JP2021047216A - Curable composition - Google Patents

Abstract

To provide a curable composition which allows for forming optical filters with superior properties for blocking UV rays near the visible light region and transmitting visible light, good heat resistance, and less defects such as foreign matter inclusion.SOLUTION: The present invention relates to a curable composition containing a first specific compound, a second specific compound, a binder with a polymerizable group, and a solvent.SELECTED DRAWING: None

Description

The present invention relates to curable compositions.

Video cameras, digital cameras, mobile phones with camera functions, and the like are equipped with a solid-state image sensor, which is an optical sensor. Specifically, as a solid-state image sensor, a CCD (Charge-Coupled Device) image sensor, a CMOS (Complementary MOS) image sensor, and the like are widely used. The sensitivity of the photodiode provided in these solid-state image sensors ranges from the ultraviolet region close to visible light to the infrared region. For this reason, the solid-state image sensor is provided with an optical filter for blocking ultraviolet rays and infrared rays close to the visible light region. With this optical filter, the sensitivity of the solid-state image sensor can be corrected so as to approach the human visual sensitivity. In addition to the solid-state image sensor, optical filters that block ultraviolet rays and the like are used for various purposes.

For the formation of the optical filter, for example, a composition containing each component such as a dye, a polymerizable compound, and a polymerization initiator for blocking light rays having a predetermined wavelength is used (see Patent Document 1). An optical filter is formed by applying and curing such a composition.

Japanese Unexamined Patent Publication No. 2013-228433

As an optical filter for shielding light rays in the ultraviolet region, an optical filter having higher ultraviolet shielding property is desired. On the other hand, in the conventional optical filter, defects such as foreign matter may occur. Defects in the optical filter may affect visible light transmission, shielding, and the like. Further, the optical filter may be required to have heat resistance, for example, its transparency and shielding property are unlikely to be lowered even when it is used at a high temperature.

The present invention has been made based on the above circumstances, and an object of the present invention is to have good ultraviolet shielding property, visible light transmission and heat resistance close to the visible light region, and to have defects such as foreign substances. It is to provide a curable composition capable of forming a small number of optical filters.

（式（１）中、Ｒ^１、Ｒ^２及びＲ^３は、それぞれ独立して、炭素数１〜３０の１価の有機基である。Ｒ^４及びＲ^５は、それぞれ独立して、炭素数１〜３０の１価の有機基又はハロゲン原子である。ａ及びｂは、それぞれ独立して、０〜３の整数である。ａが２以上の場合、複数のＲ^４は、同一でも異なっていてもよい。ｂが２以上の場合、複数のＲ^５は、同一でも異なっていてもよい。）

（式（２）中、Ａは、１又は複数の五員環又は六員環から構成される環構造である。Ｒ^６は、ハロゲン原子、ヒドロキシ基、ニトロ基又は炭素数１〜４０の１価の有機基である。Ｒ^７は、＊−ＣＯ−、＊−ＣＯＯ−、＊−ＳＣＯ−、＊−ＣＯＳ−、＊−Ｓ−ＣＯＯ−、＊−ＣＯＮＨ−、＊−ＮＨＣＯ−、又は＊−ＮＨＣＯＯ−（＊は、酸素原子との結合位置を示す。）である。Ｒ^８は、炭素数１〜２０の１価の有機基である。ｃは、０〜４の整数である。ｄは、１〜３の整数である。ｅは、１〜１０の整数である。ｅが１の場合、Ｘは１価の有機基であり、ｅが２以上の場合、Ｘはｅ価の連結基である。Ｒ^６、Ｒ^７又はＲ^８が複数である場合、複数のＲ^６、複数のＲ^７又は複数のＲ^８は、同一でも異なっていてもよい。） The invention made to solve the above problems includes a first compound represented by the following formula (1), a second compound represented by the following formula (2), a binder containing a compound having a polymerizable group, and a solvent. It is a curable composition containing.

(In the formula (1), R ¹ , R ² and R ³ are independently monovalent organic groups having 1 to 30 carbon atoms. R ⁴ and R ⁵ are independent of each other and have carbon numbers. .a and b is a monovalent organic group or a halogen atom having 1 to 30 are each independently, if .a is 2 or an integer of 0-3, a plurality of R ⁴ may be the same or different If even better .b is 2 or more, plural R ⁵ may be the same or different.)

(In the formula (2), A is a ring structure composed of one or more five-membered rings or six-membered rings. R ⁶ is a halogen atom, a hydroxy group, a nitro group or 1 of 1 to 40 carbon atoms. A valent organic group, R ⁷ is * -CO-, * -COO-, * -SCO-, * -COS-, * -S-COO-, * -CONH-, * -NHCO-, or *. -NHCOO- (* indicates the bonding position with the oxygen atom). R ⁸ is a monovalent organic group having 1 to 20 carbon atoms. C is an integer of 0 to 4. d. Is an integer of 1 to 3. e is an integer of 1 to 10. When e is 1, X is a monovalent organic group, and when e is 2 or more, X is a concatenation of e valences. When there are a plurality of ^{R 6} , R ⁷ or R ^{8 , the plurality of R 6} , the plurality of R ^7s or the plurality of R ^8s may be the same or different.

According to the present invention, there is provided a curable composition capable of forming an optical filter having good ultraviolet shielding property, visible light transmission and heat resistance close to the visible light region and few defects such as foreign substances. be able to.

[Curable composition]
The curable composition according to one embodiment of the present invention is represented by the first compound represented by the formula (A) (1) (hereinafter, also referred to as “(A) compound”) and the formula (2). It contains the second compound represented (hereinafter, also referred to as “(B) compound”), (C) binder, and (D) solvent. (C) The binder contains a compound having a polymerizable group.

The curable composition has good ultraviolet shielding properties, visible light transmission and heat resistance close to the visible light region, and can form an optical filter having few defects such as foreign substances. What is formed from the curable composition may be a cured product, a cured film, a shielding film, or the like. The reason why the above effect occurs in the curable composition is not clear, but the following reasons are presumed. The compound (A) is an oxime-based polymerization initiator in which a nitro group is bonded to a carbazole skeleton. In the compound (A), after functioning as a polymerization initiator, it is presumed that a compound having a carbazole skeleton to which a nitro group is bonded tends to remain in the cured product (optical filter) as a residue. By having a carbazole skeleton to which a nitro group is bonded, this residue has sufficient transparency to visible light in the cured product, and is close to the visible light region (for example, wavelength 350 to 395 nm). (Ultraviolet rays) can be sufficiently absorbed. On the other hand, the residue is likely to cause defects, and specifically, it is presumed that defects such as foreign substances are generated by the generation of radicals derived from the residue in the cured product. On the other hand, the compound (B) ^{has a structure in which the protecting group (-R 7-} R ⁸ ) is eliminated at a high temperature, and the function of capturing radicals is exhibited only after the elimination. Therefore, the compound (B) does not capture radicals generated from the compound (A) which is a polymerization initiator during heating for curing, and is derived from a residue generated in the cured product (optical filter) after curing. Radicals and the like can be sufficiently captured. Therefore, according to the curable composition containing the compound (A) and the compound (B), the shielding property of ultraviolet rays close to the visible light region and the transmission of visible light are good, and foreign substances and the like are present. It is presumed that an optical filter with few defects can be formed. Further, by using the compound (A) as the polymerization initiator, the heat resistance of the formed optical filter is also improved.

[(A) Compound]
The compound (A) is a compound represented by the following formula (1). As described above, while the compound (A) functions well as a polymerization initiator, it remains in the obtained optical filter and absorbs ultraviolet rays close to the visible light region.

In formula (1), R ¹ , R ² and R ³ are independently monovalent organic groups having 1 to 30 carbon atoms. R ⁴ and R ⁵ are independently monovalent organic groups or halogen atoms having 1 to 30 carbon atoms. a and b are independently integers of 0 to 3. When a is 2 or more, the plurality of R ^4s may be the same or different. When b is 2 or more, the plurality of R ^5s may be the same or different.

Here, the "organic group" means a group containing at least one carbon atom.

Examples of the monovalent organic group having 1 to 30 carbon atoms represented by R ^{1 to} R ⁵ include a monovalent hydrocarbon group, a divalent group at the carbon-carbon end of the above hydrocarbon group or at the end on the bond hand side. Examples thereof include a group containing a hetero atom-containing group, a group in which a part or all of the hydrogen atoms of the above hydrocarbon group and the group containing the hetero atom-containing group are substituted with a monovalent hetero atom-containing group, and the like.

Examples of the monovalent hydrocarbon group include a chain hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group and the like.

Examples of the chain hydrocarbon group include alkyl groups such as methyl group, ethyl group, propyl group, butyl group and pentyl group;
Alkenyl groups such as ethenyl group, propenyl group, butenyl group, pentenyl group;
Examples thereof include an alkynyl group such as an ethynyl group, a propynyl group, a butynyl group and a pentynyl group.

Examples of the alicyclic hydrocarbon group include a monocyclic cycloalkyl group such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group;
Polycyclic cycloalkyl groups such as norbornyl group, adamantyl group, tricyclodecyl group, tetracyclododecyl group;
Monocyclic cycloalkenyl groups such as cyclopropenyl group, cyclobutenyl group, cyclopentenyl group, cyclohexenyl group;
Examples thereof include polycyclic cycloalkenyl groups such as norbornenyl group and tricyclodecenyl group.
The alicyclic hydrocarbon group may be a hydrocarbon group in which a chain structure and an alicyclic structure are combined, such as a cycloalkylalkyl group such as a 2-cyclopentylethyl group or a 2-cyclohexylethyl group.

Examples of the aromatic hydrocarbon group include aryl groups such as phenyl group, tolyl group, xsilyl group, naphthyl group and anthryl group;
Examples thereof include an aralkyl group such as a benzyl group, a phenethyl group, a naphthylmethyl group and an anthrylmethyl group.

Examples of the heteroatom contained in the monovalent or divalent heteroatom-containing group include an oxygen atom, a sulfur atom, a nitrogen atom, a silicon atom, a phosphorus atom and the like. Among these, an oxygen atom, a sulfur atom, and a nitrogen atom are preferable, and an oxygen atom is more preferable.

Examples of the divalent heteroatom-containing group include -O-, -CO-, -CS-, -NR'-, a group combining these, and the like. R'is a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms.

Examples of the monovalent heteroatom-containing group include a hydroxy group, a carboxy group, a sulfanyl group (-SH), an amino group, a cyano group and the like.

Examples of the halogen atom represented by R ^{4 to} R ⁵ include a fluorine atom, a chlorine atom, a bromine atom and the like.

As R ¹ , a hydrocarbon group having a substituent or an unsubstituted group is preferable, and a hydrocarbon group having a substituent is more preferable. As the hydrocarbon group, an alkyl group, a cycloalkyl group, a cycloalkylalkyl group and an aryl group are preferable. When R ¹ has a substituent or is an unsubstituted aryl group, the shielding property of ultraviolet rays near the visible light region in the obtained optical filter tends to be further enhanced. On the other hand, when R ¹ has a substituent or is an unsubstituted alkyl group, a cycloalkyl group or a cycloalkylalkyl group, the visible light transmittance in the obtained optical filter tends to increase.

Examples of the substituent that the hydrocarbon group represented by R ¹ may have include an alkoxy group having a substituent or an unsubstituted group. An alkoxy group is a group in which a hydrocarbon group is bonded to an oxygen atom. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a phenyloxy group and the like. Examples of the substituent that the alkoxy group may have include an alkoxy group and a heterocyclic group. Examples of the heterocyclic group include a pyridyl group, a pyrimidyl group, a frill group, a thienyl group, a tetrahydrofuryl group, a dioxolanyl group, a benzoxazole-2-yl group, a tetrahydropyranyl group, a pyrrolidyl group, an imidazolidyl group, a pyrazolydyl group and a thiazolizyl group. Examples thereof include 5- to 7-membered heterocycles such as an isothiazolyzyl group, an oxazolidyl group, an isooxazolyzyl group, a piperidyl group, a piperazyl group and a morpholinyl group. These heterocyclic groups may further have a substituent such as an alkyl group. The heterocyclic group is preferably a group composed of a carbon atom, a hydrogen atom and an oxygen atom. The ^{substituent that the hydrocarbon group represented by R 1} may have is preferably a group composed of a carbon atom, a hydrogen atom and an oxygen atom.

Further, R ¹ is preferably a hydrocarbon group or a group composed of a carbon atom, a hydrogen atom and an oxygen atom, and more preferably a group composed of a carbon atom, a hydrogen atom and an oxygen atom. When R ¹ contains an oxygen atom, the oxygen atom is preferably an oxygen atom forming an ether bond. That is, R ¹ is preferably a hydrocarbon group or a group containing an oxygen atom between carbons of the hydrocarbon group.

