particles TiN-1 were obtained.

About the obtained titanium nitride containing particle TiN-1, the content of a titanium (Ti) atom, an iron (Fe) atom, and a silicon (Si) atom was measured by ICP emission spectroscopy. In addition, for the ICP emission spectroscopy analysis method, an ICP emission spectroscopy analyzer "SPS3000" (brand name) manufactured by Seiko Instruments Inc. was used.

The content of the nitrogen atom was measured using an oxygen/nitrogen analyzer "EMGA-620W/C" (brand name) manufactured by Horiba Seisakusho, and calculated by the inert gas melting-thermal conductivity method. As a result of the above, the mass ratio of each atom contained in the titanium nitride-containing particles TiN was Ti/N/Fe/Si=57/34/0.0030/0.0020.

The X-ray diffraction of the titanium nitride-containing particles TiN-1 was measured by filling a powder sample in a standard sample holder made of aluminum and using a wide-angle X-ray diffraction method (manufactured by Rigaku Denki, brand name "RU-200R"). As the measurement conditions, X-ray source is CuKα ray, output is 50kV/200mA, slit meter is 1°-1°-0.15mm-0.45mm, measurement step (2θ) is 0.02°, scan speed is 2°/min. did.

Then, the diffraction angle of the peak originating from the TiN (200) plane observed near the diffraction angle 2θ (42.6°) was measured. Further, rather than the half width of the peak derived from this (200) plane, the crystallite size constituting the particles was calculated using Scherrer's equation. As a result, the diffraction angle of the peak was 42.62°, and the crystallite size was 10 nm. In addition, no X-ray diffraction peak due to TiO ₂ was observed.

(TiN-2 particles containing titanium nitride)

As the Ti particles, instead of "TC-200" manufactured by Toho Tech, "578347" manufactured by Sigma Aldrich was used, and Fe powder and Si powder were used so that the mass ratio of each was Ti/Fe/Si=residue/0.5/1. Except for mixing, 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.

(TiN-3 particles containing titanium nitride)

Titanium nitride-containing particles TiN-3 were obtained in the same manner as TiN-1 except that the Fe powder and Si powder were mixed so that the respective mass ratios were Ti/Fe/Si=residue/1/2.

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)

Titanium oxide MT-150A (trade name, manufactured by Daika Co., Ltd.) with an average particle diameter of 15 nm was 100 g, silica particles with a specific surface area of 300 m ² /g (BET (Brunauer, Emmett, Teller)) AEROSIL300 (registered trademark) 300/30 (Evonik Co., Ltd.) was weighed 25 g, and Disperbyk190 (trade name, manufactured by Vicchemy) was weighed in 100 g, and these were added to 71 g of ion-exchanged water to obtain a mixture. Thereafter, using a KURABO MAZERSTAR KK-400W, a homogeneous aqueous mixture solution was obtained by treating the mixture at a revolution speed of 1,360 rpm and a rotation speed of 1,047 rpm for 30 minutes. This aqueous mixture solution was charged into a quartz container, and heated to 920°C in an oxygen atmosphere using a small rotary kiln (manufactured by Motoyama Co., Ltd.). Thereafter, the inside of the small rotary kiln was replaced with nitrogen, and ammonia gas was flowed at the same temperature at 100 mL/min for 5 hours to perform nitriding reduction treatment. After completion, the recovered powder was pulverized with a mortar, and titanium black [a dispersion object containing titanium black particles and Si atoms] having a powdery specific surface area of 73 m ² /g including Si atoms was obtained (hereinafter referred to as "titanium Black A-1").

(Preparation of niobium nitride-containing particles (NbN) containing Fe atom)

Niobium nitride-containing particles containing Fe atoms were produced by the following method.

First, niobium (powder) <100-325mesh> manufactured by Mitsuwa Chemical Yakuhin was prepared as a raw material (hereinafter, also referred to as "metal raw material powder").

Next, the metal raw material powder was subjected to plasma treatment in Ar gas to form Nb nanoparticles. The plasma treatment conditions were in accordance with the following plasma treatment (1).

