JP6649507B2 - Curable composition - Google Patents

Description

  The present invention relates to a curable composition, a method for curing the curable composition, a cured product obtained by curing the curable composition, and a wavelength cut filter using the cured product obtained by curing the curable composition.

  The sensitivities of solid-state imaging devices (CCD, C-MOS, etc.) used in digital still cameras, video cameras, mobile phone cameras, and the like range from the ultraviolet region to the infrared region of the wavelength of light. On the other hand, human visibility is only in the visible region of the wavelength of light. Therefore, by providing an infrared cut filter, which is a type of wavelength cut filter, between the imaging lens and the solid-state imaging device, the sensitivity of the solid-state imaging device is corrected so as to approach human visibility.

  As such an infrared cut filter, filters manufactured by various methods have conventionally been used. For example, a reflective filter described in Patent Document 1 or the like and an absorption filter described in Patent Document 2 or the like are used. The reflection-type filter described in Patent Literature 1 combines layers containing a substance having no absorption characteristics, such as metal, to form a multilayer, and uses the difference in the refractive index between them. The absorption type filter described above has a resin substrate containing an organic compound having a squarylium structure. These wavelength cut filters have durability that light absorption is particularly steep so as to approach human visibility, that is, the half width of λmax is small, and the function is not lost by light or heat. Is required to be high.

  Since the characteristics of the reflection type filter described in Patent Document 1 and the like change depending on the incident angle of light, there are adverse effects such as a change in color tone between the center and the periphery of the screen. Further, there is also a problem that reflected light becomes stray light in an optical path and causes degradation of resolution, image spots and unevenness, and multiple images called ghosts.

  On the other hand, the absorption type filters described in Patent Literature 2 and the like do not change in characteristics due to the incident angle of light, but may require a considerable thickness to obtain desired characteristics. In addition, as a material of a resin substrate containing a light absorber using an organic compound, a curable resin such as an acrylic resin or a plastic resin such as a cyclic olefin resin or a polycarbonate resin is used. Is often inferior.

  In addition, curing methods for curable resins such as acrylic resins include photopolymerization using a photopolymerization initiator such as a photoacid generator and a photoradical initiator, and thermal polymerization using a thermal polymerization initiator such as a thermal acid generator. There is. Patent Document 3 includes a three-dimensional crosslinked polymer matrix precursor material containing a non-ester-based alicyclic epoxy compound and a thermal acid generator, a radical polymerizable compound, and a radical polymerization initiator, There is disclosed a photosensitive composition for volume hologram recording containing a sensitizing dye. In Patent Document 3, a dye is used as a sensitizer for a radical polymerization initiator. The document states that the sensitizing dye is preferably one that is decomposed by heating or irradiated with ultraviolet light or visible light and becomes colorless and transparent. As can be seen from the above, in the curable resin containing a dye, the dye is easily decomposed at the time of curing, and when this is used as an optical filter, it may be a cause that a sufficient wavelength absorbing ability cannot be obtained.

  Patent Document 4 discloses a photocurable composition using a cationic dye such as a cyanine compound, a cationically polymerizable organic substance such as an epoxy compound, and a photoacid generator.

US2005 / 253048A1 JP 2012-008532 A JP 2011-118363 A WO 2013/172145

  The cured product obtained from the photocurable composition described in Patent Literature 4 has a problem in that it has poor wet heat resistance, and has a problem that a dye is precipitated in the cured product.

  Therefore, an object of the present invention is to provide a curable composition having excellent wet heat resistance and capable of forming a cured product suitable for a wavelength cut filter. Another object of the present invention is to provide a method for curing the curable composition and a cured product obtained by curing the curable composition. Still another object of the present invention is to provide a wavelength cut filter using the above cured product and having excellent wet heat resistance.

  The present inventors have conducted intensive studies and found that a curable composition containing two or more cationic dyes, a cationically polymerizable organic substance, and an acid generator is excellent in wet heat resistance, The inventors have found that this curable composition is suitable for producing a wavelength cut filter, and have reached the present invention.

That is, the present invention provides a curable composition containing two or more cationic dyes (A), a cationically polymerizable organic substance (B), and an acid generator (C).
The present invention also provides a method for curing the curable composition, wherein the curable composition further containing an organic solvent is applied to a substrate and then cured by active energy rays or heating.
Further, the present invention provides a cured product of the curable composition, and a wavelength cut filter including the cured product in at least a part thereof.

It is sectional drawing which shows the outline of an example of the layer structure of the wavelength cut filter of this invention. It is sectional drawing which shows the outline of another example of the layer structure of the wavelength cut filter of this invention.

Hereinafter, the curable composition of the present invention will be described based on preferred embodiments.
The curable composition of the present invention contains two or more cationic dyes (A), a cationically polymerizable organic substance (B), and an acid generator (C). Hereinafter, each component will be described in order.

First, two or more cationic dyes (A) will be described.
The two or more cationic dyes (A) used in the curable composition of the present invention are not particularly limited, and known dyes can be used. Examples thereof include polymethine dyes such as quinoline blue, malachite green, and crystal. Triphenylmethane dyes such as violet, diphenylmethane dyes such as auramine, thiazine dyes such as methylene blue, xanthene dyes such as rhodamine B, azo dyes such as safranine, oxazine dyes such as Basic Blue 3, acridine orange, etc. Dyes such as acridine dyes and pyrylium dyes such as anthocyanidins can be used. The term “two or more types” used herein includes, for example, a case where two or more dyes of the same type are used (for example, a polymethine dye and a different type of polymethine type dye), and two or more types of dyes of different types are used. (For example, a polymethine dye and a triphenylmethane dye).

It is preferable that at least one of the two or more cationic dyes (A) is a polymethine-based dye from the viewpoint of resistance to moist heat, and that the two or more cationic dyes are a polymethine-based dye and a different type of polymethine-based dye. Is more preferred.
A polymethine dye is a compound composed of a cation part and an anion part. In the present invention, the case where both the cation portion and the anion portion have the same structure is the same type of polymethine dye. If the structure of the cation portion is the same, but the structure of the anion portion is different, different types of polymethine dyes are used. When these are used, two types of polymethine dyes are used. Also, even if the structure of the anion portion is the same, if the structure of the cation portion is different, a different type of polymethine dye is used.If both the structure of the cation portion and the structure of the anion portion are different, naturally, a different type of polymethine dye is used. It is a system dye. In the present invention, any of those having the same cationic portion but different anionic portion, those having different cationic portions and the same anionic portion, and those having both different cationic and anionic portions, as different types of polymethine dyes From the viewpoint of resistance to moist heat, it is preferable that the cation moiety is different and the anion moiety is the same, or that both the cation moiety and the anion moiety are different.

In the present invention, the content ratio of two or more cationic dyes is not particularly limited. However, since the wet heat resistance of the cured product of the curable composition becomes particularly good, the content ratio of the two or more cationic dyes (A) is The proportion of one type of cationic dye is preferably 25% to 95%, more preferably 35% to 80%, even more preferably 40% to 60% by mass. In particular, it is preferable that two or more kinds of the cationic dyes (A) are composed of two kinds of the cationic dyes, and the ratio of one kind of the two kinds of the cationic dyes is within the above range.
The content ratio of the two types is preferably 99.99: 0.01 to 0.01: 99.99, more preferably 98: 2, in terms of mass ratio, because the wet heat resistance is good. 2:98, more preferably 95: 5 to 25:75, even more preferably 60:40 to 40:60.

  Examples of the polymethine dye include a compound represented by the following general formula (1). In the present specification, * in the chemical formula indicates a bond.

(Wherein, A represents a group selected from the following group I (a) to (m), A ′ represents a group selected from the following group II (a ′) to (m ′), Represents a linking group containing a methine chain represented by the following general formula (1-A), An ^q- represents a q-valent anion, q represents 1 or 2, and p keeps a charge neutral. Represents a coefficient.)

(Wherein, ring C and ring C ′ each independently represent a benzene ring, a naphthalene ring, a phenanthrene ring or a pyridine ring;
In the formula, R ¹ and R ¹ ′ each independently represent a hydrogen atom, a hydroxyl group, a halogen atom, a nitro group, a cyano group, a carboxyl group, an amino group, a dialkylamino group having 2 to 16 carbon atoms, a carbon atom having 12 to 12 carbon atoms. 40 diarylamino groups, arylalkylamino groups having 7 to 28 carbon atoms, amide groups, aryl groups having 6 to 20 carbon atoms, arylalkyl groups having 7 to 30 carbon atoms or alkyl having 1 to 8 carbon atoms A hydrogen atom of a dialkylamino group, a diarylamino group, an arylalkylamino group, an aryl group, an arylalkyl group and an alkyl group in R ¹ and R ¹ ′ are each independently a hydroxyl group, a halogen atom, a nitro group , a cyano group, a carboxyl group, an amino group, may be substituted with a amido group or a ferrocenyl group, Jiarukirua in said R ¹ and R ^{1 '} M, a diarylamino group, an arylalkylamino group, an aryl group, an arylalkyl group and a methylene group in the alkyl group each independently represent -O-, -S-, -CO-, -COO-, -OCO-. _{, -SO 2 -, - NH -} , - CONH -, - NHCO -, - N = CH- or may be replaced by -CH = CH-,
In the formula, R ^{2 to} R ⁹ and R ² ′ to R ⁹ ′ each independently represent a hydrogen atom, a hydroxyl group, a halogen atom, a nitro group, a cyano group, a carboxyl group, an amino group, an amide group, a carbon atom number of 6 to 20. An aryl group, an arylalkyl group having 7 to 30 carbon atoms or an alkyl group having 1 to 8 carbon atoms, wherein the aryl group, the arylalkyl group and the aryl group in R ^{2 to} R ⁹ and R ² ′ to R ⁹ ′ The hydrogen atom of the alkyl group may be independently substituted with a hydroxyl group, a halogen atom, a nitro group, a cyano group, a carboxyl group, an amino group, an amide group or a ferrocenyl group, and the R ^{2 to} R ⁹ and R ² ′ aryl groups in to R ⁹ ', a methylene group in the arylalkyl and alkyl groups are each independently, -O -, - S -, - CO -, - COO -, - OCO -, - SO 2 -, -NH-, -CONH- -NHCO -, - N = CH- or may be replaced by -CH = CH-,
In the formula, X and X ′ each independently represent an oxygen atom, a sulfur atom, a selenium atom, —CR ⁵¹ R ⁵² —, a cycloalkane-1,1-diyl group having 3 to 6 carbon atoms, —NH— or —. NY ² - ^{represents, R 51} and ^{R 52} each independently represent a hydrogen atom, a hydroxyl group, a halogen atom, a nitro group, a cyano group, a carboxyl group, an amino group, an amide group, an aryl group having 6 to 20 carbon atoms, a carbon Represents an arylalkyl group having 7 to 30 atoms or an alkyl group having 1 to 8 carbon atoms, and hydrogen atoms of the aryl group, the arylalkyl group and the alkyl group in R ⁵¹ and R ⁵² are each independently a hydroxyl group, a halogen atom, May be substituted with an atom, a nitro group, a cyano group, a carboxyl group, an amino group, an amide group or a ferrocenyl group, and the aryl group, arylalkyl group and alkyl group in R ⁵¹ and R ⁵² may be substituted. Methylene groups in the kill groups are each independently, -O -, - S -, - CO -, - COO -, - OCO -, - SO 2 -, - NH -, - CONH -, - NHCO -, - May be substituted with N = CH- or -CH = CH-,
In the formula, Y, Y ′ and Y ² each independently represent a hydrogen atom, a hydroxyl group, a halogen atom, a cyano group, a carboxyl group, an amino group, an amide group, a nitro group, an aryl group having 6 to 20 carbon atoms, a carbon atom arylalkyl group or an alkyl group having 1 to 8 carbon atoms in the C7-30, the Y, Y 'and Y ² in the aryl group, a hydrogen atom in the arylalkyl and alkyl groups are each independently, a hydroxyl group, a halogen group, a cyano group, a carboxyl group, an amino group, an amido group, may be substituted with a ferrocenyl group or a nitro group, said Y, Y 'and Y ² in the aryl group, arylalkyl group, and the alkyl group methylene groups are each independently, -O -, - S -, - CO -, - COO -, - OCO -, - SO 2 -, - NH -, - CONH -, - NHCO -, - N = CH -Or -CH = C - it may be substituted with,
In the formula, r and r ′ are 0 or (a) to (e), (g) to (j), (1), (m), (a ′) to (e ′), (g ′) to (J '), (l') and (m ') represent one or more possible substituents. )

(In the formula, k represents an integer of 0 to 4,
In the formula, the hydrogen atoms of the methine chain are each independently a hydroxyl group, a halogen atom, a cyano group, -NRR ', an aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms or a carbon atom. It may be substituted with an alkyl group of 1 to 8, and the alkyl group becomes a corresponding alkylene group and bonds to any two carbon atoms of the methine chain to form a ring structure having 3 to 10 carbon atoms. And each hydrogen atom of the ring structure is independently a hydroxyl group, a halogen atom, a cyano group, -NRR ', an aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a carbon atom. May be substituted with an alkyl group having 1 to 8 atoms,
R and R ′ in the methine chain and the ring structure each independently represent an aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or an alkyl group having 1 to 8 carbon atoms. The hydrogen atom in the methine chain and -NRR 'in the ring structure, the aryl group, the arylalkyl group and the alkyl group may be further independently substituted with a hydroxyl group, a halogen atom, a cyano group or -NRR'. And the aryl group in the methine chain and the ring structure, the methylene group in the arylalkyl group and the methylene group in the alkyl group are each independently -O-, -S-, -CO-, -COO-, -OCO-, _{-SO 2 -, - NH -,} - CONH -, - NHCO -, - N = CH- or may be replaced by -CH = CH-. )