As ^{the upper limit of the number of carbon atoms of R 1} , 20 is preferable, 15 is more preferable, and 10 is further preferable. When the ^{number of carbon atoms of R 1} is not more than the above upper limit, the visible light transmittance in the obtained optical filter tends to increase. The lower limit of the number of carbon atoms of R ^{1 may be preferably 3, 5 or 9.} When the ^{number of carbon atoms of R 1} is at least the above lower limit, the shielding property of ultraviolet rays near the visible light region in the obtained optical filter tends to be further enhanced.

The R ^2, preferably a hydrocarbon group, more preferably an alkyl group and an aryl group, further preferably an alkyl group. The upper limit of the number of carbon atoms of R ^2, preferably 10, more preferably 6, 3 is more preferable. The R ^2, particularly preferably a methyl group and an ethyl group, most preferably a methyl group.

The R ^3, preferably a hydrocarbon group, an alkyl group is more preferable. As ^{the upper limit of the number of carbon atoms of R 3} , 10 is preferable, 6 is more preferable, and 3 is further preferable. As R ^3, a methyl group, particularly preferably an ethyl group and propyl group, and most preferably an ethyl group.

As R ⁴ and R ⁵ , a hydrocarbon group is preferable, and an alkyl group is more preferable, respectively. As ^{the upper limit of the number of carbon atoms of R 4} and R ⁵ , 10 is preferable, 6 is more preferable, and 3 is further preferable, respectively.

A is preferably 0. b is preferably 0.

In the compound (A), the nitro group (-NO ₂ ) is preferably bonded to the 3-position of the carbazole skeleton.

Specific examples of the compound (A) include the compounds described in paragraph [0037] of International Publication No. 2017/010575. The compound (A) can be used alone or in admixture of two or more.

The lower limit of the content of the compound (A) in the total solid content (components other than the solvent (D)) in the curable composition is preferably 0.1% by mass, more preferably 0.3% by mass. When the content of the compound (A) is at least the above lower limit, the shielding property of ultraviolet rays close to the visible light region in the obtained optical filter is further enhanced, and good curability, heat resistance and the like can be exhibited. .. On the other hand, the upper limit of this content is preferably 30% by mass, more preferably 10% by mass, and even more preferably 5% by mass or 2% by mass. When the content of the compound (A) is not more than the above upper limit, defects such as foreign substances in the obtained optical filter are further reduced, and visible light transmission is also improved.

[(A') compound]
The curable composition may further contain a compound (A') which is a polymerization initiator other than the compound (A). As the (A') compound, a conventionally known polymerization initiator can be used. Examples of the (A') compound include O-acyloxime compounds other than the (A) compound, thioxanthone compounds, acetophenone compounds, biimidazole compounds, triazine compounds, onium salt compounds, benzoin compounds, and benzophenone compounds. Examples thereof include compounds, α-diketone compounds, polynuclear quinone compounds, diazo compounds, imide sulfonate compounds, onium salt compounds and the like. Among these, O-acyloxime compounds are preferable.

As the compound (A'), a compound having a phenylthio skeleton and an oxime ester structure is more preferable. By using such a compound in combination with the (A') compound, the visible light transmittance of the obtained optical filter tends to be improved.

As the compound having a phenylthio skeleton and an oxime ester structure, a compound represented by the following formula (5) is preferable.

In formula (5), R ⁹ and R ¹⁰ are independently monovalent organic groups having 1 to 30 carbon atoms. R ¹¹ is a hydrogen atom, a benzoyl group, a hydroxy group, a carboxy group, a monovalent hydrocarbon group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms or having no substituents. R ¹² and R ¹³ are independently monovalent organic groups or halogen atoms having 1 to 30 carbon atoms. f and g are independently integers of 0 to 4. When f is 2 or more, the plurality of R ^12s may be the same or different. When g is 2 or more, the plurality of R ^13s may be the same or different.

The monovalent organic group having 1 to 30 carbon atoms represented by ^{R 9} , R ¹⁰ , R ¹² and R ¹³ is the same as the monovalent organic group having 1 to 30 carbon atoms represented by ^{R 1 and the like.} ..

As R ⁹ , a hydrocarbon group having a substituent or an unsubstituted group is preferable, and an unsubstituted hydrocarbon group is more preferable. As the above-mentioned hydrocarbon group, an alkyl group, a cycloalkyl group, a cycloalkylalkyl group and an aryl group are preferable, and an alkyl group is more preferable. Examples of the substituent that the hydrocarbon group represented by R ⁹ may have include the same group as the substituent that the hydrocarbon group represented by ^{R 1 may have.}

As ^{the upper limit of the number of carbon atoms of R 9} , 20 is preferable, 10 is more preferable, and 6 is more preferable. The lower limit of the number of carbon atoms of R ^{9 is 1.}

As R ¹⁰ , a hydrocarbon group is preferable, and an alkyl group and an aryl group are more preferable. As ^{the upper limit of the number of carbon atoms of R 10} , 10 is preferable, and 6 is more preferable. The R ^10, a methyl group, an ethyl group, a propyl group and phenyl group are particularly preferred.

Examples of the ^{substituent that the alkoxy group represented by R 11} may have include a hydroxy group, a carboxy group, an alkoxy group and the like, and a hydroxy group is preferable.

The R ^11, a hydrogen atom, a C1-10 hydrocarbon group, and is preferably or unsubstituted alkoxy group having 1 to 10 carbon atoms having a substituent group, of having or unsubstituted hydrogen atom, and substituents Alkoxy groups having 1 to 10 carbon atoms are more preferable. Among the alkoxy groups having 1 to 10 carbon atoms having a substituent or unsubstituted, an alkoxy group having a hydroxy group as a substituent and having 1 to 10 carbon atoms is preferable, and an alkoxy group having a hydroxy group as a substituent has 1 to 4 carbon atoms. Alkoxy group is more preferable.

As R ¹² and R ¹³ , a hydrocarbon group is preferable, and an alkyl group is more preferable, respectively. As ^{the upper limit of the number of carbon atoms of R 12} and R ¹³ , 10 is preferable, 6 is more preferable, and 3 is further preferable, respectively.

g is preferably 0. f is preferably 0.

The compound (A') can be used alone or in admixture of two or more.

When the curable composition contains the (A') compound, the lower limit of the content of the (A') compound in the total solid content of the curable composition is preferably 1% by mass, preferably 2% by mass. More preferred. On the other hand, as the upper limit of this content, 20% by mass is preferable, and 10% by mass is more preferable.

The lower limit of the total content of the compound (A) and the compound (A') in the total solid content of the curable composition is preferably 1% by mass, more preferably 3% by mass. When the total content is at least the above lower limit, the shielding property of ultraviolet rays near the visible light region in the obtained optical filter is further enhanced, and the heat resistance can also be enhanced. On the other hand, the upper limit of this content is preferably 30% by mass, more preferably 10% by mass. When the total content is not more than the above upper limit, defects such as foreign substances in the obtained optical filter are further reduced, and visible light transmission is also improved.

When the compound (A) and a compound having a phenylthio skeleton and an oxime ester structure are used in combination in the curable composition, the content ratio (mass ratio) thereof is preferably 1:20 to 20: 1. 15 to 15: 1 is more preferred. By using the compound (A) in combination with a compound having a phenylthio skeleton and an oxime ester structure in such a ratio, the ultraviolet shielding property, visible light transmittance, etc., which are close to the visible light region of the obtained optical filter, can be further improved. improves.

[(B) Compound]
The compound (B) is a compound represented by the following formula (2). As described above, the compound (B) is a potential radical scavenger whose radical scavenging ability is exhibited only after heating. When the curable composition contains the compound (B), defects in the obtained optical filter are reduced, and as a result, good visible light transmission is exhibited.

In formula (2), A is a ring structure composed of one or more five-membered or six-membered rings. R ⁶ is a halogen atom, a hydroxy group, a nitro group, or a monovalent organic group having 1 to 40 carbon atoms. R ⁷ is * -CO-, * -COO-, * -SCO-, * -COS-, * -S-COO-, * -CONH-, * -NHCO-, or * -NHCOO- (* is It shows the bond position with the oxygen atom.). R ⁸ is a monovalent organic group having 1 to 20 carbon atoms. c is an integer from 0 to 4. d is an integer of 1 to 3. e is an integer from 1 to 10. When e is 1, X is a monovalent organic group, and when e is 2 or more, X is an e-valent linking group. When there are a plurality of ^{R 6} , R ⁷ or R ^{8 , the plurality of R 6} , the plurality of R ^7s or the plurality of R ^8s may be the same or different.

Examples of the ring structure represented by A include a carbon ring, a heterocycle and the like. Examples of the carbon ring include an alicyclic ring such as a cyclopentane ring, a cyclohexane ring, a cyclopentene ring and a cyclohexene ring, and an aromatic ring such as a benzene ring and a naphthalene ring. Heterocycles include furan ring, thiophene ring, pyrrol ring, pyrrolidine ring, pyrazolidine ring, pyrazole ring, imidazole ring, imidazolidine ring, oxazole ring, isoxazole ring, isooxazolidine ring, thiazole ring, isothiazole ring, and isothiazolidine ring. , Piperidine ring, piperazine ring, morpholine ring, thiomorpholin ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, triazine ring and the like. The heterocycle may be an aromatic ring or a non-aromatic ring.

The number of carbon atoms in the ring structure represented by A is preferably 5 or more and 12 or less, more preferably 5 or 6, and even more preferably 6. The ring structure represented by A is preferably a carbon ring, more preferably a benzene ring.

Examples of the monovalent organic group having 1 to 40 carbon atoms represented by R ⁶ include those exemplified as the monovalent organic group having 1 to 30 carbon atoms represented by ^{R 1 and the like.}

As R ⁶ , a hydrocarbon group is preferable, an alkyl group is more preferable, and a tertiary alkyl group such as a t-butyl group is further preferable. As ^{the upper limit of the number of carbon atoms of R 6} , 10 is preferable, and 6 is more preferable. As ^{the lower limit of the number of carbon atoms of R 6} , 2 is preferable, and 4 is more preferable.

As R ⁷ , * -COO-, * -COS-, or * -CONH- is preferable, and * -COO- is more preferable. When R ⁷ is such a linking group, dissociation due to heating during curing occurs more effectively, and defects in the obtained optical filter are more sufficiently reduced.

The monovalent organic group having 1 to 20 carbon atoms represented by ^{R 8} has 1 to 20 carbon atoms among those exemplified as the monovalent organic group having 1 to 30 carbon atoms represented by ^{R 1 and the like.} Things etc. can be mentioned.

The R ^8, preferably a hydrocarbon group, more preferably an alkyl group, tertiary alkyl group a t- butyl group and the like are more preferred. As ^{the upper limit of the number of carbon atoms of R 8} , 16 is preferable, 8 is more preferable, and 2 is further preferable. When R ⁸ is such a group, the defects of the obtained optical filter tend to be reduced more sufficiently.

c is preferably 2 or more, and more preferably 2.

d is preferably 1.

The lower limit of e is preferably 2, more preferably 3, and even more preferably 4. When e is not more than the above lower limit, the defects of the obtained optical filter tend to be sufficiently reduced. The upper limit of e may be 8, 6 or 4.

When c is 2 and d is 1, the ^{groups represented by R 6} are attached to the atoms on both sides of the atom of the ring structure A to which the groups represented by −OR ^{7 −R 8 are bonded.} It is preferable that they are bonded. Specific examples of such a compound (B) include a compound represented by the following formula (6).

In the formula ^(6), R 6 ^{to R} 8, X and e are the same meaning as ^R 6 ^{to R} 8, X and e in formula (2).

Examples of the monovalent organic group e is represented by X in the case of 1, such as those exemplified as the monovalent organic group having 1 to 30 carbon atoms represented by R ^1, and the like.

When e is 2 or more, the e-valent linking group represented by X includes an e-valent organic group, -O-, and -NR'-(R'is a hydrogen atom or 1 to 10 carbon atoms. It is a monovalent hydrocarbon group.) And the like. Examples of the e-valent organic group include a group obtained by further removing (e-1) hydrogen atoms from the above-mentioned monovalent organic group.

As X, an e-valent organic group is preferable. As the organic group, a hydrocarbon group and a group containing -O-, -CO- or -COO- between the carbon and carbon of the hydrocarbon group are preferable, and the hydrocarbon group and the carbon-carbon of the hydrocarbon group are used. Groups containing −COO− are more preferred. The organic group represented by X may contain a plurality of species of -O-, -CO- and -COO-, or a plurality of -O-, a plurality of -CO- or a plurality of -CO-. -COO- may be included.