Plasma treatment (1)

Plasma treatment (1) was performed by the following method. Plasma treatment was performed under the following conditions using an apparatus similar to the black composite fine particle production apparatus described above.

High frequency voltage applied to the coil for high frequency oscillation: frequency about 4MHz, voltage about 80kVA

Plasma gas: Argon gas (supply amount 100L/min)

Carrier gas: Argon gas (supply amount 10L/min)

Atmosphere in the chamber: Argon gas (supply amount 1,000L/min, flow rate in the chamber 5m/sec)

・Atmosphere in cyclone: Argon gas, internal pressure 50kPa

Material feed rate from the chamber to the cyclone: 10 m/s (average value)

Next, Fe powder (JIP270M, manufactured by JFE Steel) 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 by the above were mixed to obtain a raw metal powder. The raw metal powder was subjected to plasma treatment in nitrogen gas to obtain niobium nitride-containing particles. The plasma treatment conditions were in accordance with the following plasma treatment (2).

Plasma treatment (2)

Plasma treatment (2) was performed by the following method. In addition, the same apparatus as the plasma treatment (1) was used.

High frequency voltage applied to the coil for high frequency oscillation: frequency about 4MHz, voltage about 80kVA

Plasma gas: argon gas and nitrogen gas (supply amount 50L/min each)

Carrier gas: nitrogen gas (supply amount 10L/min)

Atmosphere in the chamber: nitrogen gas (supply amount 1,000L/min, flow rate in the chamber 5m/sec)

・Atmosphere in cyclone: nitrogen gas, internal pressure 50kPa

Material feed rate from the chamber to the cyclone: 10 m/s (average value)

After the plasma treatment (2) was completed, nitrogen gas at 20°C was introduced using Ar gas using a fractional humidity supply device SRH manufactured by Nippon Shintech Co., Ltd. under conditions of a relative humidity of 95% in the air, and allowed to stand for 24 hours. . Thereafter, the obtained particles were classified using a TTSP separator manufactured by Hosokawa Micron under the condition of a yield of 10%, and niobium nitride-containing particles (NbN) were obtained. Further, nitrogen gas was supplied to the separator.

About the obtained niobium nitride-containing particle|grains, when the content of iron (Fe) atom was measured by ICP emission spectroscopy, it was 50 mass ppm.

(Production of vanadium nitride-containing particles (VN) containing Fe atoms)

In the preparation of the niobium nitride-containing particles containing Fe atoms, the Fe atom was carried out in the same manner except for using the metal vanadium powder VHO made by Daiyo Goko instead of the niobium (powder) <100-325 mesh> manufactured by Mitsuwa Chemical Co., Ltd. A vanadium nitride containing particle (VN) containing was produced. About the obtained vanadium nitride-containing particle|grains, when the content of iron (Fe) atom was measured by ICP emission spectroscopy, it was 50 mass ppm.

<Dispersant>

As the dispersant, a dispersant A having the following structure was used. The numerical value described in each structural unit is intended for the mass% of each structural unit with respect to all structural units.

·Dispersant A

[Formula 38]

<Binder resin>

As the binder resin, the following resin A was used. The numerical value described in each structural unit intends the mole% of each structural unit with respect to all structural units. In addition, in the formula of Resin A, each symbol represents the following.

BzMA: benzyl methacrylate

MMA: methyl methacrylate

·Resin A

<Polymerizable compound>

-Polymerizable compound M1: dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku, brand name "KAYARAD", refer to the following formula)

[Formula 39]

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

<Photopolymerization initiator>

OXE-01: Irgacure OXE01 (trade name, manufactured by BASF Japan, corresponding to oxime compounds)

[Formula 40]

OXE-02: Irgacure OXE02 (trade name, BASF Japan company, corresponds to oxime compounds)

[Formula 41]

PI-3: photopolymerization initiator having the following structure (corresponding to oxime compounds)

[Formula 42]

NCI-831 (trade name, manufactured by ADEKA, corresponds to oxime compounds)

[Formula 43]

IRG-379: IRGACURE 379EG (brand name, BASF Japan company, does not correspond to oxime compounds)

[Formula 44]

<Surfactant>

F-1: Compound represented by the following formula (weight average molecular weight (Mw) = 15,311)

However, in the following formula, the structural units represented by formulas (A) and (B) are 62 mol% and 38 mol%, respectively. Among the structural units represented by formula (B), a, b, and c satisfy the relationship of a+c=14 and b=17, respectively.