Examples of the halogen atom represented by R ^{1 to} R ⁹ and R ¹ ′ to R ⁹ ′ in the general formula (1) and R ⁵¹ and R ⁵² in X and X ′ include fluorine, chlorine, bromine, and iodine. Can be

The aryl group having 6 to 20 carbon atoms represented by R ^{1 to} R ⁹ and R ¹ ′ to R ⁹ ′ in the general formula (1) and R ⁵¹ and R ⁵² in X and X ′ is phenyl, Naphthyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 4-vinylphenyl, 3-iso-propylphenyl, 4-iso-propylphenyl, 4-butylphenyl, 4-iso-butylphenyl, 4- tert-butylphenyl, 4-hexylphenyl, 4-cyclohexylphenyl, 4-octylphenyl, 4- (2-ethylhexyl) phenyl, 4-stearylphenyl, 2,3-dimethylphenyl, 2,4-dimethylphenyl, 2, 5-dimethylphenyl, 2,6-dimethylphenyl, 3,4-dimethylphenyl, 3,5-dimethylphenyl, , 4-Di-tert-butylphenyl, 2,5-di-tert-butylphenyl, 2,6-di-tert-butylphenyl, 2,4-di-tert-pentylphenyl, 2,5-di-tert -Amylphenyl, 2,5-di-tert-octylphenyl, 2,4-dicumylphenyl, 4-cyclohexylphenyl, (1,1'-biphenyl) -4-yl, 2,4,5-trimethylphenyl, Ferrocenyl and the like.

The arylalkyl group having 7 to 30 carbon atoms represented by R ^{1 to} R ⁹ and R ¹ ′ to R ⁹ ′ in the general formula (1) and R ⁵¹ and R ⁵² in X and X ′ is benzyl. Phenethyl, 2-phenylpropan-2-yl, diphenylmethyl, triphenylmethyl, styryl, cinnamyl, ferrocenylmethyl, ferrocenylpropyl, 4-isopropylphenethyl and the like.

Examples of the alkyl group having 1 to 8 carbon atoms represented by R ^{1 to} R ⁹ and R ¹ ′ to R ⁹ ′ in the general formula (1) and R ⁵¹ and R ⁵² in X and X ′ include methyl, Ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, tert-butyl, iso-butyl, amyl, iso-amyl, tert-amyl, n-hexyl, 2-hexyl, 3-hexyl, cyclohexyl, Examples thereof include 1-methylcyclohexyl, n-heptyl, 2-heptyl, 3-heptyl, iso-heptyl, tert-heptyl, 1-octyl, iso-octyl, and tert-octyl.

Examples of the dialkylamino group having 2 to 16 carbon atoms represented by R ¹ and R ¹ ′ in the general formula (1) include an amino group having the alkyl group, and a diaryl having 12 to 40 carbon atoms. Examples of the amino group include an amino group having the aryl group. Examples of the arylalkylamino group having 7 to 28 carbon atoms include the amino group having the aryl group and the alkyl group.

The dialkylamino group having 2 to 16 carbon atoms, the diarylamino group having 12 to 40 carbon atoms, the arylalkylamino group having 7 to 28 carbon atoms, the aryl group having 6 to 20 carbon atoms, and the 7 to carbon atoms The hydrogen atoms in the 30 arylalkyl groups and the alkyl groups having 1 to 8 carbon atoms are each independently substituted with a hydroxyl group, a halogen atom, a nitro group, a cyano group, a carboxyl group, an amino group, an amide group or a ferrocenyl group. In some cases, the methylene group in the dialkylamino group, diarylamino group, arylalkylamino group, aryl group, arylalkyl group and alkyl group is each independently -O-, -S-, -CO-,- _{COO -, - OCO -, -} SO 2 -, - NH -, - CONH -, - NHCO -, - N = CH- or field to be replaced by -CH = CH- There are, number and position of these substitutions are arbitrary.

For example, as a group in which a hydrogen atom in the alkyl group having 1 to 8 carbon atoms is substituted with a halogen atom, for example, chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, nonafluoro Butyl and the like,
Examples of the group in which the methylene group in the alkyl group having 1 to 8 carbon atoms is substituted with -O- include methyloxy, ethyloxy, iso-propyloxy, propyloxy, butyloxy, pentyloxy, iso-pentyloxy, hexyl Alkoxy groups such as oxy, heptyloxy, octyloxy, 2-ethylhexyloxy, 2-methoxyethyl, 2- (2-methoxy) ethoxyethyl, 2-ethoxyethyl, 2-butoxyethyl, 4-methoxybutyl, Alkoxyalkyl groups such as methoxybutyl and the like,
Examples of the group in which a hydrogen atom in the alkyl group having 1 to 8 carbon atoms is substituted with a halogen atom and a methylene group in the alkyl group is substituted with -O- include, for example, chloromethyloxy, dichloromethyloxy , Trichloromethyloxy, fluoromethyloxy, difluoromethyloxy, trifluoromethyloxy, nonafluorobutyloxy and the like.

  In the general formula (1), the cycloalkane-1,1-diyl group having 3 to 6 carbon atoms represented by X and X ′ includes cyclopropane-1,1-diyl, cyclobutane-1,1-diyl. Diyl, 2,4-dimethylcyclobutane-1,1-diyl, 3,3-dimethylcyclobutane-1,1-diyl, cyclopentane-1,1-diyl, cyclohexane-1,1-diyl and the like.

In the general formula (1), Y, the halogen atom represented by Y 'and Y ^2, fluorine, chlorine, bromine, and iodine.

The aryl group having 6 to 20 carbon atoms represented by Y, Y ′ and Y ² includes phenyl, naphthyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 4-vinylphenyl, 3-iso -Propylphenyl, 4-iso-propylphenyl, 4-butylphenyl, 4-iso-butylphenyl, 4-tert-butylphenyl, 4-hexylphenyl, 4-cyclohexylphenyl, 4-octylphenyl, 4- (2- Ethylhexyl) phenyl, 4-stearylphenyl, 2,3-dimethylphenyl, 2,4-dimethylphenyl, 2,5-dimethylphenyl, 2,6-dimethylphenyl, 3,4-dimethylphenyl, 3,5-dimethylphenyl , 2,4-di-tert-butylphenyl, 2,5-di-tert-butylphenyl 2,6-di-tert-butylphenyl, 2,4-di-tert-pentylphenyl, 2,5-di-tert-amylphenyl, 2,5-di-tert-octylphenyl, 2,4-dicumyl Phenyl, 4-cyclohexylphenyl, (1,1′-biphenyl) -4-yl, 2,4,5-trimethylphenyl, ferrocenyl and the like.

Y, the aryl alkyl group having 7 to 30 carbon atoms represented by Y 'and ^{Y 2,} benzyl, phenethyl, 2-phenylpropan-2-yl, diphenylmethyl, triphenylmethyl, styryl, cinnamyl, Ferose Nylmethyl, ferrocenylpropyl, 4-isopropylphenethyl and the like.

Y, the alkyl group having 1 to 8 carbon atoms represented by Y 'and ^{Y 2,} methyl, ethyl, n- propyl, iso- propyl, n- butyl, sec- butyl, tert- butyl, iso- butyl , Amyl, iso-amyl, tert-amyl, n-hexyl, 2-hexyl, 3-hexyl, cyclohexyl, 1-methylcyclohexyl, n-heptyl, 2-heptyl, 3-heptyl, iso-heptyl, tert-heptyl, Examples include 1-octyl, iso-octyl, tert-octyl and the like.

Y, Y ', aryl group in Y ^2, a hydrogen atom in the arylalkyl and alkyl groups are each independently a hydroxyl group, a halogen group, a cyano group, a carboxyl group, an amino group, an amide group, ferrocenyl group or a nitro group And the number and position of these substitutions are arbitrary.

In the general formula (1), the aryl group in Y, Y ′ and Y ² , the arylalkyl group and the methylene group in the alkyl group each independently represent —O—, —S—, —CO—, _{-COO -, - OCO -, -} SO 2 -, - NH -, - CONH -, - NHCO -, - may N = CH- or substituted with -CH = CH-, the number of these substitutions and The position is arbitrary.
For example, when the above methylene group is substituted with the above -O-, -S- or the like, methyl, ethyl, propyl, iso-propyl, butyl, sec-butyl, tert-butyl, iso-butyl, amyl , Iso-amyl, tert-amyl, hexyl, 2-hexyl, 3-hexyl, cyclohexyl, 1-methylcyclohexyl, heptyl, 2-heptyl, 3-heptyl, iso-heptyl, tert-heptyl, 1-octyl, iso- Alkyl groups such as octyl, tert-octyl, 2-ethylhexyl, nonyl, iso-nonyl, decyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl and octadecyl; 2-methylphenyl, 3-methylphenyl, 4-methylphenyl , 4-vinylphenyl, 3 iso-propylphenyl, 4-iso-propylphenyl, 4-butylphenyl, 4-iso-butylphenyl, 4-tert-butylphenyl, 4-hexylphenyl, 4-cyclohexylphenyl, 4-octylphenyl, 4- (2 -Ethylhexyl) phenyl, 4-stearylphenyl, 2,3-dimethylphenyl, 2,4-dimethylphenyl, 2,5-dimethylphenyl, 2,6-dimethylphenyl, 3,4-dimethylphenyl, 3,5-dimethyl Aryl groups such as phenyl, 2,4-di-tert-butylphenyl and cyclohexylphenyl; and arylalkyl groups such as benzyl, phenethyl, 2-phenylpropan-2-yl, diphenylmethyl, triphenylmethyl, styryl, cinnamyl and the like. Methylene group in the -O-,- And the like, for example, 2-methoxyethyl, 3-methoxypropyl, 4-methoxybutyl, 2-butoxyethyl, methoxyethoxyethyl, methoxyethoxyethoxyethyl, 3-methoxybutyl, 2-phenoxyethyl, 3 -Phenoxypropyl, 2-methylthioethyl, 2-phenylthioethyl and the like.

  In the general formula (1), A is a group selected from (a), (b), (c), (i), (k) and (m), and A ′ is (a ′), (b ′) ), (C '), (i'), (k ') and (m') are preferred from the viewpoint of easy availability of industrial raw materials, and A is (a) or (c) And A ′ is more preferably a group selected from (a ′) and (c ′).

In the general formula (1), A and A ′ may be mutually symmetric groups or asymmetric groups. The mutually symmetric groups are, for example, A is (a), A ′ is (a ′), and the ring C, Y, R ¹ , r, X in (a) is (a ′) ) Is the same as ring C ′, Y ′, R ¹ ′, r ′, X ′. Asymmetrical groups are not symmetrical to each other.

In the linking group represented by the general formula (1-A), a methine chain and a halogen atom which may substitute a ring structure having 3 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, and a carbon atom having 7 carbon atoms may be substituted. To 30 arylalkyl groups or an alkyl group having 1 to 8 carbon atoms; an aryl group having 6 to 20 carbon atoms represented by R and R 'in the general formula (1-A); The arylalkyl group having 1 to 30 carbon atoms or the alkyl group having 1 to 8 carbon atoms includes R ^{1 to} R ⁹ and R ¹ ′ to R ⁹ ′ in the above general formula (1) and R ⁵¹ and R in X and X ′. ^{The same} thing as the thing represented by ⁵² is mentioned.

  As the linking group represented by the general formula (1-A), a group represented by any one of the following (Q-1) to (Q-11) is preferable because production is easy. Further, the moist heat resistance is particularly high because the methine chain is short, and therefore the groups represented by the following (Q-1) to (Q-3) and (Q-11) are more preferable. Q-2) and (Q-11) are more preferred. Further, (Q-4) to (Q-9) are more preferable because they have a high moist heat resistance because they have a ring structure in the methine chain.

(Where R ¹⁴ , R ^Fifteen , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ And Z ′ are each independently a hydrogen atom, a hydroxyl group, a halogen atom, a cyano group, —NRR ′, an aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms or 1 to carbon atoms. 8 represents an alkyl group, R and R 'each independently represents an aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms or an alkyl group having 1 to 8 carbon atoms, The R ¹⁴ , R ^Fifteen , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ And -NRR 'in Z', an aryl group, an arylalkyl group and a hydrogen atom in the alkyl group are each independently a hydroxyl group, a halogen atom, a cyano group, -NRR ', a carboxyl group, an amino group, an amide group, a ferrocenyl. A methylene group in the aryl group, the arylalkyl group and the alkyl group may be each independently -O-, -S-, -CO-, -COO-, -OCO -, -SO ₂ -, -NH-, -CONH-, -NHCO-, -N = CH- or -CH = CH- in some cases. )

Examples of the halogen atom represented by R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ and Z ′ include fluorine, chlorine, bromine and iodine.