As the upper limit of the number of carbon atoms of X, 40 is preferable, 30 is more preferable, and 24 is further preferable. As the lower limit of the number of carbon atoms, 1 is preferable, 4 is more preferable, 8 is more preferable, and 12 is even more preferable.

When A is a benzene ring, X is preferably bonded to the para position with respect to the group represented by -OR ^{7- R 8.}

Specific examples of the compound (B) include the compounds described in paragraphs [0061] to [0082] of International Publication No. 2014/021023. The compound (B) can be used alone or in admixture of two or more. The compound (B) can be obtained by reacting, for example, a phenolic compound with an acid anhydride, a acid anhydride, a Boclation reagent, an alkyl halide compound, a silyl chloride compound, an allyl ether compound, or the like.

The lower limit of the content of the compound (B) in the total solid content of the curable composition is preferably 0.1% by mass, more preferably 0.2% by mass, still more preferably 0.3% by mass. When the content of the compound (B) is at least the above lower limit, sufficient radical scavenging ability is exhibited in the obtained optical filter, and defects can be further reduced. On the other hand, as the upper limit of this content, 10% by mass is preferable, 5% by mass is more preferable, and 2% by mass is further preferable.

[(B') compound]
The curable composition preferably further comprises a compound (B') which is an antioxidant that is not protected by a protecting group. By further containing the (B') compound in the curable composition, radicals that can be generated in the curable composition before curing can be sufficiently captured, so that storage stability is enhanced, and for example, the curing after long-term storage is performed. Defects in the optical filter obtained with the sex composition are also reduced.

Examples of the (B') compound include 2,2-thiobis (4-methyl-6-t-butylphenol), 2,6-di-t-butylphenol, and pentaerythritol tetrakis [3-() as conventionally known antioxidants. 3,5-di-t-butyl-4-hydroxyphenyl) propionate], 3,9-bis [2- [3- (3-t-butyl-4-hydroxy-5-methylphenyl) -propionyloxy]- 1,1-Dimethylethyl] -2,4,8,10-Tetraoxa-spiro [5.5] undecane, thiodiethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] And so on.

As the compound (B'), a compound represented by the following formula (4) is preferable.

In formula (4), A'is a ring structure composed of one or more five-membered or six-membered rings. R 6 ^'is a halogen atom, hydroxy group, a monovalent organic group of the nitro group or having 1 to 40 carbon atoms. c'is an integer from 0 to 4. d'is an integer from 1 to 3. e'is an integer from 1 to 10. When e'is 1, X'is a monovalent organic group, and when e'is 2 or more, X'is an e'valent linking group. ^'If there are a plurality, the plurality of R ^6' R 6 may be the same or different.

The ring structure composed of one or more five-membered rings or six-membered rings represented by A'is exemplified as a ring structure composed of one or more five-membered rings or six-membered rings represented by A. And so on.

The number of carbon atoms in the ring structure represented by A'is preferably 5 or more and 12 or less, more preferably 5 or 6, and even more preferably 6. As the ring structure represented by A', a carbon ring is preferable, and a benzene ring is more preferable.

Examples of the monovalent organic group having 1 to 40 carbon atoms represented by R ⁶ ′ include those exemplified as the monovalent organic group having 1 to 30 carbon atoms represented by ^{R 1 and the like.}

As R ⁶ ', a hydrocarbon group is preferable, an alkyl group is more preferable, and a tertiary alkyl group such as a t-butyl group is further preferable. As ^{the upper limit of the number of carbon atoms of R 6} ', 10 is preferable, and 6 is more preferable. As ^{the lower limit of the number of carbon atoms of R 6} ', 2 is preferable, and 4 is more preferable.

The c'is preferably 2 or more, and more preferably 2.

The d'is preferably 1.

The lower limit of e'is preferably 2, more preferably 3, and even more preferably 4. When e'is equal to or greater than the above lower limit, the defects of the obtained optical filter tend to be sufficiently reduced. The upper limit of e'may be 8, may be 6, or may be 4.

c 'is 2, d' when it is 1, the groups hydroxy group (-OH) is represented by 'each R ⁶ to atoms on both sides of the atoms bonded to that ring structure ^(A)' is bound It is preferable to do so.

Examples of the monovalent organic group represented by X'and the e'valent linking group include those exemplified as the monovalent organic group represented by X and the e-valent linking group.

As X', an e'valent organic group is preferable. As the organic group, a hydrocarbon group and a group containing -O-, -CO- or -COO- between the carbon and carbon of the hydrocarbon group are preferable, and the hydrocarbon group and the carbon-carbon of the hydrocarbon group are used. Groups containing −COO− are more preferred. The organic group represented by X'may contain a plurality of types of -O-, -CO- and -COO-, and a plurality of -O-, a plurality of -CO- or a plurality of -O-. -COO- may be included.

As the upper limit of the number of carbon atoms of X', 40 is preferable, 30 is more preferable, and 24 is further preferable. As the lower limit of the number of carbon atoms, 1 is preferable, 4 is more preferable, 8 is more preferable, and 12 is even more preferable.

When A'is a benzene ring, it is preferable that X'is bonded to the hydroxy group (-OH) at the para position.

The (B') compound can be used alone or in admixture of two or more.

When the curable composition contains the (B') compound, the lower limit of the content of the (B') compound in the total solid content of the curable composition is preferably 0.1% by mass, and 0. 2% by mass is more preferable, and 0.3% by mass is further preferable. When the content of the compound (B') is at least the above lower limit, the storage stability is sufficiently improved and defects can be further reduced. On the other hand, as the upper limit of this content, 5% by mass is preferable, and 2% by mass is more preferable.

The lower limit of the total content of the compound (B) and the compound (B') in the total solid content of the curable composition is preferably 0.1% by mass, more preferably 0.3% by mass, and 0.5. Mass% is more preferred. When the total content is at least the above lower limit, defects in the obtained optical filter can be further reduced. On the other hand, as the upper limit of this content, 10% by mass is preferable, 5% by mass is more preferable, and 2% by mass is further preferable. When the total content is not more than the above upper limit, the visible light transmittance and the like tend to be improved.

When the compound (B) and the compound (B') are used in combination in the curable composition, the content ratio (mass ratio) thereof is preferably 1: 9 to 9: 1, preferably 3: 7 to 7 :. 3 is more preferable, and 4: 6 to 6: 4 is even more preferable. By using the compound (B) and the compound (B') in combination at such a ratio, it is possible to effectively capture unfavorable radicals that may occur before and after curing, and the resulting optical filter is defective. It will be further reduced.

[(C) Binder]
(C) The binder is usually a component that serves as a base material in the obtained cured product such as an optical filter and a shielding film. (C) One kind or two or more kinds of binders can be used.

(C) The binder contains a compound having a polymerizable group. When the curable composition contains a compound having a polymerizable group, good curability and good heat resistance of the obtained optical filter can be exhibited. The compound having a polymerizable group may have one or more polymerizable groups, but is preferably a compound having two or more polymerizable groups. Examples of the polymerizable group include a (meth) acryloyl group, a vinyl group, an oxylanyl group, an oxetanyl group, an N-alkoxymethylamino group, an alkoxysilyl group and the like. The compound having a polymerizable group may be a monomer (non-polymer) or a polymer.

[(C-1) Polymerizable compound]
The binder (C) preferably contains a monomeric (C-1) polymerizable compound as a compound having a polymerizable group. As the (C-1) polymerizable compound, a compound having two or more (meth) acryloyl groups and a compound having two or more N-alkoxymethylamino groups are preferable, and two or more (meth) acryloyl groups. The compound having is more preferable. (C-1) The polymerizable compound can be used alone or in admixture of two or more.

Examples of the compound having two or more (meth) acryloyl groups include a polyfunctional (meth) acrylate which is a reaction product of an aliphatic polyhydroxy compound and a (meth) acrylic acid, and a caprolactone-modified polyfunctional (meth) acrylate. , Alkylene oxide-modified polyfunctional (meth) acrylate, polyfunctional urethane (meth) acrylate which is a reaction product of (meth) acrylate having a hydroxyl group and polyfunctional isocyanate, (meth) acrylate having a hydroxyl group and acid anhydride. Examples thereof include a polyfunctional (meth) acrylate having a carboxyl group, which is a reaction product with and the like.

Here, examples of the above-mentioned aliphatic polyhydroxy compound include divalent aliphatic polyhydroxy compounds such as ethylene glycol, propylene glycol, polyethylene glycol, and polypropylene glycol, and glycerin, trimethylolpropane, pentaerythritol, dipentaerythritol, and the like. Aliphatic polyhydroxy compounds having a trivalent or higher valence can be mentioned. Examples of the (meth) acrylate having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, and glycerol dimethacrylate. And so on. Examples of the polyfunctional isocyanate include tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, isophorone diisocyanate and the like. Examples of the acid anhydride include dibasic acid anhydrides such as succinic anhydride, maleic anhydride, glutacon anhydride, itaconic anhydride, phthalic anhydride, and hexahydrophthalic anhydride, pyromellitic anhydride, and biphenyltetracarboxylic acid. Examples thereof include tetrabasic acid dianhydrides such as acid dianhydrides and benzophenone tetracarboxylic acid dianhydrides.

Specific examples of the compound having two or more (meth) acryloyl groups include, for example, ω-carboxypolycaprolactone mono (meth) acrylate, ethylene glycol (meth) acrylate, 1,6-hexanediol di (meth) acrylate, and 1 , 9-Nonandiol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, bisphenoxyethanol full orange (meth) acrylate, dimethylol tricyclode Candi (meth) acrylate, 2-hydroxy-3- (meth) acryloyloxypropyl methacrylate, 2- (2'-vinyloxyethoxy) ethyl (meth) acrylate, trimethylpropantri (meth) acrylate, pentaerythritol tri ( Meta) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tri (2- (meth) acryloyloxyethyl) phosphate, ethylene oxide-modified dipenta Examples thereof include erythritol hexaacrylate, succinic acid-modified pentaerythritol triacrylate, and urethane (meth) acrylate compound.

Among the compounds having two or more (meth) acryloyl groups, a polyfunctional (meth) acrylate is preferable, and a polyfunctional (meth) acrylate having three or more and ten or less (meth) acryloyl groups is more preferable. Specifically, trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol hexaacrylate are preferable.

Examples of the compound having two or more N-alkoxymethylamino groups include a compound having a melamine structure, a benzoguanamine structure, and a urea structure. Specific examples of compounds having two or more N-alkoxymethylamino groups include N, N, N', N', N'', N''-hexa (alkoxymethyl) melamine, N, N, N'. , N'-tetra (alkoxymethyl) benzoguanamine, N, N, N', N'-tetra (alkoxymethyl) glycoluryl and the like.

The lower limit of the content of the (C-1) polymerizable compound in the total solid content of the curable composition is preferably 5% by mass, more preferably 10% by mass, and even more preferably 20% by mass. On the other hand, as the upper limit of this content, 60% by mass is preferable, 50% by mass is more preferable, and 40% is further more preferable.

[(C-2) polymer]
The binder (C) preferably contains the polymer (C-2). (C-2) A part or all of the polymer may be a polymer or the like used as a dispersant. The polymer (C-2) preferably has a polymerizable group, and more preferably has a structural unit containing a polymerizable group, in order to improve strength, sensitivity, heat resistance, and the like. As the polymerizable group, a (meth) acryloyl group, an oxylanyl group, an oxetanyl group, an alkoxysilyl group or a combination thereof is preferable, and a (meth) acryloyl group is more preferable.

Examples of the monomer giving a structural unit containing a polymerizable group include glycidyl (meth) acrylate, 3- (meth) acryloyloxymethyl-3-ethyloxetane, 3,4-epoxycyclohexylmethyl (meth) acrylate, 2, 3-epoxycyclohexylmethyl (meth) acrylate, 3,4-epoxytricyclo [5.2.1.0 ^2.6] decyl (meth) acrylate, 3-methacryloxy may be mentioned propyl triethoxysilane.

Further, for example, by reacting a resin having a structural unit having a carboxy group with a compound having a group (oxylanyl group, oxetanyl group, etc.) that reacts with the carboxy group and a polymerizable group such as a (meth) acryloyl group. Also, structural units containing polymerizable groups can be introduced.

The lower limit of the content of the structural unit having a polymerizable group in the (C-2) polymer is preferably 5% by mass, more preferably 10% by mass, based on 100% by mass of the (C-2) polymer. 15% by mass is even more preferable, and 30% by mass, 50% by mass or 75% by mass may be even more preferable. On the other hand, as the upper limit of this content, 95% by mass is preferable, 90% by mass is more preferable, and 85% by mass is further preferable.