[Formula 45]

<Organic Solvent>

PGMEA: Propylene glycol monomethyl ether acetate

·Cyclopentanone

・Butyl acetate

[Preparation of colorant dispersion]

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

<Dispersion condition>

Bead diameter: φ0.05mm (Nikkato zirconia beads, YTZ)

・Bead filling rate: 65% by volume

·Mill circumference speed: 10m/sec

Separator circumferential speed: 13m/s

Mixed liquid volume to be dispersed: 15kg

·Circulation flow (pump supply): 90kg/hour

·Treatment liquid temperature: 19~21℃

Coolant: water

・Processing time: about 22 hours

[Performance evaluation]

[Exposure sensitivity]

On the Si substrate having the surface treated with SiO ₂ , each curable composition was used, the rotation speed was adjusted so that a cured film having a thickness of 1.5 μm was obtained, and a coating film (curable composition layer) was formed by spin coating. The formed coating film was dried on a hot plate by heat treatment (prebaking) at 100° C. for 2 minutes. With respect to the substrate with a coating film (curable composition layer) after the prebaking, an i-line stepper (FPA3000i5+ manufactured by Canon) was used, and a photomask having a 200 μm length×20 μm width line pattern formed thereon was passed, and the coating layer was exposed. The coated film after exposure was puddle developed for 30 seconds using tetramethylammonium hydroxide as a developer using a coater developer ACT8 manufactured by Tokyo Electron. After image development, a shower rinse treatment was performed for 20 seconds with pure water. After development, the pattern was not peeled off and the lowest exposure amount maintained was evaluated as exposure sensitivity. In addition, the exposure sensitivity is preferably less than 500 mJ/cm ^{2 for} practical use under the above test conditions. The results were put together in Table 4 and shown.

〔Adhesion〕

In the pattern-shaped cured film produced in the above exposure sensitivity test, whether or not pattern defects occurred was observed with a SEM (Scanning Electron Microscope), and evaluated based on the following criteria. The results were put together in Table 4 and shown.

-Evaluation standard-

A: No pattern defect was observed.

B: There were 1-3 defects per pattern square 1.0 μm.

C: Pattern defects were 4 or more and 10 or less per 1.0 μm square pattern.

D: Pattern defects were 11 or more per 1.0 μm square pattern.

In addition, evaluation "B" or more is a practical range.

[Pattern shape]

The pattern-shaped cured film produced in the evaluation of the exposure sensitivity was post-baked (temperature: 220°C, time: 300 seconds). The pattern shape of the cured film after post-baking was measured by measuring SEM (Scanning Electron Microscope). Specifically, the film thickness at the end of the line pattern and the film thickness at the center were measured, the ratio (film thickness at the pattern end/film thickness at the center) was calculated, and evaluated according to the following criteria. In addition, evaluation "2" or more is a practical use range.

*7: The ratio is more than 0.98 and 1.00 or less, and there is no difference in the film thickness of the center portion and the end of the pattern when observed by SEM.

*6: The ratio is more than 0.96 and not more than 0.98, and there is a slight difference in the film thickness of the central portion and the end of the pattern.

* 5: The ratio is more than 0.94 and not more than 0.96, and there is a difference in the film thickness of the central portion and the end of the pattern.

*4: The ratio is more than 0.92 and 0.94 or less, the film thickness at the end is thin, and the level is slightly deformed, but practically no problem.

3: The ratio is more than 0.90 and 0.92 or less, the film thickness at the end is thin, and the level is deformed, but practically no problem.

*2: The ratio is more than 0.80 and 0.90 or less, and the film thickness at the end is thin, but the level is practical.

* 1: The ratio is 0.80 or less, and the film thickness at the end is thin, and is not permitted.