The aryl group having 6 to 20 carbon atoms represented by R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , Z ′, R and R ′ includes phenyl, naphthyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 4-vinylphenyl, 3-iso-propylphenyl, 4-iso-propylphenyl, 4-butylphenyl, 4-iso-butylphenyl, 4-tert-butylphenyl, 4- Hexylphenyl, 4-cyclohexylphenyl, 4-octylphenyl, 4- (2-ethylhexyl) phenyl, 4-stearylphenyl, 2,3-dimethylphenyl, 2,4-dimethylphenyl, 2,5-dimethylphenyl, 2, 6-dimethylphenyl, 3,4-dimethylphenyl, 3,5-dimethylphenyl, 2,4-di-t rt-butylphenyl, 2,5-di-tert-butylphenyl, 2,6-di-tert-butylphenyl, 2,4-di-tert-pentylphenyl, 2,5-di-tert-amylphenyl, 2 , 5-di-tert-octylphenyl, 2,4-dicumylphenyl, 4-cyclohexylphenyl, (1,1′-biphenyl) -4-yl, 2,4,5-trimethylphenyl, ferrocenyl and the like. .

The arylalkyl group having 7 to 30 carbon atoms represented by R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , Z ′, R and R ′ includes benzyl, phenethyl, 2-phenylpropane -2-yl, diphenylmethyl, triphenylmethyl, styryl, cinnamyl, ferrocenylmethyl, ferrocenylpropyl, 4-isopropylphenethyl and the like.

Examples of the alkyl group having 1 to 8 carbon atoms represented by R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , Z ′, R and R ′ include methyl, ethyl, propyl, and iso-propyl. Butyl, sec-butyl, tert-butyl, iso-butyl, amyl, iso-amyl, tert-amyl, hexyl, 2-hexyl, 3-hexyl, cyclohexyl, 1-methylcyclohexyl, heptyl, 2-heptyl, 3- Heptyl, iso-heptyl, tert-heptyl, 1-octyl, iso-octyl, tert-octyl and the like.

  Hydrogen atoms in these aryl groups, arylalkyl groups and alkyl groups are each independently substituted with a hydroxyl group, a halogen group, a cyano group, -NRR ', a carboxyl group, an amino group, an amide group, a ferrocenyl group or a nitro group. The number and position of these substitutions are arbitrary.

The q-valent anion represented by pAn ^q- in the general formula (1), methanesulfonic acid anion, dodecyl sulfonate anion, benzenesulfonic acid anion, toluenesulfonic acid anion, trifluoromethanesulfonic acid anion, naphthalenesulfonic Acid anion, diphenylamine-4-sulfonic acid anion, 2-amino-4-methyl-5-chlorobenzenesulfonic acid anion, 2-amino-5-nitrobenzenesulfonic acid anion, JP-A-10-235999, JP-A-10-337959 JP-A-11-102888, JP-A-2000-108510, JP-A-2000-168233, JP-A-2001-209969, JP-A-2001-322354, JP-A-2006-248180 , JP Organic sulfonic acids such as sulfonic acid anions described in 2006-297907, JP-A-8-253705, JP-T-2004-503379, JP-A-2005-336150, and WO 2006/280006. Other than anions, chloride ion, bromide ion, iodide ion, fluoride ion, chlorate ion, thiocyanate ion, perchlorate ion, hexafluorophosphate ion, hexafluoroantimonate ion, tetrafluoroborate ion, Octyl phosphate ion, dodecyl phosphate ion, octadecyl phosphate ion, phenyl phosphate ion, nonylphenyl phosphate ion, 2,2′-methylenebis (4,6-di-t-butylphenyl) phosphonate ion, tetrakis (pentane) Fluorophenyl) borate ion, A quencher anion having a function of de-exciting (quenching) an active molecule in an excited state, ferrocene, luteocene, etc. having an anionic group such as a carboxyl group, a phosphonic acid group or a sulfone group on a cyclopentadienyl ring. Metallocene compound anions.

  Among these, organic sulfonic acid anion, hexafluorophosphate ion, and tetrakis (pentafluorophenyl) borate ion are preferable, and N, N-bis (trifluoromethanesulfonyl) imidate anion, N, N-bis (fluorosulfonyl) imidate anion, N, N-bis (nonafluorobutanesulfonyl) imidate anion, trifluoromethanesulfonic acid anion, tris (trifluoromethanesulfonyl) methide anion, hexafluorophosphate ion, Tetrakis (pentafluorophenyl) borate ion is more preferred.

  Note that the symbol * in the above general formulas (1) and (1-A) indicates that the compound is bonded to an adjacent group at the position marked with *.

  Specific examples of the polymethine compound used in the present invention include the following compound No. 1 to 107. In addition, in the following examples, it shows with the compound which omitted the anion.

  The method for producing the polymethine compound is not particularly limited, and can be obtained by a method utilizing a well-known general reaction. For example, as described in JP-A-2010-209191, the corresponding It can be obtained by a method of synthesizing by reacting a compound having the compound with an imine derivative.

  In addition, the cationic dye (A) used in the present invention preferably has a maximum absorption wavelength (λmax) of 650 to 1200 nm of the cured product of the curable composition of the present invention because of its high infrared cut performance. Those having a thickness of up to 900 nm are more preferable.

Next, the cationically polymerizable organic substance (B) will be described.
The cationically polymerizable organic substance (B) used in the curable composition of the present invention is a compound that undergoes polymerization or crosslinking reaction by an acid generator (C) activated by heat or active energy ray irradiation. Any compound can be used, and it is not particularly limited, but an epoxy compound, an oxetane compound, a cyclic acetal compound, an oxolan compound, a cyclic lactone compound, a cyclic thioether compound, a spiro orthoester compound, a vinyl compound, and the like can be used. And one or more of these can be used. Among these, it is preferable to use one or more selected from the group consisting of an epoxy compound, an oxetane compound, and a cyclic acetal compound because the wet heat resistance and transparency of the cured product are particularly good. An epoxy compound is more preferred because it is particularly high, and an alicyclic epoxy compound, an aromatic epoxy compound, an aliphatic epoxy compound, and the like are more preferred.

  Specific examples of the alicyclic epoxy compound include polyglycidyl ether of a polyhydric alcohol having at least one alicyclic ring, or cyclohexene oxide obtained by epoxidizing a cyclohexene or cyclopentene ring-containing compound with an oxidizing agent. And cyclopentene oxide-containing compounds. For example, hydrogenated bisphenol A diglycidyl ether, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-1-methylcyclohexyl-3,4-epoxy-1-methylhexanecarboxylate , 6-methyl-3,4-epoxycyclohexylmethyl-6-methyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-3-methylcyclohexylmethyl-3,4-epoxy-3-methylcyclohexanecarboxylate 3,4-epoxy-5-methylcyclohexylmethyl-3,4-epoxy-5-methylcyclohexanecarboxylate, 2- (3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane- Metazioki Bis (3,4-epoxycyclohexylmethyl) adipate, 3,4-epoxy-6-methylcyclohexylcarboxylate, methylene bis (3,4-epoxycyclohexane), dicyclopentadiene diepoxide, ethylenebis (3,4- Epoxycyclohexanecarboxylate), dioctyl epoxyhexahydrophthalate, di-2-ethylhexyl epoxyhexahydrophthalate, 1-epoxyethyl-3,4-epoxycyclohexane, 1,2-epoxy-2-epoxyethylcyclohexane, 3, Examples thereof include 4-epoxycyclohexylmethyl acrylate and 3,4-epoxycyclohexylmethyl methacrylate.

Commercial products that can be suitably used as the alicyclic epoxy compound include UVR-6100, UVR-6105, UVR-6110, UVR-6128, UVR-6200 (all manufactured by Union Carbide Co., Ltd.), Celloxide 2021, Celloxide 2021P, Celloxide 2081, Celloxide 2083, Celloxide 2085, Celloxide 2000, Celloxide 3000, Cyclomer A200, Cyclomer M100, Cyclomer M101, Epolide GT-301, Epolide GT-302, Epolide 401, Epolide 403, ETHB, Epolide HD300, EHPE- 3150 (above, manufactured by Daicel Co., Ltd.), ADEKA ARKLE'S KRM-2110, ADEKA ARKLE'S KRM-2199 (above, manufactured by ADEKA Corporation) and the like. It can gel.
Among the alicyclic epoxy compounds, epoxy resins having a cyclohexene oxide structure are preferred because they cure quickly.

  Specific examples of the aromatic epoxy compound include a polyglycidyl ether of a polyhydric phenol having at least one aromatic ring or an alkylene oxide adduct thereof, for example, bisphenol A, bisphenol F or an alkylene oxide further added thereto. Glycidyl ethers of compounds, epoxy novolak resins and the like are mentioned.

  As specific examples of the aliphatic epoxy compound, polyglycidyl ether of aliphatic polyhydric alcohol or an alkylene oxide adduct thereof, polyglycidyl ester of aliphatic long-chain polybasic acid, glycidyl acrylate or glycidyl methacrylate was synthesized by vinyl polymerization. Examples thereof include homopolymers and copolymers synthesized by vinyl polymerization of glycidyl acrylate or glycidyl methacrylate with other vinyl monomers. Representative compounds include 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, triglycidyl ether of glycerin, triglycidyl ether of trimethylolpropane, tetraglycidyl ether of sorbitol, and dipentaerythritol. Glycidyl ethers of polyhydric alcohols such as hexaglycidyl ether, diglycidyl ether of polyethylene glycol, diglycidyl ether of polypropylene glycol, and one or more alkylenes in aliphatic polyhydric alcohols such as propylene glycol, trimethylolpropane, and glycerin Polyglycidyl ethers of polyether polyols obtained by adding oxides, and diglycidyl esters of aliphatic long-chain dibasic acids. It is. Furthermore, monoglycidyl ethers of higher aliphatic alcohols, phenol, cresol, butylphenol or monoglycidyl ethers of polyether alcohols obtained by adding alkylene oxides to these, glycidyl esters of higher fatty acids, epoxidized soybean oil, epoxy stearin Octyl acid, butyl epoxystearate, epoxidized polybutadiene and the like can be mentioned.

  Commercially available products that can be suitably used as the aromatic and aliphatic epoxy compounds include jER801, jER828, jER-1001, jER-1004, jER-1010, jERYX-4000, jERYDE-305, jER871, and jER872 (Mitsubishi Chemical Corporation). PY-306, 0163, DY-022 (all manufactured by Ciba-Geigy), Adeka Arkles KRM-2720, Adeka Resin EP-4100, Adeka Resin EP-4000, Adeka Resin EP-4080, Adeka Resin EP-4088, Adeka Resin EP-4900, Adeka Glysilol ED-505, Adeka Glysilol ED-506 (all manufactured by ADEKA Corporation), Epolite M-1230, Epolite EHDG-L, Epolite 40E, Epolite 100E Epolite 200E, Epolite 400E, Epolite 70P, Epolite 200P, Epolite 400P, Epolite 1500NP, Epolite 1600, Epolite 80MF, Epolite 100MF, Epolite 4000, Epolite 3002, Epolite FR-1500 (all manufactured by Kyoeisha Chemical Co., Ltd.), Suntoto ST3000 , Epotote YD-716, YH-300, PG-202, PG-207, Epotote YD-172, YDPN638 (all manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.) Denacol EX321, Denacol EX313, Denacol 314, Denacol EX-411, EM -150 (manufactured by Nagase ChemteX Corporation), EPPN-201, EOCN-1020, EPPN-501H (Nippon Kayaku Co., Ltd.), OGSOL PG-10 And OGSOL EG-200 (manufactured by Osaka Gas Chemical Co., Ltd.).