The polymer (C-2) preferably has a ring structure in the main chain in order to improve heat resistance. The number of ring members of this ring structure may be, for example, 3 to 12, but 5 to 8 is preferable.

Examples of the monomer that gives a structural unit containing a ring structure to the main chain include N-substituted maleimide-based monomers and cycloolefins.

The N-substituted maleimide-based monomer is a compound in which a hydrogen atom bonded to a nitrogen atom in maleimide is substituted with a substituent. As the substituent, a hydrocarbon group is preferable, a hydrocarbon group having a ring structure is more preferable, and an aromatic hydrocarbon group is more preferable. Examples of the N-substituted maleimide-based monomer include N-phenylmaleimide, N-naphthylmaleimide, N-cyclohexylmaleimide, N-cyclooctylmaleimide, and N-methylmaleimide.

Examples of the cycloolefin include norbornene-based olefins, tetracyclododecene-based olefins, dicyclopentadiene-based olefins, and the like.

In addition, a phenol resin or the like can also be used as the (C-2) polymer having a ring structure in the main chain.

The content of the structural unit containing a ring structure in the main chain of the (C-2) polymer is preferably 1% by mass to 50% by mass, more preferably 1% by mass, based on 100% by mass of the (C-2) polymer. It is 5% by mass to 30% by mass.

The polymer (C-2) preferably has an acidic group. Examples of the acidic group include a carboxy group, an acid anhydride group, a phenolic hydroxyl group, a sulfo group and the like. Among the above, the carboxy group is preferable as the acidic group. The polymer (C-2) is preferably a resin containing a structural unit having one or more acidic groups. (C-2) When the polymer has an acidic group, it can exhibit good alkali solubility. (C-2) When the polymer has alkali solubility, alkaline development can be performed, and an optical filter having a desired pattern shape can be formed.

Examples of the monomer giving a structural unit containing an acidic group include unsaturated monocarboxylic acids such as (meth) acrylic acid, crotonic acid, α-chloroacrylic acid, and itaconic acid; malein. Unsaturated dicarboxylic acids such as acids, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, mesaconic acid, or anhydrides thereof; monosuccinate [2- (meth) acryloyloxyethyl] , Mono [(meth) acryloyloxyalkyl] ester of a divalent or higher valent carboxylic acid such as mono [2- (meth) acryloyloxyethyl]; ω-carboxypolycaprolactone mono (meth) acrylate and the like. Examples thereof include mono (meth) acrylate of a polymer having a carboxy group and a hydroxyl group at both ends.

Examples of the monomer having a phenolic hydroxyl group include 4-vinylphenol, 4-isopropenylphenol, 4-hydroxyphenyl (meth) acrylate and the like.

The content of the structural unit containing an acidic group in the (C-2) polymer is preferably 1% by mass to 50% by mass, more preferably 3% by mass, based on 100% by mass of the (C-2) polymer. ~ 30% by mass.

(C-2) The polymer can further contain other structural units. Examples of the monomer giving other structural units include aromatic vinyl compounds such as styrene, α-methylstyrene, p-hydroxystyrene, p-hydroxy-α-methylstyrene, p-vinylbenzylglycidyl ether, and acenaphthylene;
Methyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, allyl (meth) acrylate, benzyl (meth) acrylate, polyethylene glycol (degree of polymerization 2- 10) Methyl ether (meth) acrylate, polypropylene glycol (polymerization degree 2 to 10) Methyl ether (meth) acrylate, polyethylene glycol (polymerization degree 2 to 10) mono (meth) acrylate, polypropylene glycol (polymerization degree 2 to 10) mono (Meta) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8-yl (meth) acrylate, dicyclopentenyl (meth) acrylate, glycerol mono (Meta) acrylate, 4-hydroxyphenyl (meth) acrylate, ethylene oxide-modified (meth) acrylate of paracumylphenol, glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 3-[(meth) (Meta) acrylic acid esters such as acryloyloxymethyl] oxetane and 3-[(meth) acryloyloxymethyl] -3-ethyloxetane;
Vinyl ethers such as cyclohexyl vinyl ether, isobornyl vinyl ether, tricyclo [5.2.1.0 ^2,6 ] decane-8-ylvinyl ether, pentacyclopentadecanyl vinyl ether, 3- (vinyloxymethyl) -3-ethyloxetane ;
Examples thereof include macromonomers having a mono (meth) acryloyl group at the end of polymer molecular chains such as polystyrene, polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate, and polysiloxane.

The polymer (C-2) can be obtained by polymerizing by a known method using each of the above-mentioned monomers. The polymer (C-2) may be used alone or in combination of two or more.

The polystyrene-equivalent weight average molecular weight (Mw) of the polymer (C-2) is preferably 2,000 to 500,000, more preferably 3,000, as measured by the gel permeation chromatography (GPC) method. It is 100,000, more preferably 4,000 to 30,000. When Mw is in the above range, a polymer (C-2) having excellent solubility in a solvent or a developing solution and having sufficient mechanical properties can be obtained.

The lower limit of the content of the (C-2) polymer in the total solid content of the curable composition is preferably 10% by mass, more preferably 20% by mass, and even more preferably 30% by mass. On the other hand, as the upper limit of this content, 60% by mass is preferable, 50% by mass is more preferable, and 45% by mass is further preferable. By setting the content of the polymer (C-2) in the above range, the characteristics related to the ultraviolet shielding property, visible light transmittance, heat resistance, etc. of the obtained optical filter are more sufficiently exhibited.

The lower limit of the content of the binder (C) in the total solid content of the curable composition is preferably 30% by mass, more preferably 40% by mass, and even more preferably 50% by mass. On the other hand, as the upper limit of this content, 90% by mass is preferable, and 80% by mass is more preferable. By setting the content of the binder (C) in the above range, the characteristics related to the ultraviolet shielding property, visible light transmittance, heat resistance, etc. of the obtained optical filter are more sufficiently exhibited.

The average polymerizable double bond equivalent of the binder (C) in the curable composition is preferably 600 or less, more preferably 400 or less, and even more preferably 200 or less. Here, the average polymerizable double bond equivalent means which of the polymerizable double bond groups such as (meth) acryloyl group and alkenyl group capable of reacting with radicals generated from the component (A) in the binder (C). It is an index showing whether or not there is only a radical. By setting the average polymerizable double bond equivalent in the above range, the solvent durability of the obtained optical filter is more sufficiently exhibited. The lower limit of the average polymerizable double bond equivalent is, for example, 30, 50, or 80.

The average polymerizable double bond equivalent is the mass (g) of the (C) binder per 1 mol of the polymerizable double bond contained in the (C) binder, and is calculated by the following formula.
Average polymerizable double bond equivalent (g / mol)
= (C) Total mass of binder (g) / (C) Amount of substance (mol) of all polymerizable double bonds contained in the binder
In other words, the average polymerizable double bond equivalent of the (C) binder is the molecular weight of the (C) binder per polymerizable double bond contained in the (C) binder.

[(D) Solvent]
The solvent (D) is a component that dissolves or disperses each of the other components. As the solvent (D), as long as it disperses or dissolves other components, does not react with these components, and has appropriate volatility, it can be appropriately selected and used. As the solvent (D), one kind or two or more kinds can be used.

Examples of the solvent (D) include (poly) alkylene glycol monoalkyl ethers, lactic acid alkyl esters, (cyclo) alkyl alcohols, keto alcohols, (poly) alkylene glycol monoalkyl ether acetates, ethers, and ketones. , Diacetates, alkoxycarboxylic acid esters, esters, aromatic hydrocarbons, amides, lactams and the like.

The solvent (D) preferably contains a compound having a cyclic structure. By using a compound having a cyclic structure as a solvent, the solubility and dispersibility become better. The cyclic structure may be a carbon ring or a heterocycle. Further, the cyclic structure may be polycyclic or monocyclic. Further, the cyclic structure may be an aromatic ring or an adipose ring.

As the solvent which is a compound having a cyclic structure, cyclic ketones, cyclic ethers, lactones (γ-butyrolactone, ε-caprolactone, etc.), lactams, aromatic hydrocarbons (toluene, etc.) and combinations thereof are preferable. Among these, cyclic ketones, lactones and aromatic hydrocarbons are preferable, cyclic ketones and lactones are more preferable, and cyclic ketones are even more preferable.

Examples of the cyclic ketone include cyclobutanone, cyclopentanone, cyclohexanone, cycloheptanone, cyclooctanone and the like. Among these, cyclopentanone, cyclohexanone and cycloheptanone are preferable, and cyclopentanone and cyclohexanone are more preferable.

Examples of the cyclic ether include tetrahydrofuran, tetrahydropyran and the like.

Examples of the lactone include γ-butyrolactone and ε-caprolactone, and γ-butyrolactone is preferable.

Examples of the lactam include pentano-4-lactam, 5-methyl-2-pyrrolidinone, hexano-6-lactam, 6-hexane lactam and the like.

The lower limit of the content of the compound having a cyclic structure in the solvent (D) is preferably 30% by mass, more preferably 50% by mass, further preferably 70% by mass, and even more preferably 75% by mass. The solvent (D) may be composed only of a compound having a substantially cyclic structure. (D) By setting the content of the compound having a cyclic structure in the solvent to the above lower limit or more, the dispersibility and solubility of other components are enhanced, and the effect of the present invention is more sufficiently exhibited.

As the lower limit of the solid content concentration (total concentration of each component excluding the solvent (D)) in the curable composition, 5% by mass is preferable, 10% by mass is more preferable, and 20% by mass is further preferable. On the other hand, as the upper limit of the solid content concentration, 60% by mass is preferable, 50% by mass is more preferable, and 40% by mass is further preferable. By setting the solid content concentration in the above range, the dispersibility, storage stability, coatability and the like become better.

[(E) Dye]
The curable composition preferably contains a dye having a maximum absorption wavelength in a wavelength region of 650 nm or more and 2,000 nm or less. When the curable composition further contains such a dye (E), it is possible to exert an infrared shielding property close to the visible light region in the obtained optical filter. That is, when the curable composition further contains the dye (E), the obtained optical filter can effectively block ultraviolet rays and infrared rays close to the visible light region, and is suitable as an optical filter for a solid-state image sensor or the like. It becomes a thing. The dye (E) may be a dye or a pigment. Further, the dye (E) may be an organic substance or an inorganic substance. As the dye (E), one kind or two or more kinds can be used.

As the dye (E), the first dye having a maximum absorption wavelength in the wavelength region of 650 nm or more and 900 nm or less (hereinafter, also referred to as “(E-1) dye”) and the maximum in the wavelength region of more than 900 nm and 2,000 nm or less. It is preferable to include at least one of the second dye having an absorption wavelength (hereinafter, also referred to as “(E-2) dye”), and it is more preferable to include both. By using such a dye, the shielding property of infrared rays close to the visible light region is further enhanced, and the obtained optical filter becomes more useful in solid-state image sensor applications and the like.

[(E-1) Dye]
The dye (E-1) preferably contains a phthalocyanine pigment, a cyanine pigment, a pyrrolopyrrole pigment, a naphthalocyanine pigment, a diimonium pigment, an azo pigment, a squarylium pigment, or a combination thereof, and is preferably a phthalocyanine pigment. Is preferably included. It is also preferable to use two or more kinds of the (E-1) dye in combination. Conventionally known dyes can be used as these dyes.

The lower limit of the maximum absorption wavelength of the dye (E-1) is preferably 680 nm, more preferably 700 nm, and even more preferably 720 nm. On the other hand, the upper limit of the maximum absorption wavelength is preferably 1,000 nm, more preferably 900 nm, further preferably 800 nm, and even more preferably 750 nm.

The dye (E-1) preferably contains a compound represented by the following formula (3), which is a phthalocyanine dye. This phthalocyanine compound has high transparency in the visible light region (for example, a wavelength region of 430 nm or more and 580 nm or less), while has high shielding property in the near infrared region (for example, a wavelength region of 700 nm or more and 800 nm or less). In addition, this phthalocyanine compound has excellent compatibility with other components. Therefore, when the curable composition contains such a phthalocyanine compound, it is possible to form an optical filter having fewer defects such as foreign substances and having better characteristics regarding visible light transmission and infrared shielding property. ..

In the formula (3), each of the plurality of ^Ras is an alkyl group having a substituent or an unsubstituted group, or an aryl group having a substituent or an unsubstituted group, respectively. Each of the plurality of R ^bs is independently a hydrogen atom, a halogen atom or an alkyl group. The plurality of R ^bs may be bonded to each other to form an aromatic ring together with the carbon chain to which they are bonded. M is a derivative of two hydrogen atoms, a divalent metal atom, or a trivalent or tetravalent metal atom. The plurality of ns are independently integers of 3 to 6.