〔Developability〕

In the pattern-shaped cured film produced in the evaluation of the exposure sensitivity, when exposed, the presence or absence of a residue in a region that was shielded by a photomask and was not irradiated with light (unexposed portion) was determined by SEM (magnification: 20,000 times) and evaluated developability. The evaluation criteria were as follows, and the results were put together in Table 4 and shown.

-Evaluation standard-

A: In the unexposed part, no residue was observed at all.

B: 1 or more and 3 or less residues were observed in 1.0 μm square of the unexposed part.

C: 4 or more and 10 or less residues were observed in 1.0 μm square of the unexposed part.

D: 11 or more residues were observed in the 1.0 μm square of the unexposed part.

In practical use, "C" or more is preferable, and "A" and "B" are evaluated as having excellent performance.

[Table 4]

From the results shown in Table 4, the curable compositions of Examples 24 to 54 and 59 (curable compositions containing black pigments) containing a predetermined polyfunctional thiol compound had excellent exposure sensitivity, and excellent It had adhesion.

On the other hand, the curable composition of Comparative Example 4 which does not contain a polyfunctional thiol compound did not have the above effect. The polyfunctional thiol compounds of Comparative Example 5 and Comparative Example 6 containing the polyfunctional thiol compound having no interactive group did not have the above effect.

The curable compositions of Examples 25 to 54 and 59, in which m of the polyfunctional thiol compound represented by Formula (2) was 3 or more, had better exposure sensitivity compared to the curable composition of Example 24.

In the curable composition in which the interaction group different from the thiol group is a hydroxy group (Example 26), an amino group (Example 27), or a pyridinyl group (Example 31), a phenyl group (Example 31) It had more excellent developability compared with Example 30) or the curable composition which was Si group (Example 32).

In the curable composition, in which an interoperable group different from a thiol group is a carboxylic acid group (Example 25), a phosphoric acid group (Example 28), or a sulfonic acid group (Example 29), a hydroxy group ( Compared with the curable composition of Example 26), an amino group (Example 27), or a pyridinyl group (Example 31), it had better developability. This is presumed to be due to the difference in solubility of the unexposed portion due to the difference in the interactive group different from the thiol group.

The curable composition of Example 33 had the same m+n, and had a more excellent pattern shape, and had more excellent adhesion to the support compared to the curable composition of Example 41 having a larger m/n. .

The curable compositions of Examples 33, 47, 48, 49, and 50 in which the photopolymerization initiator was an oxime compound had better exposure sensitivity compared to the curable composition of Example 59.

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

Except having used the polymeric compound M2 instead of the polymeric compound M1, it carried out similarly to Example 33, and produced the curable composition, and when evaluated, the same result as Example 33 was obtained.

In place of the polymerizable compound M1, a mixture of the polymerizable compounds M1 and M2 (the content mass ratio of M1 and M2 in the mixture is the content mass of M1: the content mass of M2 = 1:1, and the mixture with respect to the entire curable composition Except for using the content of the polymerizable compound M1 in Example 33), a curable composition was prepared and evaluated in the same manner as in Example 33, and the same result as in Example 33 was obtained. Was obtained.

[Preparation of carbon black dispersion (CB dispersion) and evaluation of curable composition]

In the preparation of the above colorant dispersion, the colorant was made into carbon black (trade name "Color Black S170", manufactured by Degussa, an average primary particle diameter of 17 nm, BET specific surface area of 200 m ² /g, carbon black manufactured by a gas black method). Except that, a carbon black dispersion (CB dispersion) was obtained by the same method.

In the preparation of the curable composition of Example 33, in place of the colorant dispersion liquid added so as to contain 58% by mass of titanium nitride-containing particles TiN-1 in the curable composition, the colorant dispersion liquid and the CB dispersion containing titanium nitride-containing particles TiN-1 Mixture (TiN-1 of titanium nitride-containing particles in the curable composition: carbon black in the curable composition = 45:13 (mass ratio), the total content of the titanium nitride-containing particles TiN-1 and carbon black in the curable composition is 58% by mass) Except having used, it carried out similarly, and prepared the curable composition, 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 chromatic pigment dispersion (PY dispersion) and evaluation of curable composition]

In the preparation of the above-described colorant dispersion, a chromatic pigment dispersion (PY dispersion) was used in the same manner except that the colorant was Pigment Yellow 150 (manufactured by Hangzhou Star-up Pigment Co., Ltd., brand name 6150 Pigment Sulfur 5GN). ).