  Specific examples of the oxetane compound include, for example, the following compounds. 3-ethyl-3-hydroxymethyloxetane, 3- (meth) allyloxymethyl-3-ethyloxetane, (3-ethyl-3-oxetanylmethoxy) methylbenzene, 4-fluoro- [1- (3-ethyl-3) -Oxetanylmethoxy) methyl] benzene, 4-methoxy- [1- (3-ethyl-3-oxetanylmethoxy) methyl] benzene, [1- (3-ethyl-3-oxetanylmethoxy) ethyl] phenyl ether, isobutoxymethyl (3-ethyl-3-oxetanylmethyl) ether, isobornyloxyethyl (3-ethyl-3-oxetanylmethyl) ether, isobornyl (3-ethyl-3-oxetanylmethyl) ether, 2-ethylhexyl (3-ethyl- 3-oxetanylmethyl) ether, ethyldiethylenegly (3-ethyl-3-oxetanylmethyl) ether, dicyclopentadiene (3-ethyl-3-oxetanylmethyl) ether, dicyclopentenyloxyethyl (3-ethyl-3-oxetanylmethyl) ether, dicyclopentenyl ( 3-ethyl-3-oxetanylmethyl) ether, tetrahydrofurfuryl (3-ethyl-3-oxetanylmethyl) ether, tetrabromophenyl (3-ethyl-3-oxetanylmethyl) ether, 2-tetrabromophenoxyethyl (3- Ethyl-3-oxetanylmethyl) ether, tribromophenyl (3-ethyl-3-oxetanylmethyl) ether, 2-tribromophenoxyethyl (3-ethyl-3-oxetanylmethyl) ether, 2-hydroxyethyl (3-ethyl -3- Xetanylmethyl) ether, 2-hydroxypropyl (3-ethyl-3-oxetanylmethyl) ether, butoxyethyl (3-ethyl-3-oxetanylmethyl) ether, pentachlorophenyl (3-ethyl-3-oxetanylmethyl) ether, pentabromo Phenyl (3-ethyl-3-oxetanylmethyl) ether, bornyl (3-ethyl-3-oxetanylmethyl) ether, 3,7-bis (3-oxetanyl) -5-oxa-nonane, 3,3 ′-(1 , 3- (2-Methylenyl) propanediylbis (oxymethylene)) bis- (3-ethyloxetane), 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, 1,2-bis [(3-ethyl-3-oxetanylmethoxy) methyl] ethane, 1,3-bi S [(3-ethyl-3-oxetanylmethoxy) methyl] propane, ethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, dicyclopentenyl bis (3-ethyl-3-oxetanylmethyl) ether, triethylene glycol Bis (3-ethyl-3-oxetanylmethyl) ether, tetraethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, tricyclodecanediyldimethylene (3-ethyl-3-oxetanylmethyl) ether, trimethylolpropane Tris (3-ethyl-3-oxetanylmethyl) ether, 1,4-bis (3-ethyl-3-oxetanylmethoxy) butane, 1,6-bis (3-ethyl-3-oxetanylmethoxy) hexane, pentaerythritol tris (3-Echi -3-oxetanylmethyl) ether, pentaerythritol tetrakis (3-ethyl-3-oxetanylmethyl) ether, polyethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol hexakis (3-ethyl-3- Oxetanylmethyl) ether, dipentaerythritol pentakis (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritoltetrakis (3-ethyl-3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol hexakis (3-ethyl-) 3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol pentakis (3-ethyl-3-oxetanylmethyl) ether, ditrimethylolpropanetetrakis (3- Tyl-3-oxetanylmethyl) ether, EO-modified bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, PO-modified bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, EO-modified hydrogenated bisphenol A bis Examples thereof include (3-ethyl-3-oxetanylmethyl) ether, PO-modified hydrogenated bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, and EO-modified bisphenol F (3-ethyl-3-oxetanylmethyl) ether. be able to.

  Commercial products that can be suitably used as the oxetane compound include Alone oxetane OXT-101, Aron oxetane OXT-121, Aron oxetane OXT-221, Aron oxetane OXT-212, and Aron oxetane OXT-211 (all of which are manufactured by Toagosei Co., Ltd.) ETANACOL EHO, ETANACOL OXBP, ETANACOL OXTP, ETANACOL OXMA (all manufactured by Ube Industries, Ltd.) and the like. These can be used alone or in combination of two or more.

  These oxetane compounds are effective and preferable when used particularly when flexibility is required.

  Examples of the cyclic acetal compound include trioxane, 1,3-dioxolan, 1,3,6-trioxane cyclooctane, and the like.

Examples of the oxolane compound include tetrahydrofuran and 2,3-dimethyltetrahydrofuran.
Examples of the cyclic lactone compound include β-propiolactone and ε-caprolactone.
Examples of the cyclic thioether compound include a tetrahydrothiophene derivative.
Examples of the spiro orthoester compound include those obtained by a reaction between an epoxy compound and a lactone.
Examples of the vinyl compound include ethylene glycol divinyl ether, alkyl vinyl ether, 2-chloroethyl vinyl ether, 2-hydroxyethyl vinyl ether, triethylene glycol divinyl ether, 1,4-cyclohexane dimethanol divinyl ether, hydroxybutyl vinyl ether, and propenyl propylene glycol. Examples include vinyl ether compounds such as ether, styrene, vinylcyclohexene, and the like.
Further, compounds that can be used as the cationic polymerizable organic substance (B) include ethylenically unsaturated compounds such as isobutylene and polybutadiene; thiirane compounds such as ethylene sulfide and thioepichlorohydrin; 1,3-propyne sulfide; Thietane compounds such as 3-dimethylthiethane and derivatives of the various compounds exemplified above as the cationically polymerizable organic substance (B) can also be mentioned.

Next, the acid generator (C) will be described.
As the acid generator (C) used in the curable composition of the present invention, any compound can be used as long as it can generate an acid by irradiation with heat or active energy rays. Although not limited, preferably, a double salt or a derivative thereof which is an onium salt that releases a Lewis acid upon irradiation with heat or active energy rays, since the cured product obtained by curing the curable composition has particularly good wet heat resistance. Among them, a double salt which is an onium salt that releases a Lewis acid upon irradiation with active energy rays or a derivative thereof is more preferable, because a cured product obtained by curing the curable composition has particularly good wet heat resistance.

A typical example of a double salt or a derivative thereof that is an onium salt that releases a Lewis acid upon irradiation with heat or active energy rays is represented by the following general formula [A] ^{m +} [B] ^m−
And a salt of a cation and an anion represented by

Here, but not limited to cation [A] m ⁺ is particularly preferably an onium which emits a Lewis acid by heat or active energy ray irradiation, the structure following general formula [(R ³⁾ _a Q] ^{m +}
Can be represented by
In the formula, R ³ is an organic group having 1 to 60 carbon atoms and which may contain atoms other than carbon atoms. a is an integer of any of 1 to 5. a number of R ³ are each independently, in some cases be different may be the same. Further, it is preferable that at least one of them is an organic group having an aromatic ring as described above, since the curable composition has good curability. Q is an atom or an atomic group selected from the group consisting of S, N, Se, Te, P, As, Sb, Bi, O, I, Br, Cl, F, and N = N. Further, when the valence of Q in the cation [A] ^{m +} is q, it is necessary that the relationship m = a−q is satisfied (however, N = N is treated as valence 0).

The anion [B] ^m- is not particularly limited, but is preferably a halide complex in terms of good curability of the curable composition, and has a structure, for example, of the following general formula [LX _b ] ^m-
Can be represented by
In the formula, L is a metal or metalloid which is a central atom of the halide complex, and B, P, As, Sb, Fe, Sn, Bi, Al, Ca, In, Ti, Zn, Sc, V, Cr, Mn, Co and the like. X is a halogen atom. b is an integer of any of 3 to 7. Further, when the valence of L in the anion [B] ^m− is p, it is necessary that the relationship m = bp is satisfied.
Specific examples of the anion [LX _b ] ^{m- in} the above general formula include tetrafluoroborate (BF ₄ ) ⁻ , hexafluorophosphate (PF ₆ ) ⁻ , hexafluoroantimonate (SbF ₆ ) ⁻ , and hexafluoroarse sulfonate _(AsF 6) ^-, hexachloroantimonate (SbCl ₆₎ ^-, and the like.

The anion [B] ^m- is represented by the following general formula [LX _b-1 (OH)] ^m-
A structure represented by the following formula can also be preferably used. L, X and b are the same as above. Other anions that can be used include perchlorate ion (ClO ₄ ) ⁻ , trifluoromethyl sulfite ion (CF ₃ SO ₃ ) ⁻ , fluorosulfonic acid ion (FSO ₃ ) ⁻ , and toluenesulfonic acid anion. ion, trinitrobenzene sulfonate anion, Kang Firth Gandolfo sulfonate, nonafluorobutane sulfonate, hexamethylene decafluoro octane sulfonate, tetraarylborate, tetrakis (pentafluorophenyl) borate _{[(C 6 F 5) 4} B] ^-, and the like can be given.

  Among these, acid generators that release a Lewis acid by heat (hereinafter, also referred to as thermal acid generators) include those having good curability of a curable composition and particularly high wet heat resistance of a cured product. The sulfonium salt represented by the formula (2) or the sulfonium salt represented by the formula (3) is more preferable.

(Wherein, R ²¹ and R ²² each independently represent an alkyl group having 1 to 10 carbon atoms, an aromatic group having 6 to 20 carbon atoms or an arylalkyl group having 7 to 30 carbon atoms; The hydrogen atom of the alkyl group, the aromatic group and the arylalkyl group are each independently a hydroxyl group, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an aromatic group having 6 to 20 carbon atoms, and a carbon atom having 7 to 7 carbon atoms. R ²¹ and R ²² may together form an alkylene chain of 2 to 7 carbon atoms, which may be substituted by 30 arylalkyl, nitro, sulfone or cyano group. May form a ring structure together with S ⁺
R ²³ and R ²⁴ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an aromatic group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, nitro Represents a group, a cyano group or a sulfone group, wherein the hydrogen atoms of the alkyl group, the aromatic group and the arylalkyl group are each independently a hydroxyl group, a halogen atom, an alkyl group having 1 to 10 carbon atoms, An aromatic group of 20, an arylalkyl group having 7 to 30 carbon atoms, a nitro group, a sulfone group or a cyano group;
An ^q′- represents a ^q′- valent anion, q ′ represents 1 or 2, and p ′ represents a coefficient for keeping a charge neutral. )

(Wherein, R ²⁵ represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an aromatic group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, a hydroxyl group, or a nitro group. , A sulfone group or a cyano group, wherein the hydrogen atoms of the alkyl group, the aromatic group, and the arylalkyl group are each independently a hydroxyl group, a halogen atom, an alkyl group having 1 to 10 carbon atoms, and a carbon atom having 6 to 20 carbon atoms. An aromatic group, an arylalkyl group having 7 to 30 carbon atoms, a nitro group, a sulfone group or a cyano group,
R ²⁶ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aromatic group having 6 to 20 carbon atoms or an arylalkyl group having 7 to 30 carbon atoms, and the alkyl group, the aromatic group and the aryl The hydrogen atom of the alkyl group is independently a hydroxyl group, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an aromatic group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a nitro group. May be substituted with a sulfone group or a cyano group,
R ²⁷ represents an alkyl group having 1 to 10 carbon atoms, in which the constituent methylene group may be substituted with a halogen atom, -O- or -S-,
An ^{q "} -represents an anion having a valency of q", q "represents 1 or 2, and p" represents a coefficient for keeping a charge neutral. )

In the compounds represented by the general formulas (2) and (3), the halogen atoms represented by R ²³ , R ²⁴ and R ²⁵ , and R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ , R ²⁶ and the halogen atom which may be substituted with group represented by R ^27, fluorine, chlorine, bromine, and iodine.

An alkyl group having 1 to 10 carbon atoms represented by R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ , R ²⁶ and R ²⁷ , and R ²¹ , R ²² , R ²³ , R ²⁴ , R ^25, and R ^In the alkyl group having 1 to 10 carbon atoms which may substitute the group represented by ²⁶ , the methylene group in the alkyl group is -O-, -S-, -CO-, -OCO-, -COO -, -C = C-, -NHCO-, -NH- or -CONH-, and specific examples include methyl, ethyl, propyl, isopropyl, butyl, s-butyl, t-butyl, Isobutyl, amyl, isoamyl, t-amyl, hexyl, cyclohexyl, heptyl, octyl, nonyl, ethyloctyl, 2-methoxyethyl, 3-methoxypropyl, 4-methoxybutyl, 2-butoxyethyl , Methoxyethoxyethyl, methoxyethoxyethoxyethyl, 3-methoxybutyl, 2-methylthioethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, bromomethyl, dibromomethyl, tribromomethyl, difluoroethyl , Trichloroethyl, dichlorodifluoroethyl, pentafluoroethyl, heptafluoropropyl, nonafluorobutyl, decafluoropentyl, tridecafluorohexyl, pentadecafluoroheptyl, heptadecafluorooctyl, methoxymethyl, 1,2-epoxyethyl, methoxy Ethyl, methoxyethoxymethyl, methylthiomethyl, ethoxyethyl, butoxymethyl, t-butylthiomethyl, 4-pentenyloxymethyl, tri Loroethoxymethyl, bis (2-chloroethoxy) methyl, methoxycyclohexyl, 1- (2-chloroethoxy) ethyl, 1-methyl-1-methoxyethyl, ethyldithioethyl, t-butoxycarbonylmethyl, ethyloxycarbonylmethyl, Ethylcarbonylmethyl, t-butoxycarbonylmethyl, acryloyloxyethyl, methacryloyloxyethyl, 2-methyl-2-adamantyloxycarbonylmethyl, acetylethyl, 2-methoxy-1-propenyl, hydroxymethyl, 2-hydroxyethyl, 1- Examples include hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 3-hydroxybutyl, 4-hydroxybutyl, 1,2-dihydroxyethyl, and the like.

^{Also, R 21, R 22, R} 23, R 24, R 25 and aromatic groups and ^R 21 having 6 to 20 carbon atoms represented by ^{R 26, R 22, R 23} , R 24, R 25 and R Examples of the aromatic group having 6 to 20 carbon atoms which may substitute the group represented by ²⁶ include phenyl, naphthyl, and anthranyl.
In ^{R 21, R 22, R 23} , R 24, R 25 and arylalkyl groups, and ^R 21 having 7 to 30 carbon atoms represented by ^{R 26, R 22, R 23} , R 24, R 25 and ^{R 26} As the arylalkyl group having 7 to 30 carbon atoms which may substitute the group represented, a combination of the alkyl group having 1 to 10 carbon atoms and the aromatic group having 6 to 20 carbon atoms described above is used. Things can be used.