^{Examples of the alkyl group represented by Ra} include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a 2-methylpropyl group, a 1-methylpropyl group, a t-butyl group and the like. Examples thereof include linear or branched alkyl groups having 1 to 30 carbon atoms. As the upper limit of the number of carbon atoms of this alkyl group, 12 is preferable, 8 is more preferable, and 4 is further preferable.

^{Examples of the aryl group represented by Ra} include a phenyl group, a tolyl group, a xsilyl group, a naphthyl group, an anthrasenyl group and the like. As the aryl group, a group composed of only an aromatic ring is preferable, and a phenyl group and a naphthyl group are more preferable.

The R ^a, in terms of heat resistance and the like of the optical filter obtained is preferably has or unsubstituted aryl group substituents.

The alkyl group and aryl group represented by the plurality of ^Ra , respectively, may or may not have a substituent, but preferably have a substituent. That is, it is preferable that each of the plurality of ^Ras is an alkyl group having a substituent or an aryl group having a substituent independently. As described above, when a plurality of ^Ras have substituents, the compatibility of the phthalocyanine compound is further enhanced, defects such as foreign substances in the obtained optical filter are further suppressed, and characteristics related to visible light transmission and infrared shielding property are also obtained. Become better. Further, when a plurality of ^Ra have substituents, the heat resistance of the obtained optical filter is also improved.

^{The substituent that can be possessed by the alkyl group and the aryl group represented by a} plurality of Ra, respectively, may be a hydrocarbon group such as an alkenyl group or an alkynyl group, but may be a group having a hetero atom. preferable. Heteroatom refers to an atom other than a hydrogen atom and a carbon atom. Alkyl and aryl groups represented by a plurality of R ^a is, by having a substituent having a hetero atom, increased more compatibility, etc., defects such as a foreign particle optical filter obtained is further suppressed, the visible light The properties related to transparency and infrared shielding are also improved. Further, a plurality of R ^a is, by having a substituent having a hetero atom, is improved heat resistance of the obtained optical filter. As the hetero atom, a halogen atom, an oxygen atom and a sulfur atom are preferable, and a halogen atom and an oxygen atom are more preferable.

Examples of the substituent having a hetero atom include a halogen atom, an alkoxy group, an alkylthio group, a cyano group, a nitro group, a carboxy group, a hydroxy group, a thiol group, an amino group and the like.

As the halogen atom, a fluorine atom is preferable. As the alkoxy group, a methoxy group and an ethoxy group are preferable, and a methoxy group is more preferable.

The alkylthio group, a methylthio group _(CH 3 -S-), ethylthio group _(-S- C ₂ H 5), can be exemplified propylthio _{(C 3} H 7 -S-) such as methylthio group and ethylthio group Is more preferable.

Among the substituents having a hetero atom, a halogen atom, an alkoxy group and an alkylthio group are preferable, and a halogen atom and an alkoxy group are more preferable. Further, it is also preferable that it is a halogen atom, a methoxy group, an ethoxy group, a methylthio group, an ethylthio group or a combination thereof. The substituent having a hetero atom may have 0 to 10 carbon atoms, preferably 1 to 4 carbon atoms.

A plurality of R ^a can which may be the same or different, but are preferably the same.

The plurality of R ^bs may be coupled to each other. Usually, among the plurality of R ^b, bonded to the same benzene ring two R ^b are bonded to each other and to form an aromatic ring together with the carbon chain to which they are attached. Examples of the aromatic ring formed include a benzene ring, a naphthalene ring, an anthracene ring and the like. The hydrogen atoms of these aromatic rings may be substituted with hydrocarbon groups or other substituents.

A hydrogen atom is preferable as ^{R b.} Further, the plurality of R ^bs may be the same or different, but are preferably the same.

Examples of the divalent metal atom represented by M include Pd, Cu, Zn, Pt, Ni, Co, Fe, Mn, Sn, In, Ru, Rh, and Pb. The divalent metal atom means a metal atom that can become a divalent cation.

Here, the derivative of a metal atom means an atomic group containing a metal atom. A trivalent metal atom is a metal atom that can become a trivalent cation. Examples of the trivalent metal atom include Al and In. A tetravalent metal atom is a metal atom that can become a tetravalent cation. Examples of the tetravalent metal atom include Si, Ge, Sn and the like. The metal atom also includes a metalloid atom. Derivatives of the trivalent or tetravalent metal atom represented by M are AlCl, AlBr, AlI, AlOH, InCl, InBr, InI, InOH, SiCl ₂ , SiBr ₂ , SiI ₂ , Si (OH) ₂ , GeCl. ₂ , GeBr ₂ , GeI ₂ , SnCl ₂ , SnBr ₂ , SnI ₂ , Sn (OH) ₂ , VO, TiO and the like can be mentioned.

As M, H ₂ (two hydrogen atoms), Pd, Cu, Zn, Pt, Ni, Co, Fe, Mn, Sn, In, SnCl ₂ , AlCl, VO and TiO are preferable, and VO is more preferable.

As the lower limit of n, 4 is preferable. As the upper limit of n, 5 is preferable, and 4 is more preferable. The plurality of ns may be the same or different, but are preferably the same.

The lower limit of the maximum absorption wavelength of the phthalocyanine compound represented by the formula (3) is preferably 680 nm, more preferably 700 nm, and even more preferably 720 nm. On the other hand, the upper limit of the maximum absorption wavelength is preferably 1,000 nm, more preferably 900 nm, further preferably 800 nm, and even more preferably 750 nm. When the maximum absorption wavelength of the phthalocyanine compound represented by the formula (3) is in the above range, it is possible to form an optical filter having better characteristics regarding visible light transmission and infrared shielding property.

The method for synthesizing the phthalocyanine compound represented by the formula (3) is not particularly limited, and known methods can be combined for synthesis. For example, it can be synthesized by reacting a phthalonitrile compound represented by the following formula (i) or a 1,3-diiminoisoindoline compound represented by the formula (ii) with a metal or a metal derivative. it can.

In formulas (i) and (ii), ^Ra , R ^b and n are synonymous with those in formula (3).

Examples of the metal or metal derivative include Al, Si, Ti, V, Mn, Fe, Co, Ni, Cu, Zn, Ge, Ru, Rh, Pd, In, Sn, Pt, Pb and their halides and carboxylates. , Sulfates, nitrates, carbonyl compounds, oxides, complexes and the like. Among these, metal halides and carboxylates are particularly preferably used. Examples of these are copper chloride, copper bromide, copper iodide, nickel chloride, nickel bromide, nickel acetate, cobalt chloride, iron chloride, zinc chloride, zinc bromide, zinc iodide, zinc acetate, vanadium chloride, oxy. Examples thereof include vanadium chloride, palladium chloride, palladium acetate, aluminum chloride, manganese chloride, lead chloride, lead acetate, indium chloride, titanium chloride and tin chloride.

The reaction temperature is, for example, 60 to 300 ° C, preferably 100 to 220 ° C. The reaction time is, for example, 30 minutes to 72 hours, preferably 1 hour to 48 hours. In the reaction, it is preferable to use a solvent. As the solvent used in the reaction, an organic solvent having a boiling point of 60 ° C. or higher is preferable, and an organic solvent having a boiling point of 80 ° C. or higher is more preferable.

Examples of organic solvents used are methanol, ethanol, n-propyl alcohol, n-butyl alcohol, isobutyl alcohol, 1-pentanol, 1-hexanol, 1-heptanol, 1-octanol, 1-dodecanol, benzyl alcohol, ethylene. Alcohol solvents such as glycol, propylene glycol, ethoxyethanol, propoxyethanol, butoxyethanol, dimethylethanol, diethylethanol, dichlorobenzene, trichlorobenzene, chloronaphthalene, sulfolane, nitrobenzene, quinoline, DMI (1,3-dimethyl-2-imidazole) High boiling point solvents such as lysinone) and urea can be mentioned.

The reaction is carried out in the presence or absence of a catalyst, preferably in the presence of a catalyst. As the catalyst, an inorganic catalyst such as ammonium molybdate, DBU (1,8-diazabicyclo [5.4.0] undec-7-ene), DBN (1,5-diazabicyclo [4.3.0] nona- A basic organic catalyst such as 5-en) can be used.

In the case of a phthalocyanine compound in which M in the formula (3) is two hydrogen atoms, a phthalocyanine compound represented by the formula (i) or a 1,3-diiminoisone indolin compound represented by the formula (ii). It can be produced by reacting a compound with metallic sodium or metallic potassium under the above reaction conditions, and then desorbing the central metal sodium or potassium with hydrochloric acid, sulfuric acid or the like.

After completion of the reaction, the solvent is distilled off, or the reaction solution is discharged into a poor solvent for the phthalocyanine compound to precipitate the target product, and the precipitate is filtered to obtain the phthalocyanine compound represented by the formula (3). be able to. If necessary, the desired product with higher purity can be obtained by further purifying by a known purification method such as recrystallization or column chromatography.

The phthalonitrile-based compound represented by the formula (i) and the 1,3-diiminoisone indoline-based compound represented by the formula (ii) can be synthesized with reference to known methods. For example, it can be synthesized with reference to the method described in Special Table 2003-516421.

As the dye (E-1), it is preferable to use the phthalocyanine compound represented by the formula (3) in combination with another phthalocyanine compound. The lower limit of the maximum absorption wavelength of other phthalocyanine compounds is preferably 600 nm, more preferably 650 nm. On the other hand, as the upper limit of the maximum absorption wavelength of the other phthalocyanine compound, 900 nm is preferable, 850 nm is more preferable, 800 nm is further preferable, and 750 nm is further preferable. The lower limit of the difference between the maximum absorption wavelength of the phthalocyanine compound represented by the formula (3) and the maximum absorption wavelength of another phthalocyanine compound is preferably 10 nm, more preferably 30 nm. On the other hand, the upper limit of this difference is preferably 100 nm, more preferably 80 nm, and even more preferably 60 nm. Examples of other phthalocyanine compounds include various conventionally known phthalocyanine compounds.

The lower limit of the content of the phthalocyanine compound represented by the formula (3) in the dye (E-1) is preferably 50% by mass, more preferably 60% by mass, further preferably 70% by mass, and 80% by mass. It may be even more preferable. On the other hand, the upper limit of the content may be 100% by mass, 99% by mass, 90% by mass, or 80% by mass.

As the lower limit of the content of the other phthalocyanine compound in the (E-1) dye, 1% by mass is preferable, 10% by mass is more preferable, and 20% by mass is further preferable. On the other hand, the upper limit of the content is preferably 50% by mass, more preferably 40% by mass.

The lower limit of the content of the (E-1) dye in the total solid content of the curable composition is preferably 1% by mass, more preferably 2% by mass, further preferably 3% by mass, and more preferably 4% by mass. More preferred. On the other hand, as the upper limit of this content, 20% by mass is preferable, 15% by mass is more preferable, 10% by mass is further preferable, and 8% by mass is further preferable. By setting the content of the dye (E-1) in the above range, the characteristics of the obtained optical filter regarding visible light transmittance and infrared shielding property become better.

[(E-2) Dye]
As the dye (E-2), an inorganic pigment can be preferably used. The dye (E-2), which is an inorganic pigment, is usually in the form of particles and is dispersed in the curable composition.

The dye (E-2) is preferably an oxide of a metal or a metalloid (silicon or the like). Specifically, the dye (E-2) is preferably cesium tungsten oxide, quartz, magnetite, alumina, titania, zirconia, spinel, tin-doped indium oxide, antimony-doped tin oxide, or a combination thereof. These inorganic compounds may be used alone or in admixture of two or more.

Among these, the dye (E-2) is preferably tungsten cesium oxide. Tungsten cesium oxide is an infrared shielding agent that absorbs high infrared rays (especially infrared rays with a wavelength of more than 900 nm and 2,000 nm or less) (that is, has high shielding property against infrared rays) and has low absorption against visible light. is there. Therefore, by using tungsten cesium oxide, it is possible to improve the infrared shielding property while maintaining the good visible light transmittance of the obtained optical filter.

Tungsten cesium oxide can be represented by, for example, the following formula (a).
Cs _x W _oy ... (a)
In the formula (a), 0.001 ≦ x ≦ 1.1. 2.2 ≦ y ≦ 3.0.

When x in the above formula (a) is 0.001 or more, infrared rays can be sufficiently shielded. The lower limit of x is preferably 0.01, more preferably 0.1. On the other hand, when x is 1.1 or less, it is possible to more reliably avoid the formation of an impurity phase in tungsten cesium oxide. The upper limit of x is preferably 1 and more preferably 0.5.