In the preparation of the curable composition of Example 33, in place of the colorant dispersion liquid added so as to contain 58% by mass of titanium nitride-containing particles TiN-1 in the curable composition, a colorant dispersion liquid containing titanium nitride-containing particles TiN-1 and the PY dispersion liquid A mixture of (TiN-1 titanium nitride-containing particles in the curable composition: Pigment Yellow 150 = 45:13 (mass ratio) in the curable composition, the total content of the titanium nitride-containing particles TiN-1 and Pigment Yellow 150 in the curable composition is 58 mass. %) was used to prepare a curable composition in the same manner, and evaluated using this. As a result of the evaluation, the same evaluation (including exposure sensitivity and adhesion) as in Example 33 was obtained. In addition, as a cured film, black light became a darker film.

[Preparation of chromatic pigment dispersion (PR dispersion)]

In the preparation of the above colorant dispersion, a chromatic color pigment dispersion (PR dispersion) was obtained by the same method except that the colorant was C. I. Pigment Red 254 (manufactured by Chiba Specialty Chemicals).

[Preparation of chromatic pigment dispersion (PB dispersion)]

In the preparation of the above colorant dispersion, a colored pigment dispersion (PB dispersion) was obtained by the same method except that the colorant was C. I. Pigment Blue 15:6 (manufactured by DIC Corporation).

[Preparation of chromatic pigment dispersion (PV dispersion)]

In the preparation of the above-described colorant dispersion, a colored pigment dispersion (PV dispersion) was obtained by the same method except that the colorant was C. I. Pigment Violet 23 (manufactured by Clariant).

In the preparation of the curable composition of Example 33, in place of the colorant dispersion added so as to contain 58% by mass of titanium nitride-containing particles TiN-1 in the curable composition, the titanium nitride-containing particles TiN-1, PY, PR, PB, And a mixture of PV dispersions (ratio of titanium nitride-containing particles TiN-1, PY, PR, PB, and PV in the curable composition; titanium nitride-containing particles TiN-1:PY:PR:PB:PV=70:17:37: 36:10 (mass ratio), the total content of titanium nitride-containing particles TiN-1, PY, PR, PB, and PV in the curable composition is 58% by mass), to prepare a curable composition in the same manner, and use this 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 property in the infrared region was obtained.

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

In the preparation of the curable composition of Example 33, in place of the colorant dispersion added so as to contain 58% by mass of titanium nitride-containing particles TiN-1 in the curable composition, the titanium nitride-containing particles TiN-1 and the following compound A-52 were Mixture (ratio of titanium nitride-containing particles TiN-1 and compound A-52 in the curable composition; titanium nitride-containing particles TiN-1: compound A-52 = 50:8 (mass ratio), titanium nitride-containing particles TiN-1 in the curable composition And the total content of the compound A-52 is 58% by mass), except that a curable composition was prepared in the same manner, and evaluation was performed using this. As a result of the evaluation, it was found that the same evaluation (including exposure sensitivity and adhesion) as in Example 33 was obtained, and a film excellent in light-shielding property 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, evaluation was carried out in the same manner except that surfactant F-1 was not used. As a result of evaluation, it turned out that the same result as Example 1 was obtained.

Claims (14)

As a curable composition containing a polyfunctional thiol compound, a polymerizable compound, a photoinitiator, and a colorant,
The polyfunctional thiol compound contains two or more thiol groups and an interactive group different from the thiol group,
The polyfunctional thiol compound is a compound represented by formula (2),
A curable composition containing 50% by mass or more of the colorant based on the total solid content.