In the general formulas (2) and (3), the anion of q ′ or q ″ valence represented by An ^q′− and An ^{q ″ —} is a methanesulfonic acid anion, a dodecylsulfonic acid anion, or a benzenesulfonic acid anion. , Toluenesulfonic acid anion, trifluoromethanesulfonic acid anion, naphthalenesulfonic acid anion, diphenylamine-4-sulfonic acid anion, 2-amino-4-methyl-5-chlorobenzenesulfonic acid anion, 2-amino-5-nitrobenzenesulfonic acid anion JP-A-10-235999, JP-A-10-337959, JP-A-11-102888, JP-A-2000-108510, JP-A-2000-168233, JP-A-2001-209969, JP 2001-322354 A, JP 2 006-248180, JP-A-2006-297907, JP-A-8-253705, JP-T-2004-503379, JP-A-2005-336150, and WO 2006/28006. In addition to organic sulfonic acid anions such as sulfonic acid anion, chloride ion, bromide ion, iodide ion, fluoride ion, chlorate ion, thiocyanate ion, perchlorate ion, hexafluorophosphate ion, hexafluoroantimonate Ion, tetrafluoroborate ion, octyl phosphate ion, dodecyl phosphate ion, octadecyl phosphate ion, phenyl phosphate ion, nonylphenyl phosphate ion, 2,2′-methylenebis (4,6-di-t-butylphenyl) ) Phosphonate ion, tetrakis (penta (Fluorophenyl) borate ion, quencher anion having a function of de-exciting (quenching) an active molecule in an excited state, anionic property such as carboxyl group, phosphonic acid group and sulfone group in cyclopentadienyl ring Metallocene compound anions such as ferrocene and luteocene having a group. Among them, hexafluorophosphate ion, hexafluoroantimonate ion, and tetrakis (pentafluorophenyl) borate ion are preferable because the wet heat resistance is particularly high.

Among the compounds represented by the formula (2), R ²¹ and R ²² together form an alkylene chain having 2 to 7 carbon atoms and form a ring structure together with S ⁺ to which they are bonded. Are preferred.

  The temperature range at which the thermal acid generator used as the acid generator (C) in the curable composition of the present invention can generate acid by heat and cure the curable composition is not particularly limited, but is preferably From the viewpoint that a cured product having excellent wet heat resistance is obtained and that the thermal stability during the process is good, 50 ° C to 250 ° C is preferable, 100 ° C to 220 ° C is more preferable, and 130 ° C to 200 ° C is more preferable. More preferred is 150 ° C to 180 ° C.

  In addition, commercially available products that can be suitably used as the thermal acid generator used as the acid generator (C) in the curable composition of the present invention include the following compounds (specific trade names are Sun Aid SI-B2A , Sun-Aid SI-B3A, Sun-Aid SI-B3, Sun-Aid SI-B4, Sun-Aid SI-60, Sun-Aid SI-80, Sun-Aid SI-100, Sun-Aid SI-110, Sun-Aid SI-150 (all manufactured by Sanshin Chemical Industry Co., Ltd.) ), Adeka Opton CP-66, Adeka Opton CP-77 (all manufactured by ADEKA Corporation), and the like. These can be used alone or in combination of two or more.

Next, as an acid generator that releases a Lewis acid upon irradiation with active energy rays (hereinafter, also referred to as a photoacid generator), since the curability of the curable composition is good, and the wet heat resistance of the cured product is particularly high, Among the onium salts, it is particularly effective to use aromatic diazonium salts, aromatic iodonium salts, aromatic sulfonium salts, and particularly the following aromatic onium salts (a) to (c). Among these, one type thereof can be used alone, or two or more types can be used in combination.
(A) aryldiazonium salts such as phenyldiazonium hexafluorophosphate, 4-methoxyphenyldiazonium hexafluoroantimonate, and 4-methylphenyldiazonium hexafluorophosphate (ii) diphenyliodonium hexafluoroantimonate, di (4-methylphenyl) iodonium Diaryliodonium salts such as hexafluorophosphate, di (4-tert-butylphenyl) iodonium hexafluorophosphate, and tricumyliodoniumtetrakis (pentafluorophenyl) borate (c) a sulfonium cation represented by the following group I or group II: , Sulfonium salts with hexafluoroantimonate ion, tetrakis (pentafluorophenyl) borate ion, etc.

  Other preferable examples include (η5-2,4-cyclopentadien-1-yl) [(1,2,3,4,5,6-η)-(1-methylethyl) benzene] -iron. An iron-arene complex such as hexafluorophosphate, an aluminum complex such as tris (acetylacetonato) aluminum, tris (ethylacetonatoacetato) aluminum, tris (salicylaldehyde) aluminum and a silanol such as triphenylsilanol. And the like.

  Among them, it is preferable to use an aromatic iodonium salt, an aromatic sulfonium salt, and an iron-arene complex from the viewpoint of practical use, photosensitivity, and wet heat resistance of the cured product. Further, among the aromatic sulfonium salts, the aromatic sulfonium salt represented by the following general formula (4) is more preferable because the wet heat resistance of the cured product becomes particularly high.

(Wherein, R ⁶¹ , R ⁶² , R ⁶³ , R ⁶⁴ , R ⁶⁵ , R ⁶⁶ , R ⁶⁷ , R ⁶⁸ , R ⁶⁹ and R ⁷⁰ each independently represent a hydrogen atom, a halogen atom, a carbon atom number of 1 to Represents an alkyl group having 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms or an ester group having 2 to 10 carbon atoms, and R ⁷¹ , R ⁷² , R ⁷³ , R ⁷⁴ , R ⁷⁵ , R ⁷⁶ , R ⁷⁷ and R ⁷⁸ each independently represent a hydrogen atom, a halogen atom or an alkyl group having 1 to 10 carbon atoms, R ⁸⁴ represents a group represented by hydrogen atom or the following general formula (4A), T ^- represents a monovalent anion Represents an ion.)

(Wherein, R ⁷⁹ , R ⁸⁰ , R ⁸¹ , R ⁸² and R ⁸³ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms or Represents an ester group having 2 to 10 carbon atoms.)

In the compound represented by the general formula (4), R ⁶¹ , R ⁶² , R ⁶³ , R ⁶⁴ , R ⁶⁵ , R ⁶⁶ , R ⁶⁷ , R ⁶⁸ , R ⁶⁹ , R ⁷⁰ , R ⁷¹ , R ⁷² , R Examples of the halogen atom represented by ⁷³ , R ⁷⁴ , R ⁷⁵ , R ⁷⁶ , R ⁷⁷ , R ⁷⁸ , R ⁷⁹ , R ⁸⁰ , R ⁸¹ , R ⁸² and R ⁸³ include fluorine, chlorine, bromine, iodine and the like. Can be

R ⁶¹ , R ⁶² , R ⁶³ , R ⁶⁴ , R ⁶⁵ , R ⁶⁶ , R ⁶⁷ , R ⁶⁸ , R ⁶⁹ , R ⁷⁰ , R ⁷¹ , R ⁷² , R ⁷³ , R ⁷⁴ , R ⁷⁵ , R ⁷⁶ , R ⁷⁷ , R ⁷⁸ , R ⁷⁹ , R ⁸⁰ , R ⁸¹ , R ⁸² and R ⁸³ , the alkyl group having 1 to 10 carbon atoms has a methylene group in the alkyl group of -O-, -S-,- It may be substituted by CO-, -OCO-, -COO-, -C = C-, -NHCO-, -NH- or -CONH-, and specific examples include methyl, ethyl, propyl, isopropyl, and butyl. , S-butyl, t-butyl, isobutyl, amyl, isoamyl, t-amyl, hexyl, cyclohexyl, heptyl, octyl, nonyl, ethyloctyl, 2-methoxyethyl, 3-methoxypropyl, 4-methoxy Chill, 2-butoxyethyl, methoxyethoxyethyl, methoxyethoxyethoxyethyl, 3-methoxybutyl, 2-methylthioethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, bromomethyl, dibromomethyl, Tribromomethyl, difluoroethyl, trichloroethyl, dichlorodifluoroethyl, pentafluoroethyl, heptafluoropropyl, nonafluorobutyl, decafluoropentyl, tridecafluorohexyl, pentadecafluoroheptyl, heptadecafluorooctyl, methoxymethyl, 1, 2-epoxyethyl, methoxyethyl, methoxyethoxymethyl, methylthiomethyl, ethoxyethyl, butoxymethyl, t-butylthiomethyl, 4-pen Tenyloxymethyl, trichloroethoxymethyl, bis (2-chloroethoxy) methyl, methoxycyclohexyl, 1- (2-chloroethoxy) ethyl, 1-methyl-1-methoxyethyl, ethyldithioethyl, t-butoxycarbonylmethyl, ethyl Oxycarbonylmethyl, ethylcarbonylmethyl, t-butoxycarbonylmethyl, acryloyloxyethyl, methacryloyloxyethyl, 2-methyl-2-adamantyloxycarbonylmethyl, acetylethyl, 2-methoxy-1-propenyl, hydroxymethyl, 2-hydroxy Ethyl, 1-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 3-hydroxybutyl, 4-hydroxybutyl, 1,2-dihydroxyethyl and the like can be mentioned.

Carbon atoms represented by R ⁶¹ , R ⁶² , R ⁶³ , R ⁶⁴ , R ⁶⁵ , R ⁶⁶ , R ⁶⁷ , R ⁶⁸ , R ⁶⁹ , R ⁷⁰ , R ⁷⁹ , R ⁸⁰ , R ⁸¹ , R ⁸² and R ⁸³ Examples of the alkoxy group of Formulas 1 to 10 include methoxy, ethoxy, propyloxy, isopropyloxy, butyloxy, s-butyloxy, t-butyloxy, isobutyloxy, pentyloxy, isoamyloxy, t-amyloxy, hexyloxy, cyclohexyloxy, cyclohexyl Methyloxy, tetrahydrofuranyloxy, tetrahydropyranyloxy, 2-methoxyethyloxy, 3-methoxypropyloxy, 4-methoxybutyloxy, 2-butoxyethyloxy, methoxyethoxyethyloxy, methoxyethoxyethoxyethyloxy, Methoxybutyloxy, 2-methylthioethyloxy, trifluoromethyloxy and the like can be mentioned.
Carbon atoms represented by R ⁶¹ , R ⁶² , R ⁶³ , R ⁶⁴ , R ⁶⁵ , R ⁶⁶ , R ⁶⁷ , R ⁶⁸ , R ⁶⁹ , R ⁷⁰ , R ⁷⁹ , R ⁸⁰ , R ⁸¹ , R ⁸² and R ⁸³ Examples of the ester group having a number of 2 to 10 include methoxycarbonyl, ethoxycarbonyl, isopropyloxycarbonyl, phenoxycarbonyl, acetoxy, propionyloxy, butyryloxy, chloroacetyloxy, dichloroacetyloxy, trichloroacetyloxy, trifluoroacetyloxy, and t-butyl. Examples include carbonyloxy, methoxyacetyloxy, benzoyloxy and the like.

Examples of the monovalent anion represented by T ⁻ include monovalent ones exemplified as the anion [B] ^m− , and specific examples thereof include tetrakis (pentafluorophenyl) borate. [(C ₆ F ₅ ) ₄ B] ⁻ , tetrafluoroborate (BF ₄ ) ⁻ , hexafluorophosphate (PF ₆ ) ⁻ , hexafluoroantimonate (SbF ₆ ) ⁻ , hexafluoroarsenate (AsF ₆ ) ⁻ , Hexachloroantimonate (SbCl ₆ ) ⁻ , perchlorate ion (ClO ₄ ) ⁻ , trifluoromethyl sulfite ion (CF ₃ SO ₃ ) ⁻ , fluorosulfonic acid ion (FSO ₃ ) ⁻ , toluenesulfonic acid anion, Nitrobenzenesulfonic acid anion, camphorsulfonate, nonafluorobutanes Foneto, hexa decafluoro octane sulfonate, tetraarylborate, may be mentioned tetrakis (pentafluorophenyl) borate.

  In the curable composition of the present invention, as the acid generator of the component (C), one or more thermal acid generators can be used, and one or more photoacid generators can be used. Alternatively, a thermal acid generator and a photoacid generator can be used in combination.

  In the curable composition of the present invention, the content of two or more cationic dyes (A) is not particularly limited, but the total of two or more cationic dyes (A) and (B) are essential components of the present invention. , (C), preferably 0.5 to 20.0% by mass, more preferably 2.0 to 15.0% by mass, and still more preferably 3.0 to 10.0% by mass in the total amount of the components. Within these ranges, the cured product has particularly good wet heat resistance. When used in a wavelength cut filter, the total content of two or more cationic dyes (A) is 3.0 in the total amount of the components (A), (B) and (C). It is preferable that the content is not less than 3.0% by mass, and if it is less than 3.0% by mass, the transmittance is increased, and the wavelength cut performance may not be sufficiently obtained.

  Further, in the curable composition of the present invention, the content of the two or more cationic dyes (A) is preferably from 0.01 to more than the total of the two or more cationic dyes with respect to the cationically polymerizable organic substance (B). The range of 30% by mass, more preferably 1% to 25% by mass, and still more preferably 1% to 10% by mass is preferable in that the wet heat resistance of the cured product becomes particularly good.