When y in the above formula (a) is 2.2 or more, the chemical stability as a material can be further improved. The lower limit of y is preferably 2.5. On the other hand, when y is 3.0 or less, infrared rays can be sufficiently shielded.

Specific examples of the cesium tungsten oxide represented by the above formula (a) include Cs _0.33 WO ₃ .

(E-2) The dye is preferably fine particles. The upper limit of the average particle size (D50) of the dye (E-2) is preferably 500 nm, more preferably 200 nm, further preferably 50 nm, even more preferably 30 nm, and even more preferably 20 nm. When the average particle size is not more than the above upper limit, the generation of agglomerated foreign matter can be suppressed and the visible light transmission can be further enhanced. On the other hand, for reasons such as ease of handling during production, the average particle size of the dye (E-2) is usually 1 nm or more, and may be 10 nm or more. The average particle size (D50) is the secondary particle size in the curable composition.

The dye (E-2) can be synthesized by a known method, but is available as a commercially available product. For example, tungsten cesium oxide is also available as a dispersion of fine particles of tungsten cesium oxide such as "YMF-02" manufactured by Sumitomo Metal Mining Co., Ltd.

The lower limit of the content of the (E-2) dye in the total solid content of the curable composition is preferably 1% by mass, more preferably 5% by mass, still more preferably 10% by mass. On the other hand, as the upper limit of this content, 50% by mass is preferable, 40% by mass is more preferable, 30% by mass is further preferable, and 20% by mass is more preferable. By setting the content of the dye (E-2) in the above range, the characteristics of the obtained optical filter regarding visible light transmittance and infrared shielding property become better.

The lower limit of the mass ratio ([E-2] / [E-1]) of the content of the dye (E-2) to the content of the dye (E-1) is preferably 1 and preferably 2. On the other hand, as the upper limit of this mass ratio ([E-2] / [E-1]), 40 is preferable, 20 is more preferable, and 10 is further preferable. By setting the content ratio of the (E-1) dye to the (E-2) dye in the above range, the characteristics related to the visible light transmittance and the infrared shielding property of the obtained optical filter become better.

[Additive]
The curable composition may contain various additives in addition to the above-mentioned components (A) to (E), if necessary.

Examples of the additive include a surfactant, an adhesion accelerator, an ultraviolet absorber, an anti-aggregation agent, a residue improving agent, a developability improving agent, a reaction adjusting agent and the like.

Examples of the surfactant include a fluorine surfactant, a silicone surfactant and the like.

Adhesion promoters include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl). -3-Aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxy Examples thereof include silane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane.

Examples of the ultraviolet absorber include 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, alkoxybenzophenones and the like.

Examples of the anti-aggregation agent include sodium polyacrylate and the like.

Residue improvers include malonic acid, adipic acid, itaconic acid, citraconic acid, fumaric acid, mesaconic acid, 2-aminoethanol, 3-amino-1-propanol, 5-amino-1-pentanol, 3-amino- Examples thereof include 1,2-propanediol, 2-amino-1,3-propanediol, 4-amino-1,2-butanediol and the like.

Developable agents include succinate mono [2- (meth) acryloyloxyethyl], phthalate mono [2- (meth) acryloyloxyethyl], ω-carboxypolycaprolactone mono (meth) acrylate and the like. Can be mentioned.

Examples of the reaction modifier include polyfunctional thiols and the like.

The lower limit of the content of the component agents other than the above-mentioned components (A) to (E) in the total solid content of the curable composition is preferably 0.1% by mass, more preferably 1% by mass. On the other hand, as the upper limit of this content, 10% by mass is preferable, and 5% by mass is more preferable.

[Preparation method]
The method for preparing the curable composition is not particularly limited, and the curable composition can be prepared by mixing each component. For example, when the curable composition contains a dye (E-2), first, a dispersion containing the dye (E-2) is prepared, and other components are added to the dispersion and mixed. The method can be adopted. The dispersion liquid or the curable composition can be subjected to a filtration treatment, if necessary, to remove agglomerates.

[Optical filter]
The curable composition is suitable for an optical filter. That is, the curable composition can be suitably used as an optical filter or a material for forming a shielding film provided on the optical filter. According to the curable composition, a shielding film in an optical filter can be suitably formed. The optical filter obtained by using the curable composition has good ultraviolet shielding property, visible light transmission and heat resistance close to the visible light region, and has few defects such as foreign substances. Further, when the curable composition contains the dye (E), the obtained optical filter can exhibit good infrared shielding property.

The optical filter can be formed by, for example, the following method. First, the curable composition is applied onto the support, and then prebaked to evaporate the solvent to form a coating film. Next, after exposing this coating film, it is developed with a developing solution to dissolve and remove the unexposed portion of the coating film. Then, by post-baking, an optical filter having a shielding film patterned in a predetermined shape is obtained. It should be noted that the development process does not have to be performed, and in this case, an unpatterned shielding film can be formed.

The transparent substrate, microlens, color filter and the like correspond to the support to which the curable composition is applied. For the above coating, an appropriate coating method such as a spray method, a roll coating method, a rotary coating method (spin coating method), a slit die coating method (slit coating method), and a bar coating method can be adopted.

The conditions for heat drying in the pre-bake are, for example, 70 ° C. or higher and 110 ° C. or lower, and 1 minute or longer and 10 minutes or shorter.

Examples of the light source of radiation used for exposing the coating film include lamp light sources such as xenon lamps, halogen lamps, tungsten lamps, high-pressure mercury lamps, ultra-high pressure mercury lamps, metal halide lamps, medium-pressure mercury lamps, and low-pressure mercury lamps, argon ion lasers, and YAG lasers. Examples thereof include a laser light source such as an XeCl excimer laser and a nitrogen laser. An ultraviolet LED can also be used as the exposure light source. The wavelength is preferably radiation in the range of 190 nm or more and 450 nm or less. Exposure of radiation, typically on the order 10J / ^{m 2} or more 50,000J / ^{m 2} or less.

As the developing solution, an alkaline developing solution is generally used. Examples of the alkaline developer include sodium carbonate, sodium hydrogen carbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline, 1,8-diazabicyclo- [5.4.0] -7-undecene, 1, An aqueous solution of 5-diazabicyclo- [4.3.0] -5-nonene or the like is preferable. An appropriate amount of a water-soluble organic solvent such as methanol or ethanol, a surfactant, or the like can be added to the alkaline developer. After development, it is usually washed with water.

As the developing method, a shower developing method, a spray developing method, a dip (immersion) developing method, a paddle (liquid filling) developing method and the like can be applied. The developing conditions are about 5 seconds or more and 300 seconds or less at room temperature.

The heating temperature in the post-bake is, for example, 120 ° C. or higher and 280 ° C. or lower, preferably 180 ° C. or higher and 250 ° C. or lower. By performing such post-baking (heat treatment), curing proceeds and the protecting group (-R ^7- R ⁸ ) of the compound (B) is eliminated. Therefore, the compound (B) can exhibit a good radical scavenging ability in the obtained shielding film. The heating time in post-baking is, for example, about 1 minute or more and 60 minutes or less.

The lower limit of the average film thickness of the shielding film thus formed is usually 0.5 μm, preferably 1 μm. On the other hand, the upper limit of the average film thickness is usually 10 μm, preferably 5 μm. When the average film thickness of the shielding film is within the above range, the balance between the shielding property of ultraviolet rays and infrared rays and the transparency of visible light becomes good.

The optical filter may be composed of only the shielding film, or may be composed of the shielding film and other constituent members. For example, the optical filter may be a laminate having the shielding film and another layer.

The shielding film is preferably incorporated in an optical sensor such as a solid-state image sensor as one component. In this case, the shielding film alone functions as an optical filter. It is preferable that the shielding film is incorporated in the optical sensor because a large process margin can be obtained. When the shielding film is incorporated in the solid-state image sensor, the shielding film is arranged, for example, on the outer surface side of the microlens of the solid-state image sensor, between the microlens and the color filter, between the color filter and the photodiode, and the like. can do. The shielding film is preferably laminated between the microlens and the color filter or between the color filter and the photodiode.

The optical filter may be one in which the infrared shielding film is laminated on the surface of a transparent substrate. As the transparent substrate, glass, a transparent resin, or the like is adopted. Examples of the transparent resin include polycarbonate, polyester, aromatic polyamide, polyamideimide, and polyimide. Such an optical filter is also suitably used as an infrared cut filter or the like in a solid-state image sensor.

Optical sensors such as solid-state image sensors equipped with the above optical filters are used in digital still cameras, mobile phone cameras, digital video cameras, PC cameras, surveillance cameras, automobile cameras, mobile information terminals, personal computers, video games, medical devices, etc. It is useful.

[Optical sensor]
The optical filter is used for an optical sensor such as a solid-state image sensor. Since the optical filter has few defects such as foreign substances and has good characteristics regarding visible light transmission, ultraviolet ray shielding property, and infrared ray shielding property, an optical sensor such as a solid-state image sensor having the optical filter has sensitivity and color reproducibility. Etc. and excellent in practicality.

Hereinafter, a solid-state image sensor will be described as an example of an optical sensor. The solid-state image sensor generally has a structure in which a layer in which a plurality of photodiodes are arranged, a color filter, and a microlens are laminated in this order. Further, a flattening layer may be provided between these layers. In the solid-state image sensor, light is incident from the microlens side. The incident light passes through the microlens and the color filter and reaches the photodiode. As for the color filter, for example, each of the R (red), G (green), and B (blue) filters is configured to transmit only light in a specific wavelength range.

In the solid-state image sensor, the optical filter (shielding film) is provided on the outer surface side of the microlens, between the microlens and the color filter, and between the color filter and the layer on which the plurality of photodiodes are arranged. It can be provided in such as. The optical filter is preferably laminated between the microlens and the color filter or between the color filter and the photodiode. Further, another layer (flattening layer or the like) may be provided between the optical filter and the microlens, color filter, photodiode or the like.

Specific examples of the solid-state image sensor include a CCD and CMOS as a camera module. The solid-state imaging element is useful for digital still cameras, mobile phone cameras, digital video cameras, PC cameras, surveillance cameras, automobile cameras, mobile information terminals, personal computers, video games, medical devices, and the like.

Hereinafter, the present invention will be specifically described based on examples, but the present invention is not limited to these examples.

<Synthesis Example 1> Synthesis of dye (E-1-1) 4,7-bis (4- (2,6-dimethoxyphenoxy) butyl) -1,3-diiminobenzoisoindoline 32.9 g, vanadium trichloride 4.76 g and 13.74 g of DBU were stirred in 100 mL of 1-pentanol at an internal temperature of 125 ° C. for 24 hours. Then, 600 mL of methanol was added, and the precipitate was collected by filtration and dried. Purification by column chromatography (silica gel / toluene) gave 11.2 g of green powder. From the analysis results below, it was confirmed that the obtained compound was the target phthalocyanine compound represented by the following formula (E-1-1).
-MS: (EI) m / z 2245M +
-Elemental analysis value: Measured value (C: 68.44%, H: 6.44%, N: 4.99%);
Theoretical value (C: 68.47%, H: 6.46%, N: 4.99%)
The toluene solution of the compound thus obtained showed maximum absorption at 734.5 nm, and the gram extinction coefficient was 6.75 × 10 ⁴ mL / g · cm.

なお、上記式中、「＊」は、結合手を示す（以下の化学式においても同様）。

In the above formula, "*" indicates a bond (the same applies to the following chemical formula).

<Synthesis Example 2> Synthesis of dye (E-1-2) 4,7-bis (4- (2,6-dimethoxyphenoxy) butyl) -1,3-diiminobenzoisoindoline 32.9 g in Synthesis Example 1. 14.5 g of green powder was obtained in the same manner as in Synthesis Example 1 except that 18.6 g of 4,7-bis (4-methoxybutyl) -1,3-diiminobenzoisoindoline was used instead of the above. From the analysis results below, it was confirmed that the obtained compound was the target phthalocyanine compound represented by the following formula (E-1-2).
-MS: (EI) m / z 1267M +
-Elemental analysis value: Measured value (C: 68.20%, H: 7.66%, N: 8.82%);
Theoretical value (C: 68.17%, H: 7.63%, N: 8.83%)
Toluene solution of the compound obtained in this way showed a maximum absorption at 734.0nm, gram absorption coefficient was ^{1.21 × 10 5 mL / g ·} cm.

<Synthesis Example 3> Synthesis of Tungsten Tungsten Cesium (E-2-1) Powder Tungsten cesium oxide (Cs _0.33 WO ₃ ) powder is synthesized by using the method described in paragraph [0113] of Japanese Patent No. 4096205. did.