In the formula, R ² represents a divalent linking group having 1 or more carbon atoms, and R ³ represents an unsubstituted divalent aliphatic hydrocarbon group, -C(=O)-, -C(=O)-O-, -OC( =O)-O-, -C(=O)-NH-, -OC(=O)-, -CH=N-, -N(R)- (R is an alkyl group), or a group combining them,
m represents an integer of 2 to 14, n represents an integer of 1 to 15, and M ¹ each independently represents a single bond, -O-, -S-, -N(R ⁴ )-, -C( =O)-, -C(=O)-O-, -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 hydroxyl group, an amino group, a pyridinyl group, a pyridinium group, an ammonium group, a phosphonium group, a carboxylic acid group or a salt thereof, a phosphoric acid group or a salt thereof, a sulfonic acid group or a salt thereof , Aryl group, -Si(R ^X ) _p (R ^Y ) _3-p (R ^X represents a hydrolyzable group, R ^Y represents a monovalent organic group excluding a hydrolyzable group, p represents an integer of 1 to 3) , And -(OR ^A ) _q -R ^Z (R ^A represents an alkylene group having 1 to 15 carbon atoms, R ^Z represents a hydrogen atom, an alkyl group, or an alkoxy group, and q represents an integer of 1 to 4) It represents a group selected from the group. Here, R ¹ represents an unsubstituted group.
In addition, R ² and R ³ 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 are, respectively It may be the same or different. The method according to claim 1,
R ¹ represents a group selected from the group consisting of a hydroxyl group, an amino group, a pyridinyl group, a pyridinium group, an ammonium group, a phosphonium group, a carboxylic acid group or a salt thereof, a phosphoric acid group or a salt thereof, and a sulfonic acid group or a salt thereof. . The method according to claim 1,
R ¹ represents a group selected from the group consisting of a hydroxyl group, an amino group, a pyridinyl group, a carboxylic acid group or a salt thereof, a phosphoric acid group or a salt thereof, and a sulfonic acid group or a salt thereof. The method according to any one of claims 1 to 3,
The curable composition, wherein the colorant contains a black pigment. The method according to any one of claims 1 to 3,
The photopolymerization initiator is an oxime compound, curable composition. A cured film obtained by curing the curable composition according to any one of claims 1 to 3. A color filter containing the cured film according to claim 6. A light-shielding film containing the cured film according to claim 6. A solid-state imaging device containing the cured film according to claim 6. An image display device containing the cured film according to claim 6. A curable composition layer formation step of forming a curable composition layer on a support using the curable composition according to any one of claims 1 to 3, and
A method for producing a cured film including an exposure step of exposing the curable composition layer. The method of claim 11,
The method for producing a cured film, wherein the curable composition layer forming step includes a step of applying the curable composition on the support to form the curable composition layer on the support. The method of claim 11,
A developing process of developing the exposed curable composition layer,
A method for producing a cured film, further comprising a washing step of washing the developed curable composition layer. A polyfunctional thiol compound which contains two or more thiol groups and an interactive group different from the thiol group, and is represented by formula (2).

In the formula, R ² represents a divalent linking group having 1 or more carbon atoms, and R ³ represents an unsubstituted divalent aliphatic hydrocarbon group, -C(=O)-, -C(=O)-O-, -OC( =O)-O-, -C(=O)-NH-, -OC(=O)-, -CH=N-, -N(R)- (R is an alkyl group), or a group combining them,
m represents an integer of 2 to 14, n represents an integer of 1 to 15, and M ¹ each independently represents a single bond, -O-, -S-, -N(R ⁴ )-, -C( =O)-, -C(=O)-O-, -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 hydroxyl group, an amino group, a pyridinyl group, a pyridinium group, an ammonium group, a phosphonium group, a carboxylic acid group or a salt thereof, a phosphoric acid group or a salt thereof, a sulfonic acid group or a salt thereof , Aryl group, -Si(R ^X ) _p (R ^Y ) _3-p (R ^X represents a hydrolyzable group, R ^Y represents a monovalent organic group excluding a hydrolyzable group, p represents an integer of 1 to 3) , And -(OR ^A ) _q -R ^Z (R ^A represents an alkylene group having 1 to 15 carbon atoms, R ^Z represents a hydrogen atom, an alkyl group, or an alkoxy group, and q represents an integer of 1 to 4) It represents a group selected from the group. Here, R ¹ represents an unsubstituted group.
In addition, R ² and R ³ 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 are, respectively It may be the same or different.