  In the curable composition of the present invention, the content of the cationically polymerizable organic substance (B) is not particularly limited, but is an essential component of the present invention (A) because the wet heat resistance of the cured product is particularly good. ), Preferably 70.0 to 99.0% by mass, more preferably 80.0 to 97.5% by mass, based on the total amount of component (B) and component (C).

  In the curable composition of the present invention, the content of the acid generator (C) is not particularly limited. However, since the wet heat resistance of the cured product of the curable composition becomes particularly good, it is an essential component of the present invention. The total amount of certain components (A), (B), and (C) is preferably 0.1 to 5.0% by mass, more preferably 0.5 to 5.0% by mass.

  Further, the use ratio of the acid generator (C) to the cationically polymerizable organic substance (B) is not particularly limited, and the acid generator (C) may be used at a generally normal use ratio within a range that does not inhibit the object of the present invention. For example, with respect to 100 parts by mass of the cationically polymerizable organic substance (B), 0.05 to 10 parts by mass, particularly 0.5 to 10 parts by mass of the acid generator (C) makes the cured product particularly excellent in wet heat resistance. It is suitable in that it becomes.

  In the curable composition of the present invention, an organic solvent (D) capable of dissolving or dispersing the above-described components and optional components described below, if necessary, for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, diacetone alcohol, methyl cellosolve , Ethyl cellosolve, chloroform, methylene chloride, hexane, heptane, octane, cyclohexane, benzene, toluene, xylene, methanol, ethanol, isopropanol, cyclohexanone, dimethylformamide, dimethylacetamide, N-methylpyrrolidinone, propylene glycol monomethyl ether acetate (PGMAc) , Ethyl acetate, propyl acetate, butyl acetate, ethyl lactate and the like. In the curable composition of the present invention, the content of the organic solvent (D) is appropriately selected according to the use of the curable composition and the like, and is not particularly limited. (Total content of all components other than the organic solvent (D)) is preferably in an amount of 1 to 100% by mass, and in particular, the organic solvent (D) is adjusted to have a solid content of 5 to 90% by mass. When it is contained, it is suitable when the curable composition of the present invention is used by application as in the production of a wavelength cut filter.

  Further, the curable composition of the present invention comprises the essential components of the cationic dye (A), the cationically polymerizable organic substance (B) and the acid generator (C), and the organic solvent ( In addition to D), as an optional component, as long as the effects of the present invention are not impaired, a phenol-based, phosphorus-based, sulfur-based antioxidant or latent antioxidant; benzotriazole-based, triazine-based, Benzoate UV absorbers; antistatic agents consisting of cationic surfactants, anionic surfactants, nonionic surfactants, amphoteric surfactants, etc .; halogen compounds, phosphoric ester compounds, phosphoric amide compounds Flame retardants such as compounds, melamine compounds, fluororesins or metal oxides, melamine (poly) phosphate, piperazine (poly) phosphate; hydrocarbons, fatty acids, and aliphatic alcohols Lubricant, aliphatic ester-based, aliphatic amide-based or metallic soap-based lubricant; pigment, colorant such as carbon black; fumed silica, fine-particle silica, silica, diatomaceous earth, clay, kaolin, silica gel, calcium silicate Silicate-based inorganic additives such as sericite, kaolinite, flint, feldspar powder, vermiculite, attapulgite, talc, mica, minesoteite, pyrophyllite and silica; fillers such as glass fiber and calcium carbonate; nucleating agents; Crystallizing agents such as crystallization accelerators, silane coupling agents, rubber elasticity imparting agents such as flexible polymers, sensitizers, other monomers, defoamers, thickeners, leveling agents, plasticizers, polymerization Various additives such as inhibitors, antistatic agents, flow regulators, coupling agents, and adhesion promoters can be contained alone or in combination of two or more. The use amount of these various additives is 50% by mass or less in total in the solid content of the curable composition of the present invention.

  The antioxidant that can be added as necessary to the curable composition of the present invention is not particularly limited, but specific products include ADK STAB AO-20 and ADK STAB AO shown below. -30, Adekastab AO-40, Adekastab AO-50, Adekastab AO-60, Adekastab AO-80, Adekastab AO-330 (all manufactured by ADEKA Corporation) and the like can be preferably used.

  The ultraviolet absorber that can be added as necessary to the curable composition of the present invention is not particularly limited, but specific products include ADK STAB LA-29 and ADK STAB LA- 31G, Adekastab LA-32, Adekastab LA-46, Adekastab LA-52, Adekastab LA-63P, Adekastab LA-68, Adekastab LA-72, Adekastab LA-77Y, Adekastab LA-81, Adekastab LA- 82, ADK STAB LA-87 (all manufactured by ADEKA Corporation) and the like can be preferably used.

  The method for curing the curable composition of the present invention is not particularly limited, and a conventional method can be used. For example, there is a method in which a curable composition also containing the organic solvent (D) is applied to a substrate, and then cured by active energy rays or heating.

  The curable composition that also contains the organic solvent (D) can be applied by a known application method so as to have an appropriate coating thickness on an appropriate substrate depending on the application. Absent. For example, when manufacturing a wavelength cut filter, as described later in detail, the wavelength cut filter is applied by a spin coating method or the like so that a coating layer having a thickness of 1 to 200 μm is formed on a glass substrate. After applying the curable composition also containing the organic solvent (D), the organic solvent (D) contained in the coating film is dried, if necessary.

  When the curable composition of the present invention contains a thermal acid generator as the acid generator (C) and is thermally cured, the composition is not particularly limited. However, a hot plate such as a hot plate, an atmospheric oven, an inert gas oven, a vacuum oven, It can be cured by heating with a hot air circulation oven or the like.

The heating temperature at the time of thermal curing of the curable composition of the present invention is not particularly limited, but is preferably 130 ° C to 200 ° C, and is preferably 150 ° C to 180 ° C in that a cured product having suitable wet heat resistance is obtained. Is more preferred. When the heating temperature exceeds 200 ° C., there is a concern that decomposition of the dye, thermal deterioration such as discoloration of the resin, or a decrease in performance due to volatilization of the components, and the like, when the heating temperature is lower than 130 ° C., the curing temperature is low, There is a risk of poor reaction.
The curing time during the thermal curing of the curable composition of the present invention is not particularly limited, but is preferably 10 minutes to 1 hour in that a cured product having suitable wet heat resistance is obtained, preferably 10 minutes to 30 minutes. Is more preferred. If the curing time exceeds 1 hour, the production time of the cured product is long, and it is not suitable for mass production. If the curing time is less than 10 minutes, the curing time is short, and there is a possibility that the reaction may be defective.

  In addition, when the curable composition of the present invention contains a photoacid generator as the acid generator (C) and is photocured, it can be cured by irradiating active energy rays such as ultraviolet rays. After 0.1 seconds to several minutes, the composition can be cured to a touch-dry state or a solvent-insoluble state. Any suitable active energy ray may be used as long as it induces decomposition of the photoacid generator, but is preferably an ultra-high, high, medium, low-pressure mercury lamp, xenon lamp, carbon arc lamp, metal halide lamp, or fluorescent lamp. 2000 angstroms obtained from tungsten lamp, excimer lamp, germicidal lamp, excimer laser, nitrogen laser, argon ion laser, helium cadmium laser, helium neon laser, krypton ion laser, various semiconductor lasers, YAG laser, light emitting diode, CRT light source Electromagnetic wave energy having a wavelength of 7000 to 7000 angstroms and high energy rays such as electron beams, X-rays, and radiations are used.

  The irradiation time of the active energy ray depends on the intensity of the energy ray, the thickness of the coating film, the kind of the cationically polymerizable organic compound and the like, but usually about 0.1 second to 10 seconds is sufficient. However, it is preferable to apply a longer irradiation time to a relatively thick painted object or the like. After 0.1 seconds to a few minutes after the irradiation of the active energy ray, most compositions are dried to the touch by cationic polymerization.However, heat energy such as heating or a thermal head may be used in combination to promote cationic polymerization. Is preferred.

  Specific applications of the curable composition and the cured product of the present invention include a wavelength cut filter, a paint, a coating agent, a lining agent, an adhesive, a printing plate, an insulating varnish, an insulating sheet, a laminate, a printed board, and a semiconductor. Sealants, molding materials, putties, glass fiber impregnants, fillers for devices, LED packages, liquid crystal fillers, organic EL, optical devices, electrical insulation, electronic components, separation membranes, etc. , Passivation films for semiconductors and solar cells, interlayer insulating films, protective films, printed circuit boards, color filters for color televisions, PC monitors, portable information terminals, CCD image sensors, electrode materials for plasma display panels, printing inks , Dental compositions, stereolithography resins, both liquid and dry films, micromechanical parts, glass fiber cable coatings, holographic recording materials Can be mentioned developing, is not particularly limited in its applications, it is preferably used as a wavelength cut filter.

  When the cured product obtained by curing the curable composition of the present invention is used as a wavelength cut filter, the main applications are a digital still camera, a digital video camera, a surveillance camera, a vehicle-mounted camera, a web camera, a camera for a mobile phone, and the like. For the visibility of solid-state imaging devices such as CCD and C-MOS in solid-state imaging devices; for automatic exposure meters; for display devices such as plasma displays; and mounted on window glasses of automobiles and buildings. It can also be used as a heat ray cut filter or the like.

  The wavelength cut filter of the present invention includes at least a part of a cured product of the curable composition of the present invention. Hereinafter, an example of an embodiment of the wavelength cut filter of the present invention will be described with reference to the drawings. Note that the wavelength cut filter of the present invention can be configured and used without being limited to the embodiment described below.

  The wavelength cut filter 1 of this embodiment has a coating layer (I) made of a cured product of the curable composition of the present invention on one surface of a glass substrate (H), and the other side of the glass substrate (H). The infrared reflective film (J) is laminated on the surface, and as shown in FIG. 1, the side having the coating layer (I) can be the light incident side, and as shown in FIG. The side having the infrared reflective film (J) may be the light incident side. Hereinafter, each layer will be described in order.

<Glass substrate (H)>
The glass substrate (H) used for the wavelength cut filter of the present embodiment can be appropriately selected from colorless or colored transparent glass materials in the visible region and used, for example, soda-lime glass, white plate glass, Borosilicate glass, tempered glass, quartz glass, phosphate glass, or the like can be used, and infrared absorbing glass, blue glass, or the like containing a trace amount of a metal component can also be used. Among them, soda-lime glass is preferred because it is inexpensive and easily available, and white plate glass, borosilicate glass and tempered glass are preferred because they are easily available, have high hardness and are excellent in workability. In addition, infrared absorbing glass and blue glass are preferable because the wavelength cut performance of the wavelength cut filter is further improved.

Further, after the glass substrate (H) is subjected to a pretreatment with a silane coupling agent or the like, the curable composition of the present invention is applied as a coating solution to form a coating layer (I) containing a dye described below. In addition, the adhesion of the coating layer (I) containing the dye after drying the coating liquid to the glass substrate is enhanced.
Examples of the silane coupling agent include epoxy-functional alkoxysilanes such as γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, and β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane. Amino-functional alkoxysilanes such as N-β (aminoethyl) -γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxy And mercapto-functional alkoxysilanes such as silane.

  Further, the wavelength cut filter of the present embodiment may have an underlayer between the glass substrate (H) and the coating layer (I). The base layer is coated with a coating liquid obtained by dispersing an aggregate of metal oxide fine particles having an average secondary particle diameter of 20 to 250 nm in which primary particles having an average primary particle diameter of 5 to 100 nm aggregated in an appropriate solvent. And the thickness is preferably 30 to 1000 nm. The aggregate of the metal oxide fine particles is preferably 0.1 to 50% by mass based on the total amount of the coating solution.

  The thickness of the glass substrate (H) is not particularly limited, but is preferably 0.05 to 8 mm, and more preferably 0.05 to 1 mm in terms of weight reduction and strength.

<Coating layer (I)>
The coating layer (I) composed of a cured product obtained by curing the curable composition of the present invention, which is used in the wavelength cut filter of the present embodiment, may be, for example, a coating liquid (curable composition of the present invention) prepared by the method described in Examples. Composition), and the obtained coating liquid is applied onto a glass substrate (H), dried, and cured by actinic radiation or heating as described in detail above. .

As a coating method of the coating liquid, spin coating, dip coating, spray coating, bead coating, air knife coating, curtain coating, roller coating, wire bar coating, gravure coating, die coating, An extrusion coating method using a hopper is exemplified.
The thickness of the coating layer (I) is preferably 1 to 200 μm, since a uniform film can be obtained and this is advantageous for thinning.

<Infrared reflective film (J)>
The infrared reflective film (J) used in the cut filter according to the present embodiment has a function of blocking light in a wavelength region of 700 to 1200 nm, and low refractive index layers and high refractive index layers are alternately laminated. It is formed of a dielectric multilayer film.

  As the material constituting the low refractive index layer, a material having a refractive index of 1.2 to 1.6 can be used, and examples thereof include silica, alumina, lanthanum fluoride, magnesium fluoride, and sodium aluminum hexafluoride. No.

  As a material constituting the high refractive index layer, a material having a refractive index of 1.7 to 2.5 can be used. For example, titanium oxide, zirconium oxide, tantalum pentoxide, niobium pentoxide, lanthanum oxide, oxidized oxide In addition to yttrium, zinc oxide, zinc sulfide, indium oxide, and the like, those containing these as main components and a small amount of titanium oxide, tin oxide, cerium oxide, or the like are also included.