<Synthesis Example 4> Synthesis of Polymer (C-2-1) In a reaction vessel, 14 parts by mass of benzyl methacrylate, 10 parts by mass of styrene, 12 parts by mass of N-phenylmaleimide, 15 parts by mass of 2-hydroxyethyl methacrylate, 2- 29 parts by mass of ethylhexyl methacrylate and 20 parts by mass of methacrylic acid were dissolved in 200 parts by mass of propylene glycol monomethyl ether acetate, and 3 parts by mass of 2,2'-azoisobutyronitrile and 5 parts by mass of α-methylstyrene dimer were further added. .. After purging the inside of the reaction vessel with nitrogen, the mixture is heated at 80 ° C. for 5 hours with stirring and nitrogen bubbling, and a solution containing the polymer (C-2-1) (polymer solution [C-2-1]: solid content concentration 35). Mass%) was obtained. For the obtained polymer (C-2-1), 3 LF-604 manufactured by Showa Denko Co., Ltd. and KF-602 were combined with a gel permeation chromatography (GPC) apparatus (GPC-104 type, column: Showa Denko Co., Ltd.). When the polystyrene-equivalent molecular weight was measured using the above-mentioned product (developing solvent: tetrahydrofuran), the weight average molecular weight (Mw) was 9,700, the number average molecular weight (Mn) was 5,700, and Mw / Mn was 1. It was .70. In this synthesis example, the charging ratio (mass ratio) of each monomer and the content ratio (mass ratio) of the structural units derived from each monomer in the obtained polymer as a binder are substantially the same. Can be regarded as the same (the same applies to the following synthetic examples).

<Synthesis Example 5> Synthesis of Polymer (C-2-2) 200 parts by mass of propylene glycol monomethyl ether was placed in a flask equipped with a cooling tube and a stirrer, and the temperature was raised to 80 ° C. At the same temperature, a mixed solution of 100 parts by mass of propylene glycol monomethyl ether, 100 parts by mass of methacrylic acid, and 5 parts by mass of 2,2'-azoisobutyronitrile was added dropwise over 3 hours, and the temperature was maintained after the addition. Polymerized for 3 hours. Then, the temperature of the reaction solution was raised to 100 to 120 ° C., and the reaction was further carried out for 2 hours. After cooling, 25 parts by mass of propylene glycol monomethyl ether, 116 parts by mass of 3,4-epoxycyclohexylmethyl acrylate, and a catalytic amount of dimethylbenzylamine are added, the temperature is raised to 110 ° C., and the polymer is reacted for 9 hours. A solution containing (C-2-2) (polymer solution [C-2-2]: solid content concentration 40% by mass) was obtained. When the molecular weight of the obtained polymer (C-2-2) was measured in the same manner as in Synthesis Example 4, the weight average molecular weight (Mw) was 15,100, the number average molecular weight (Mn) was 7,000, and Mw. / Mn was 2.16.

<Synthesis Example 6> Synthesis of Polymer (C-2-3) 200 parts by mass of propylene glycol monomethyl ether was placed in a flask equipped with a cooling tube and a stirrer, and the temperature was raised to 80 ° C. At the same temperature, a mixed solution of 200 parts by mass of propylene glycol monomethyl ether, 67 parts by mass of methacrylic acid, 33 parts by mass of N-cyclohexylmaleimide, and 5 parts by mass of 2,2'-azoisobutyronitrile was added dropwise over 3 hours. After dropping, the temperature was maintained and polymerization was carried out for 3 hours. Then, the temperature of the reaction solution was raised to 100 to 120 ° C., and the reaction was further carried out for 3 hours. After cooling, 28 parts by mass of propylene glycol monomethyl ether, 119 parts by mass of 3,4-epoxycyclohexylmethyl acrylate, and a catalytic amount of dimethylbenzylamine are added, and the temperature is raised to 110 ° C. for 30 hours to react the polymer. A solution containing (C-2-3) (polymer solution [C-2-3]: solid content concentration 40% by mass) was obtained. When the molecular weight of the obtained polymer (C-2-3) was measured in the same manner as in Synthesis Example 4, the weight average molecular weight (Mw) was 17,000, the number average molecular weight (Mn) was 7,700, and Mw. / Mn was 2.21.

<Synthesis Example 7> Synthesis of Polymer (C-2-4) In a flask equipped with a cooling tube and a stirrer, 5 parts by mass of 2,2-azobisisobutyronitrile, 140 parts by mass of methyl 3-methoxypropionate, And 60 parts by mass of propylene glycol monomethyl ether, 32 parts by mass of glycidyl methacrylate, 40 parts by mass of 3-methacryloxypropyltriethoxysilane, 11 parts by mass of benzyl methacrylate, 3 parts by mass of n-butyl methacrylate and 14 parts by mass of methacrylate. Was charged and substituted with nitrogen, and then the temperature of the solution was raised to 80 ° C. with gentle stirring. By holding at this temperature for 5 hours and polymerizing, a solution containing the polymer (C-2-4) (polymer solution [C-2-4] solid content concentration 35% by mass) was obtained. When the molecular weight of the obtained polymer as a binder was measured in the same manner as in Synthesis Example 4, the weight average molecular weight (Mw) was 9,500, the number average molecular weight (Mn) was 5,800, and Mw / Mn was It was 1.64.

<Synthesis Example 8> Synthesis of Polymer (C-2-5) 600 parts by mass of propylene glycol monomethyl ether and 20 parts by mass of propylene glycol methyl ethyl acetate are charged in a flask equipped with a cooling tube and a stirrer, and the temperature is raised to 80 ° C. Rose. At the same temperature, 100 parts by mass of propylene glycol monomethyl ether, 60 parts by mass of propylene glycol methyl ethyl acetate, 41 parts by mass of methacrylic acid, 8 parts by mass of benzyl methacrylate, 8 parts by mass of styrene, 21 parts by mass of N-phenylmaleimide, 2-hydroxyethyl. A mixed solution of 17 parts by mass of methacrylate, 4 parts by mass of 2-ethylhexyl methacrylate, and 8 parts by mass of 2,2'-azoisobutyronitrile was added dropwise over 3 hours, and after the addition, the temperature was maintained and polymerization was carried out for 3 hours. Then, the temperature of the reaction solution was raised to 100 to 120 ° C., and the reaction was further carried out for 1 hour. After cooling, 20 parts by mass of propylene glycol monomethyl ether, 41 parts by mass of 3,4-epoxycyclohexylmethylacrylate, and a catalytic amount of dimethylbenzylamine are added, the temperature is raised to 110 ° C., and the polymer is reacted for 12 hours. A solution containing (C-2-5) (polymer solution [C-2-5]: solid content concentration of 35% by mass) was obtained. When the molecular weight of the obtained polymer (C-2-5) was measured in the same manner as in Synthesis Example 4, the weight average molecular weight (Mw) was 16,000, the number average molecular weight (Mn) was 5,800, and Mw. / Mn was 2.76.

<Synthetic Example 9> Synthesis of Dispersant (β) According to the method described in the literature (Macromolecules 1992, 25, p5907-5913), 45 parts by mass of dimethylaminoethyl methacrylate, 20 parts by mass of 2-ethylhexyl methacrylate, n-butyl. 5 parts by mass of methacrylate, 30 parts by mass of PME-200 (methoxypolyethylene glycol monomethacrylate and _{compound represented by CH 2} = C (CH ₃ ) COO (C ₂ H ₄ O) _{n −} CH ₃ (n≈4)) Was polymerized in a batch to obtain a reaction solution containing a random copolymer. Subsequently, the reaction solution was quenched with methanol, and the obtained reaction solution was washed with a 7% by mass aqueous sodium hydrogen carbonate solution and then with water. Then, the solvent was substituted with propylene glycol monomethyl ether acetate (PGMEA) to obtain a dispersant solution [β] containing the dispersant (β) in a yield of 80% by mass. The amine value of the obtained dispersant (β) was 160 mgKOH / g, Mw was 9500, Mw / Mn was 1.21, and the solid content of the dispersant solution [β] was 39.6% by mass.

The components used are shown below.
-Compound (A-1)
International Publication No. 2017/169819, paragraph [0037], contains Compound No. Compound represented by the following formula described as 1.

-Compound (A-2)
International Publication No. 2017/169819, paragraph [0037], contains Compound No. Compound represented by the following formula described as 2.

-Compound (A-3)
International Publication No. 2017/169819, paragraph [0037], contains Compound No. Compound represented by the following formula described as 8.

-Compound (A'-1)
In paragraph [0035] of Japanese Patent No. 4818458, compound No. The compound represented by the following formula described as 26.

-Compound (A'-2)
Compound "Irgacure OXE01" represented by the following formula (manufactured by BASF)

-Compound (A'-3)
In paragraph [0017] of JP-A-2014-227533, Compound No. Compound represented by the following formula described as 5.

-Compound (B-1)
Compounds represented by the following formulas described in the bottom left of paragraph [0076] of International Publication No. 2014/021023.

-Compound (B-2)
Compounds represented by the following formulas described in the lower right corner of paragraph [0076] of International Publication No. 2014/021023.

-Compound (B-3)
A compound represented by the following formula described at the top of paragraph [0077] of International Publication No. 2014/021023.

-Compound (B'-1)
Compound "Irganox 1010" represented by the following formula (manufactured by BASF)

-Polymerizable compound (C-1-1)
Mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (C-1-1) "KAYARAD DPHA" (manufactured by Nippon Kayaku Co., Ltd.)

-Polymer (C-2-1) to (C-2-5)
Polymers (C-2-1) to (C-2-5) obtained in Synthesis Examples 4 to 8 above.

-Solvent (D-1)
Cyclopentanone (CPN)

-Solvent (D-2)
Propylene Glycol Monomethyl Ether Acetate (PGMEA)

-Dyes (E-1-1) to (E-1-2)
Phthalocyanine dyes (E-1-1) to (E-1-2) obtained in Synthetic Examples 1 and 2 above.

・ Dye (E-1-3)
Phthalocyanine dye (E-1-3) according to Example 1 of JP-A-05-25177 (maximum absorption wavelength 692 nm).

・ Dye (E-2-1)
Tungsten cesium oxide (E2-1) obtained in Synthesis Example 3 above.

・ Dispersant solution [α]
"BYK-LPN6919" manufactured by Big Chemie (solid content concentration 60% by mass, amine value 120 mgKOH / g)

・ Dispersant solution [β]
Dispersant solution [β] obtained in Synthesis Example 9 above

・ Additive (F-1)
Fluorine-based surfactant "FTX-218D" (manufactured by Neos)

・ Additive (F-2)
Polyfunctional thiol "Karensu MT PEI" (manufactured by Showa Denko KK), which is a reaction modifier

As for both the components not described in the above synthesis example and the components not described in the trade name, a commercially available product or a compound synthesized by a known method was used.

[Preparation Example 1] Preparation of Pigment Dispersion Solution (Dispersion Solution [E2-1]) 25.00 parts by mass of tungsten cesium oxide (E2-1), 13.30 parts by mass of dispersant solution [α], and 61.70 parts by mass of CPN as a solvent (dispersion medium) was prepared. These were filled in a container together with 2,000 parts by mass of zirconia beads having a diameter of 0.1 mm and dispersed with a paint shaker to obtain a dispersion liquid [E-2-1] having an average particle diameter (D50) of 19 nm. .. The average particle size was measured by the DLS method using a light scattering measuring device (“ALV-5000” manufactured by ALV of Germany).

[Preparation Example 2] Preparation of Pigment Dispersion Solution (Dispersion Solution [E-2-2]) Preparation except that the dispersant solution was changed to 20.20 parts by mass of the dispersant solution [β] and the solvent was changed to 54.80 parts by mass of CPN. A dispersion solution [E-2-2] having an average particle size of 19 nm was obtained in the same manner as in Example 1.

[Preparation Example 3] Preparation of dye solution (solution [E-1-1], etc.) Weigh 7.00 parts by mass of dye (E-1-1) and 93.00 parts by mass of CPN as a solvent into a container and use a stirrer. Mixed. The obtained solution is pressure-filtered using a 0.2 μm PTFE filter under a constant pressure condition of 0.05 MPa to obtain a solution [E-1-1] containing a dye (E-1-1). Obtained.
Further, the solution [E-1-2] and the solution [E-1-2] and the solution [E-1-2] and the solution [E-1-2] and A solution [E-1-3] was obtained.

[Preparation Example 4] Preparation of Surfactant Solution (Solution [F-1]) Weigh 5.00 parts by mass of the additive (F-1), which is a surfactant, and 95.00 parts by mass of CPN as a solvent into a container. , A solution containing a surfactant [F-1] was obtained by mixing with a stirrer.

[Preparation Example 5] Preparation of reaction adjusting agent solution (solution [F-2]) Weigh 5.00 parts by mass of the additive (F-2) which is a reaction adjusting agent and 95.00 parts by mass of CPN as a solvent into a container. , A solution containing a reaction modifier [F-2] was obtained by mixing with a stirrer.

[Preparation Example 6] Preparation of antioxidant solution (solution [B-1], etc.) 5.00 parts by mass of compound (B-1) and 95.00 parts by mass of CPN as a solvent are weighed in a container and mixed with a stirrer. As a result, a solution [B-1] containing the compound (B-1) was obtained.
In addition, the solution [B-2], the solution [B-2], except that the compound (B-2), the compound (B-3) or the compound (B'-1) was used instead of the compound (B-1). A solution [B-3] and a solution [B'-1] were obtained.

[Example 1]
Compound (A-1) 1.6 parts by mass,
Solution [B-1] 4.3 parts by mass,
Polymerizable compound (C-1-1) 8 parts by mass,
Solution [C-2-1] 22.9 parts by mass,
Solvent (D-1) 17.5 parts by mass Solution [E-1-1] 21.1 parts by mass,
Dispersion solution [E-2-1] 16.6 parts by mass,
1.6 parts by mass of the solution [F-1] and 6.4 parts by mass of the solution [F-2] were weighed in a container and mixed with a stirrer. About 100 mL of this mixture was pressure-filtered using a 0.5 μm PTFE (polytetrafluoroethylene) filter under a constant pressure condition of 0.05 MPa to obtain a curable composition of Example 1.

[Examples 2 to 17, Comparative Examples 1 to 4]
The curable compositions of Examples 2 to 17 and Comparative Examples 1 to 4 were obtained in the same manner as in Example 1 except that the types and amounts of the blended components were as shown in Tables 1 and 2. It was. Except for the components (A), (A'), (C-1) and (D), they are blended in the state of a solution or a dispersion, and Tables 1 and 2 show the blending amount of the solution or the dispersion. In Tables 1 and 2, the components blended as a solution or dispersion are shown in parentheses []. In addition, in the curable compositions of Examples 1, 11, 14, 15, 20 and Comparative Example 1, the average polymerizable double bond equivalent of the binder is also shown.

[Evaluation]
The following evaluations were carried out using each of the obtained curable compositions. The evaluation results are shown in Tables 1 and 2.

Each curable composition was applied onto a glass substrate by a spin coating method so as to have a predetermined film thickness. Then, the coating film was heated at 100 ° C. for 120 seconds and exposed to ^{500 mJ / cm 2 with an i-line stepper.} Then, by heating at 220 ° C. for 300 seconds, a shielding film having an average film thickness of 3.0 μm was produced on the glass substrate. The film thickness was measured with a stylus type step meter (“Alpha Step IQ” manufactured by Yamato Scientific Co., Ltd.). Next, the transmittance of the shielding film produced on the glass substrate in each wavelength region was measured using a spectrophotometer (“V-7300” manufactured by JASCO Corporation) in comparison with the glass substrate. From the obtained spectrum, evaluation was performed according to the following evaluation criteria.

(Ultraviolet light shielding property)
The average transmittance of 350-395 nm was calculated. When the average transmittance is less than 30%, it is presumed to be highly practical because it has a high noise shielding function when used as an optical filter. The average transmittance was evaluated according to the following criteria.
A: Less than 25% B: 25% or more and less than 30% C: 30% or more

(Visible light transmission)
The average transmittance of 430-600 nm was calculated. If the average transmittance is less than 80%, the sensitivity when used as an optical filter decreases. In addition, the average transmittance was evaluated according to the following criteria.
A: 85% or more B: 80% or more and less than 85% C: less than 80%

(Infrared shielding 1)
A range in which the transmittance in the range of 700 to 900 nm was continuously 20% or less was determined. When the continuous range of 20% or less is 40 nm or more, it is presumed to be highly practical because it has a high noise shielding function when used as an optical filter. In addition, the infrared shielding range was evaluated according to the following criteria.
A: 55 nm or more B: 40 nm or more and less than 55 nm C: less than 40 nm

(Infrared shielding 2)
The average transmittance of 900-1200 nm was calculated. When the average transmittance is less than 45%, it is presumed to be highly practical because it has a high noise shielding function when used as an optical filter. In addition, the average transmittance was evaluated according to the following criteria.
A: Less than 32% B: 32% or more and less than 45% C: 45% or more

(260 ° C heat resistance)
The shielding film formed on the glass substrate is heated at 260 ° C. for 300 seconds using a hot plate, and the transmittance in each wavelength region before and after heating is measured with a spectrophotometer (“V-7300” by JASCO Corporation). It was measured in comparison with a glass substrate. At this time, the absorbance of the prepared infrared shielding film at the wavelength where the transmittance is lowest in the range of 700 to 800 nm is (α1), the absorbance after heating at 260 ° C. at the same wavelength is (α2), and the absorbance retention rate = 100. The heat resistance at 260 ° C. was evaluated based on the following criteria as × (α1) / (α2). When the retention rate is 80% or more, when used as a shielding film, it is possible to maintain high heat resistance by using it in combination with a protective film or the like, and it is presumed to be highly practical.
A: Retention rate is 90% or more B: Retention rate is 80% or more and less than 90% C: Retention rate is less than 80%

(Defect inhibitory property 1)
Each curable composition was applied to a silicon substrate by a spin coating method, and this coating film was cured to form a cured film (shielding film) having a film thickness of about 1 μm. The defect density of the cured film was measured using a defect / foreign matter inspection device (“KLA 2351” manufactured by KLA-Tencor). It can be judged that the smaller the value of the defect density is, the higher the defect suppressing property is. The defect refers to a detection point having a size of 1 μm or more. Based on the above defect density, the defect suppression property was evaluated according to the following criteria.
A: 10 / cm ² or less B: 10 / cm ^{2 or} more 50 / cm ² or less C: 50 / cm ^{2 or} more

(Defect inhibitory property 2)
After each curable composition was stored at 5 ° C. for 1 month, it was applied to a silicon substrate by a spin coating method, and this coating film was cured to form a cured film (shielding film) having a film thickness of about 1 μm. The defect density of the cured film was measured using a defect / foreign matter inspection device (“KLA 2351” manufactured by KLA-Tencor). It can be judged that the smaller the value of the defect density is, the higher the defect suppressing property is. The defect refers to a detection point having a size of 1 μm or more. Based on the above defect density, the defect suppression property was evaluated according to the following criteria.
A: 10 / cm ² or less B: 10 / cm ^{2 or} more 50 / cm ² or less C: 50 / cm ^{2 or} more

(Solvent resistance)
The transmittance in each wavelength region before and after immersing the shielding film prepared on the glass substrate in the acetone solution using the curable compositions of Examples 1, 11, 14, 15, 20 and Comparative Example 1 was determined. The measurement was performed in comparison with a glass substrate using a spectrophotometer (“V-7300” manufactured by JASCO Corporation). At this time, the transmittance at the wavelength at which the transmittance is the lowest in the range of 700 to 800 nm of the prepared shielding film is (T1), the absorbance after immersion in acetone at the same wavelength is (T2), and the change in transmittance = | (T1). )-(T2) |, the solvent resistance was evaluated according to the following criteria. It is presumed that the smaller the change in transmittance, the higher the practicality when used as a shielding film.
A: Transmittance change is 1% or less B: Transmittance change is more than 1% and 5% or less C: Transmittance change is more than 5%

As shown in Tables 1 and 2, the curable compositions of Examples 1 to 17 have good ultraviolet shielding properties, visible light transmittance, and heat resistance close to the visible light region, and have defects such as foreign substances. It can be seen that less optical filters can be formed. Further, it can be seen that the optical filters formed from the curable compositions of Examples 1 to 17 also have good infrared shielding properties.

On the other hand, the optical filter formed from the curable compositions of Comparative Examples 1 to 4 was inferior in at least one of ultraviolet shielding property, heat resistance and defect suppressing property. Specifically, in Comparative Examples 1 and 2 in which a compound (A'-1) having no carbazole skeleton to which a nitro group was bonded was used instead of the component (A) which is a compound represented by the formula (1). The result was that the UV shielding property was low. In Comparative Example 3 in which the compound (A'-3) was used instead of the component (A), which is the compound represented by the formula (1), the result was that the heat resistance was low. Compound (A'-3) has a carbazole skeleton to which a nitro group is attached, but does not have an oxime ester structure. It is considered that the UV shielding property and heat resistance of the formed optical filter are exhibited by using the compound represented by the formula (1). Further, in Comparative Example 4 containing the component (A) but not containing the component (B), which is a compound represented by the formula (2), the defect suppressing property was low.

The curable composition of the present invention can be suitably used as a material for forming an optical filter of an optical sensor such as a solid-state image sensor.

Claims (12)

The first compound represented by the following formula (1),
The second compound represented by the following formula (2),
A curable composition containing a binder containing a compound having a polymerizable group and a solvent.

(In the formula (1), R ¹ , R ² and R ³ are independently monovalent organic groups having 1 to 30 carbon atoms. R ⁴ and R ⁵ are independent of each other and have carbon numbers. .a and b is a monovalent organic group or a halogen atom having 1 to 30 are each independently, if .a is 2 or an integer of 0-3, a plurality of R ⁴ may be the same or different If even better .b is 2 or more, plural R ⁵ may be the same or different.)

(In the formula (2), A is a ring structure composed of one or more five-membered rings or six-membered rings. R ⁶ is a halogen atom, a hydroxy group, a nitro group or 1 of 1 to 40 carbon atoms. A valent organic group, R ⁷ is * -CO-, * -COO-, * -SCO-, * -COS-, * -S-COO-, * -CONH-, * -NHCO-, or *. -NHCOO- (* indicates the bonding position with the oxygen atom). R ⁸ is a monovalent organic group having 1 to 20 carbon atoms. C is an integer of 0 to 4. d. Is an integer of 1 to 3. e is an integer of 1 to 10. When e is 1, X is a monovalent organic group, and when e is 2 or more, X is a concatenation of e valences. When there are a plurality of ^{R 6} , R ⁷ or R ^{8 , the plurality of R 6} , the plurality of R ^7s or the plurality of R ^8s may be the same or different. The curable composition according to claim 1, which is for an optical filter. The curable composition according to claim 1 or 2, further comprising a first dye having a maximum absorption wavelength in a wavelength region of 650 nm or more and 900 nm or less. The curable composition according to claim 3, wherein the first dye contains a phthalocyanine pigment, a cyanine pigment, a pyrolopyrrole pigment, a naphthalocyanine pigment, a diimonium pigment, an azo pigment, a squarylium pigment, or a combination thereof. Stuff. The curable composition according to claim 3, wherein the first dye contains a compound represented by the following formula (3).

(In the formula (3), each of the plurality of ^Ra is an alkyl group having a substituent or an unsubstituted group, or an aryl group having a substituent or an unsubstituted group. The plurality of R ^bs are each independently. Independently, it is a hydrogen atom, a halogen atom or an alkyl group. A plurality of R ^bs may be bonded to each other to form an aromatic ring together with a carbon chain to which they are bonded. M is two hydrogen atoms, It is a divalent metal atom or a derivative of a trivalent or tetravalent metal atom. A plurality of ns are independently integers of 3 to 6). The curable composition according to any one of claims 1 to 5, further comprising a second dye having a maximum absorption wavelength in a wavelength region of more than 900 nm and 2,000 nm or less. The curable composition according to any one of claims 1 to 6, wherein ^{R 1} in the formula (1) in the first compound is a hydrocarbon group having a substituent or an unsubstituted group. ^{From claim 1 in which R 7} in the formula (2) in the second compound is * -COO-, * -COS-, or * -CONH- (* indicates a bond position with an oxygen atom). The curable composition according to any one of claims 7. The curable composition according to any one of claims 1 to 8, wherein the binder contains a polymer. The curable composition according to any one of claims 1 to 9, wherein the solvent contains a compound having a cyclic structure. The curable composition according to any one of claims 1 to 10, further comprising a compound having a phenylthio skeleton and an oxime ester structure. The curable composition according to any one of claims 1 to 11, further comprising a compound represented by the following formula (4).

(In the formula (4), A 'is 1 or a is .R 6 ring structure composed of a plurality of five-membered ring or six-membered ^ring' is halogen atom, hydroxy group, the number nitro group or C 1-40 C'is an integer from 0 to 4. d'is an integer from 1 to 3. e'is an integer from 1 to 10. e'is an integer of 1. If, X 'is a monovalent organic group, e' when is 2 or more, X ^'when it is more than that, a plurality of R ^6' 'is e' .R 6 is a linking group number is the same But it can be different.)