The method of laminating the low-refractive-index layer and the high-refractive-index layer is not particularly limited as long as a dielectric multilayer film in which these layers are laminated is formed. For example, a CVD method, a sputtering method, And a method of forming a dielectric multilayer film in which low-refractive-index layers and high-refractive-index layers are alternately laminated by a vacuum deposition method or the like. Alternatively, a dielectric multilayer film can be formed in advance, and this can be bonded to a glass substrate with an adhesive.
The number of layers is preferably from 10 to 80 layers, more preferably from 25 to 50 layers, from the viewpoint of process and strength.

The thickness of the low refractive index layer and the thickness of the high refractive index layer are usually 0.1λ to 0.5λ, respectively, where λ (nm) is the wavelength of the light beam to be blocked. When the thickness is less than 0.1λ or more than 0.5λ, the product (nd) of the refractive index (n) and the physical thickness (d) greatly differs from the optical thickness expressed by a multiple of λ / 4. There is a possibility that blocking or transmission of a specific wavelength may not be possible.
As the infrared reflective film (J), in addition to the above dielectric multilayer film, a film containing a dye having a maximum absorption wavelength of 700 to 1100 nm, a laminate of polymers, and a film formed by applying a cholesteric liquid crystal A material using an organic material such as the above can also be used.

  Hereinafter, the present invention will be described in more detail with reference to Examples and the like, but the present invention is not limited to these Examples and the like.

[Examples 1 to 24] Preparation of curable compositions 1 to 24 In the formulations shown in Tables 1 to 4, the cationically polymerizable organic substance (B) and the organic solvent (D) were mixed until no insoluble matter was present. After stirring, a solution α was obtained. In addition, in the formulations shown in Tables 1 to 4, the cationic dye (A), the acid generator (C), the organic solvent (D), and optionally the additive (E) were mixed, and the mixture was stirred until insolubles disappeared. Thus, a solution β was obtained. The solution α and the solution β were mixed immediately before being used for preparing a test piece to be described later, and the mixture was stirred until it became uniform, thereby obtaining curable compositions 1 to 24 corresponding to Examples 1 to 24.

[Comparative Examples 1 to 6] Preparation of Comparative Curable Compositions 1 to 6 Comparative Examples 1 to 6 were prepared in the same manner as in the preparation method of the above curable compositions 1 to 24 except that the formulations shown in Table 5 were used. Corresponding curable compositions 1 to 6 were obtained. In addition, each of the curable compositions for comparison 1 to 6 contains only one kind of the cationic dye (A).

  Each symbol in Tables 1 to 5 represents the following, respectively.

Cationic dye (A)
A-1: Compound No. N, N-bis (trifluoromethanesulfonyl) imidate A-2 of Compound No. 100: Compound No. 100 100 tetrakis (pentafluorophenyl) borate A-3: Compound No. N, N-bis (nonafluorobutanesulfonyl) imidate A-4: Compound No. 100 N, N-bis (trifluoromethanesulfonyl) imidate A-5 of Compound No. 65: Compound No. 65 N, N-bis (trifluoromethanesulfonyl) imidate A-6: Compound No. 102 Tetrakis (pentafluorophenyl) borate A-7: Compound No. 103 105 tetrakis (pentafluorophenyl) borate A-8: Compound No. 105 N, N-bis (fluorosulfonyl) imidate A-9: Compound No. 100 103, N, N-bis (fluorosulfonyl) imidate A-10: Compound No. 103 104, N, N-bis (trifluoromethanesulfonyl) imidate A-11: Compound No. 104 Trifluoromethanesulfonate A-12: Compound No. 104 Nonafluorobutanesulfonate A-13: Compound No. 104 Tetrakis (pentafluorophenyl) borate A-14: Compound No. 104 No. 104 tris (trifluoromethanesulfonyl) methide salt A-15: Compound No. 104 Hexafluorophosphate A-16 of Compound No. 104: Compound No. 104 No. 106 tetrakis (pentafluorophenyl) borate A-17: Compound No. 106 107 tetrakis (pentafluorophenyl) borate A-18: Compound No. 107 76 tetrakis (pentafluorophenyl) borate A-19: Compound No. 76 99 tetrakis (pentafluorophenyl) borate A-20: Compound No. 99 101 tetrakis (pentafluorophenyl) borate A-21: Compound No. 101 Trifluoromethanesulfonate A-22: Compound No. 103 N, N-bis (nonafluorobutanesulfonyl) imidate A-23: Compound No. 104 N, N-bis (fluorosulfonyl) imidate A-24: Compound No. 104 Hexafluorophosphate A-25 of Compound 103: Compound No. 103 N, N-bis (nonafluorobutanesulfonyl) imidate A-26: Compound No. 101 Tris (pentafluoroethyl) trifluorophosphate A-27: Compound No. 100 103 tris (pentafluoroethyl) trifluorophosphate A-28: Compound No. 103 76, N, N-bis (trifluoromethanesulfonyl) imidate A-29: Compound No. 76 No. 104 tris (pentafluoroethyl) trifluorophosphate A-30: Compound No. 104 100 hexafluorophosphate

Cationic polymerizable organic substance (B)
B-1: Celloxide 2021P (Epoxy compound manufactured by Daicel Corporation)
B-2: Adekaglycylol ED-503 (epoxy compound manufactured by ADEKA Corporation)
B-3: Adeka Resin EP-4100E (epoxy compound manufactured by ADEKA Corporation)
B-4: Aron oxetane OXT-101 (oxetane compound manufactured by Toagosei Co., Ltd.)
B-5: EHPE-3150 (Epoxy compound manufactured by Daicel Corporation)
B-6: Aron oxetane OXT-221 (oxetane compound manufactured by Toagosei Co., Ltd.)
B-7: ADEKA Resin EP-4088S (epoxy compound manufactured by ADEKA Corporation)
B-8: EPPN-201 (Nippon Kayaku Co., Ltd. epoxy compound)

Acid generator (C)
C-1: Sun-Aid SI-100 (thermal acid generator manufactured by Sanshin Chemical Industry Co., Ltd.)
C-2: Sun-Aid SI-110 (thermal acid generator manufactured by Sanshin Chemical Industry Co., Ltd.)
C-3: Compound represented by the following structural formula 1 (photoacid generator)
C-4: San-Aid SI-60 (thermal acid generator manufactured by Sanshin Chemical Industry Co., Ltd.)
C-5: Sun-Aid SI-80 (thermal acid generator manufactured by Sanshin Chemical Industry Co., Ltd.)
C-6: San-Aid SI-150 (thermal acid generator manufactured by Sanshin Chemical Industry Co., Ltd.)
C-7: CPI-100P (San Apro Co., Ltd. photoacid generator)

Organic solvent (D)
D-1: methyl ethyl ketone D-2: diacetone alcohol D-3: dimethylacetamide D-4: cyclohexanone additive (E)
E-1: ADK STAB AO-60 (Antioxidant manufactured by ADEKA Corporation)
E-2: ADK STAB AO-20 (Antioxidant manufactured by ADEKA Corporation)
E-3: ADK STAB AO-40 (Antioxidant manufactured by ADEKA Corporation)
E-4: ADK STAB AO-50 (Antioxidant manufactured by ADEKA Corporation)
E-5: ADK STAB AO-80 (Antioxidant manufactured by ADEKA Corporation)

<Preparation of test pieces for evaluation by thermosetting>
Curable compositions 1-4, 6-9, 11-14, 16-19, 21-24 (corresponding to Examples 1-4, 6-9, 11-14, 16-19, 21-24, respectively) Each was spin-coated on a glass substrate under the condition of 800 rpm × 10 seconds, and dried on a hot plate (90 ° C., 10 minutes). After drying the solvent, the coated glass substrate was placed in an oven, and heat-cured at 180 ° C. for 20 minutes to prepare a test piece for evaluation.
In addition, the curable compositions for comparison 1 to 3 and 6 (corresponding to Comparative Examples 1 to 3 and 6, respectively) were thermally cured in the same manner to prepare test pieces for evaluation.

<Preparation of test pieces for evaluation by light curing>
Each of the curable compositions 5, 10, 15, and 20 (corresponding to Examples 5, 10, 15, and 20, respectively) was spin-coated on a glass substrate under the conditions of 800 rpm × 10 seconds, and dried on a hot plate (90 ° C., 10 minutes). After drying the solvent, the coated glass substrate was exposed to light (300 mJ / cm ² ) with a high-pressure mercury lamp and photo-cured to prepare a test piece for evaluation.
In addition, the curable compositions for comparison 4 and 5 (corresponding to Comparative Examples 4 and 5) were similarly photocured to prepare test specimens for comparison.

<Moisture and heat resistance test>
The test piece for evaluation obtained above was placed in a thermo-hygrostat at a temperature of 85 ° C. and a humidity of 85%, and the dye was precipitated from the test piece every 5 hours, 10 hours, 20 hours, and 50 hours. Was visually observed and evaluated according to the following evaluation criteria. The results are shown in Tables 6-1, 6-2 and 6-3.
(Evaluation criteria)
：: No precipitation △: Partial precipitation (less than 10% of test piece surface area)
×: Precipitation (10% or more of the test piece surface area)

  In Tables 6-1, 6-2 and 6-3, the types (A-1 to A-30) of the cationic dyes used are described. Are described as “identical” when the structures are the same, and as “different” when the structures are different. The ratio of the cationic dye to the component (B) of the curable composition is also described. Furthermore, the ratio of each cationic dye to the total amount of the cationic dye is also described.

<Wavelength cut filter transmittance measurement>
For the test pieces for evaluation of Examples 1 to 5 and Comparative Example 6, in order to evaluate the performance as a wavelength cut filter, the transmittance at the maximum absorption wavelength in the range of 650 to 1200 nm was measured. The transmittance was measured with an ultraviolet-visible-near-infrared spectrophotometer V-570 manufactured by JASCO Corporation. Table 7 shows the results. It can be said that the smaller the numerical value of the transmittance, the better the wavelength cut performance.

From the results of Tables 6-1, 6-2 and 6-3, the case where two or more cationic dyes are contained (Example) is clearly more resistant to moisture than the case where only one kind is used (Comparative Example). It turns out that it is excellent in heat property.
When two cationic dyes had the same cation portion but different anion portions (Examples 5, 11, 18, 19, and 20), the dye was precipitated by 10% or more in a moist heat resistance test of 50 hours. However, when the cation part is different and the anion part is the same, or when both the cation part and the anion part are different (Examples 1-4, 6-10, 12-17, 21-24), the moist heat resistance test 50 With respect to the time, there was no X-determination, indicating that the wet heat resistance was better than when two kinds of cationic dyes having the same cation portion but different anion portions were used.

  From the results of Examples 1 to 5 in Table 7, it can be seen that the cured product of the curable composition of the present invention is useful for a wavelength cut filter since it has low transmittance and excellent wavelength cut performance. Also, from the results of Comparative Example 6, it is understood that when the total content of the dye is small, the transmittance is increased and the wavelength cut performance is inferior.

  As described above, a cured product obtained by curing the curable composition of the present invention containing two or more kinds of cationic dye (A), cationically polymerizable organic substance (B) and acid generator (C) has wet heat resistance and wavelength cutoff. It shows that the curable composition of the present invention has excellent performance and is useful for a wavelength cut filter.

The cured product obtained by curing the curable composition of the present invention has excellent wet heat resistance. A cured product obtained by curing the curable composition is suitable for a wavelength cut filter.

Claims (10)

It contains two or more cationic dyes (A), a cationically polymerizable organic substance (B), and an acid generator (C) ,
A curable composition wherein the two or more cationic dyes (A) are polymethine compounds represented by the following general formula (1) and have at least two cationic dyes having different cation moieties .

(Wherein, A represents a group selected from the following group I (a) to (m), A ′ represents a group selected from the following group II (a ′) to (m ′), Represents a linking group containing a methine chain represented by the following general formula (1-A), An ^q- represents a q-valent anion, q represents 1 or 2, and p keeps a charge neutral. Represents the coefficient,
When A is a group selected from (a) to (d) and (h) to (k), A ′ is selected from (a ′) to (d ′) and (h ′) to (k ′). When A is a group selected from (e) to (g) and (l) to (m), A ′ is (e ′) to (g ′), (l ′) to (m ′) ). )


(Wherein, ring C and ring C ′ each independently represent a benzene ring, a naphthalene ring, a phenanthrene ring or a pyridine ring;
In the formula, R ¹ and R ¹ ′ each independently represent a hydrogen atom, a hydroxyl group, a halogen atom, a nitro group, a cyano group, a carboxyl group, an amino group, a dialkylamino group having 2 to 16 carbon atoms, a carbon atom having 12 to 12 carbon atoms. 40 diarylamino groups, arylalkylamino groups having 7 to 28 carbon atoms, amide groups, aryl groups having 6 to 20 carbon atoms, arylalkyl groups having 7 to 30 carbon atoms or alkyl having 1 to 8 carbon atoms A hydrogen atom of a dialkylamino group, a diarylamino group, an arylalkylamino group, an aryl group, an arylalkyl group and an alkyl group in R ¹ and R ¹ ′ are each independently a hydroxyl group, a halogen atom, a nitro group , a cyano group, a carboxyl group, an amino group, may be substituted with a amido group or a ferrocenyl group, Jiarukirua in said R ¹ and R ^{1 '} M, a diarylamino group, an arylalkylamino group, an aryl group, an arylalkyl group and a methylene group in the alkyl group each independently represent -O-, -S-, -CO-, -COO-, -OCO-. _{, -SO 2 -, - NH -} , - CONH -, - NHCO -, - N = CH- or may be replaced by -CH = CH-,
In the formula, R ^{2 to} R ⁹ and R ² ′ to R ⁹ ′ each independently represent a hydrogen atom, a hydroxyl group, a halogen atom, a nitro group, a cyano group, a carboxyl group, an amino group, an amide group, a carbon atom number of 6 to 20. An aryl group, an arylalkyl group having 7 to 30 carbon atoms or an alkyl group having 1 to 8 carbon atoms, wherein the aryl group, the arylalkyl group and the aryl group in R ^{2 to} R ⁹ and R ² ′ to R ⁹ ′ The hydrogen atom of the alkyl group may be independently substituted with a hydroxyl group, a halogen atom, a nitro group, a cyano group, a carboxyl group, an amino group, an amide group or a ferrocenyl group, and the R ^{2 to} R ⁹ and R ² ′ aryl groups in to R ⁹ ', a methylene group in the arylalkyl and alkyl groups are each independently, -O -, - S -, - CO -, - COO -, - OCO -, - SO 2 -, -NH-, -CONH- -NHCO -, - N = CH- or may be replaced by -CH = CH-,
In the formula, X and X ′ each independently represent an oxygen atom, a sulfur atom, a selenium atom, —CR ⁵¹ R ⁵² —, a cycloalkane-1,1-diyl group having 3 to 6 carbon atoms, —NH— or —. NY ² - ^{represents, R 51} and ^{R 52} each independently represent a hydrogen atom, a hydroxyl group, a halogen atom, a nitro group, a cyano group, a carboxyl group, an amino group, an amide group, an aryl group having 6 to 20 carbon atoms, a carbon Represents an arylalkyl group having 7 to 30 atoms or an alkyl group having 1 to 8 carbon atoms, and hydrogen atoms of the aryl group, the arylalkyl group and the alkyl group in R ⁵¹ and R ⁵² are each independently a hydroxyl group, a halogen atom, May be substituted with an atom, a nitro group, a cyano group, a carboxyl group, an amino group, an amide group or a ferrocenyl group, and the aryl group, arylalkyl group and alkyl group in R ⁵¹ and R ⁵² may be substituted. Methylene groups in the kill groups are each independently, -O -, - S -, - CO -, - COO -, - OCO -, - SO 2 -, - NH -, - CONH -, - NHCO -, - May be substituted with N = CH- or -CH = CH-,
In the formula, Y, Y ′ and Y ² each independently represent a hydrogen atom, a hydroxyl group, a halogen atom, a cyano group, a carboxyl group, an amino group, an amide group, a nitro group, an aryl group having 6 to 20 carbon atoms, a carbon atom arylalkyl group or an alkyl group having 1 to 8 carbon atoms in the C7-30, the Y, Y 'and Y ² in the aryl group, a hydrogen atom in the arylalkyl and alkyl groups are each independently, a hydroxyl group, a halogen group, a cyano group, a carboxyl group, an amino group, an amido group, may be substituted with a ferrocenyl group or a nitro group, said Y, Y 'and Y ² in the aryl group, arylalkyl group, and the alkyl group methylene groups are each independently, -O -, - S -, - CO -, - COO -, - OCO -, - SO 2 -, - NH -, - CONH -, - NHCO -, - N = CH -Or -CH = C - it may be substituted with,
In the formula, r and r ′ are 0 or (a) to (e), (g) to (j), (1), (m), (a ′) to (e ′), (g ′) to (J '), (l') and (m ') represent one or more possible substituents. )
(In the formula, k represents an integer of 0 to 4,
In the formula, the hydrogen atoms of the methine chain are each independently a hydroxyl group, a halogen atom, a cyano group, -NRR ', an aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms or a carbon atom. It may be substituted with an alkyl group of 1 to 8, and the alkyl group becomes a corresponding alkylene group and bonds to any two carbon atoms of the methine chain to form a ring structure having 3 to 10 carbon atoms. And each hydrogen atom of the ring structure is independently a hydroxyl group, a halogen atom, a cyano group, -NRR ', an aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a carbon atom. May be substituted with an alkyl group having 1 to 8 atoms,
R and R ′ in the methine chain and the ring structure each independently represent an aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or an alkyl group having 1 to 8 carbon atoms. A hydrogen atom in the -NRR 'in the methine chain and the ring structure, an aryl group, an arylalkyl group and an alkyl group may be further independently substituted with a hydroxyl group, a halogen atom, a cyano group or -NRR'. And the aryl group in the methine chain and the ring structure, the methylene group in the arylalkyl group and the methylene group in the alkyl group are each independently -O-, -S-, -CO-, -COO-, -OCO-, _{-SO 2 -, - NH -,} - CONH -, - NHCO -, - N = CH- or may be replaced by -CH = CH-. ) A curable composition containing two or more cationic dyes (A), a cationically polymerizable organic substance (B), and an acid generator (C), and is used for a wavelength cut filter . The curable composition according to claim 2 , wherein the cationic dye (A) is a polymethine compound represented by the following general formula (1).
(Wherein, A represents a group selected from the following group I (a) to (m), A ′ represents a group selected from the following group II (a ′) to (m ′), Represents a linking group containing a methine chain represented by the following general formula (1-A), An ^q- represents a q-valent anion, q represents 1 or 2, and p keeps a charge neutral. the coefficient table,
When A is a group selected from (a) to (d) and (h) to (k), A ′ is selected from (a ′) to (d ′) and (h ′) to (k ′). When A is a group selected from (e) to (g) and (l) to (m), A ′ is (e ′) to (g ′), (l ′) to (m ′) ). )
(Wherein, ring C and ring C ′ each independently represent a benzene ring, a naphthalene ring, a phenanthrene ring or a pyridine ring;
In the formula, R ¹ and R ¹ ′ each independently represent a hydrogen atom, a hydroxyl group, a halogen atom, a nitro group, a cyano group, a carboxyl group, an amino group, a dialkylamino group having 2 to 16 carbon atoms, a carbon atom having 12 to 12 carbon atoms. 40 diarylamino groups, arylalkylamino groups having 7 to 28 carbon atoms, amide groups, aryl groups having 6 to 20 carbon atoms, arylalkyl groups having 7 to 30 carbon atoms or alkyl having 1 to 8 carbon atoms A hydrogen atom of a dialkylamino group, a diarylamino group, an arylalkylamino group, an aryl group, an arylalkyl group and an alkyl group in R ¹ and R ¹ ′ are each independently a hydroxyl group, a halogen atom, a nitro group , a cyano group, a carboxyl group, an amino group, may be substituted with a amido group or a ferrocenyl group, Jiarukirua in said R ¹ and R ^{1 '} M, a diarylamino group, an arylalkylamino group, an aryl group, an arylalkyl group and a methylene group in the alkyl group each independently represent -O-, -S-, -CO-, -COO-, -OCO-. _{, -SO 2 -, - NH -} , - CONH -, - NHCO -, - N = CH- or may be replaced by -CH = CH-,
In the formula, R ^{2 to} R ⁹ and R ² ′ to R ⁹ ′ each independently represent a hydrogen atom, a hydroxyl group, a halogen atom, a nitro group, a cyano group, a carboxyl group, an amino group, an amide group, a carbon atom number of 6 to 20. An aryl group, an arylalkyl group having 7 to 30 carbon atoms or an alkyl group having 1 to 8 carbon atoms, wherein the aryl group, the arylalkyl group and the aryl group in R ^{2 to} R ⁹ and R ² ′ to R ⁹ ′ The hydrogen atom of the alkyl group may be independently substituted with a hydroxyl group, a halogen atom, a nitro group, a cyano group, a carboxyl group, an amino group, an amide group or a ferrocenyl group, and the R ^{2 to} R ⁹ and R ² ′ aryl groups in to R ⁹ ', a methylene group in the arylalkyl and alkyl groups are each independently, -O -, - S -, - CO -, - COO -, - OCO -, - SO 2 -, -NH-, -CONH- -NHCO -, - N = CH- or may be replaced by -CH = CH-,
In the formula, X and X ′ each independently represent an oxygen atom, a sulfur atom, a selenium atom, —CR ⁵¹ R ⁵² —, a cycloalkane-1,1-diyl group having 3 to 6 carbon atoms, —NH— or —. NY ² - ^{represents, R 51} and ^{R 52} each independently represent a hydrogen atom, a hydroxyl group, a halogen atom, a nitro group, a cyano group, a carboxyl group, an amino group, an amide group, an aryl group having 6 to 20 carbon atoms, a carbon Represents an arylalkyl group having 7 to 30 atoms or an alkyl group having 1 to 8 carbon atoms, and hydrogen atoms of the aryl group, the arylalkyl group and the alkyl group in R ⁵¹ and R ⁵² are each independently a hydroxyl group, a halogen atom, May be substituted with an atom, a nitro group, a cyano group, a carboxyl group, an amino group, an amide group or a ferrocenyl group, and the aryl group, arylalkyl group and alkyl group in R ⁵¹ and R ⁵² may be substituted. Methylene groups in the kill groups are each independently, -O -, - S -, - CO -, - COO -, - OCO -, - SO 2 -, - NH -, - CONH -, - NHCO -, - May be substituted with N = CH- or -CH = CH-,
In the formula, Y, Y ′ and Y ² each independently represent a hydrogen atom, a hydroxyl group, a halogen atom, a cyano group, a carboxyl group, an amino group, an amide group, a nitro group, an aryl group having 6 to 20 carbon atoms, a carbon atom arylalkyl group or an alkyl group having 1 to 8 carbon atoms in the C7-30, the Y, Y 'and Y ² in the aryl group, a hydrogen atom in the arylalkyl and alkyl groups are each independently, a hydroxyl group, a halogen group, a cyano group, a carboxyl group, an amino group, an amido group, may be substituted with a ferrocenyl group or a nitro group, said Y, Y 'and Y ² in the aryl group, arylalkyl group, and the alkyl group methylene groups are each independently, -O -, - S -, - CO -, - COO -, - OCO -, - SO 2 -, - NH -, - CONH -, - NHCO -, - N = CH -Or -CH = C - it may be substituted with,
In the formula, r and r ′ are 0 or (a) to (e), (g) to (j), (1), (m), (a ′) to (e ′), (g ′) to (J '), (l') and (m ') represent one or more possible substituents. )
(In the formula, k represents an integer of 0 to 4,
In the formula, the hydrogen atoms of the methine chain are each independently a hydroxyl group, a halogen atom, a cyano group, -NRR ', an aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms or a carbon atom. It may be substituted with an alkyl group of 1 to 8, and the alkyl group becomes a corresponding alkylene group and bonds to any two carbon atoms of the methine chain to form a ring structure having 3 to 10 carbon atoms. And each hydrogen atom of the ring structure is independently a hydroxyl group, a halogen atom, a cyano group, -NRR ', an aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a carbon atom. May be substituted with an alkyl group having 1 to 8 atoms,
R and R ′ in the methine chain and the ring structure each independently represent an aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or an alkyl group having 1 to 8 carbon atoms. The hydrogen atom in the methine chain and -NRR 'in the ring structure, the aryl group, the arylalkyl group and the alkyl group may be further independently substituted with a hydroxyl group, a halogen atom, a cyano group or -NRR'. And the aryl group in the methine chain and the ring structure, the methylene group in the arylalkyl group and the methylene group in the alkyl group are each independently -O-, -S-, -CO-, -COO-, -OCO-, _{-SO 2 -, - NH -,} - CONH -, - NHCO -, - N = CH- or may be replaced by -CH = CH-. )   The curable composition according to claim 1, wherein A and A ′ satisfy the following condition 1 or 2.
Condition 1: A is a group selected from (a), (b), (c), (i), and (k), and A ′ is (a ′), (b ′), (c ′), And a group selected from (i ') and (k').
Condition 2: A is a group selected from (a), (b), (c), (h) and (k), and A ′ is
(A ′), (b ′), (c ′), (h ′) and (k ′), or A is a group selected from (e), (l) and (m) A ′ is a group selected from (e ′), (l ′) and (m ′). The curable composition according to any one of claims 1 to 4 , wherein the cationically polymerizable organic substance (B) is at least one selected from the group consisting of an epoxy compound, an oxetane compound, and a cyclic acetal compound. The curable composition according to any one of claims 1 to 5 , wherein the acid generator (C) is at least one selected from the group of compounds represented by the following general formulas (2) to (4).
(Wherein, R ²¹ and R ²² each independently represent an alkyl group having 1 to 10 carbon atoms, an aromatic group having 6 to 20 carbon atoms or an arylalkyl group having 7 to 30 carbon atoms; The hydrogen atoms of the alkyl group, the aromatic group and the arylalkyl group are each independently a hydroxyl group, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an aromatic group having 6 to 20 carbon atoms, and a carbon atom having 7 to 7 carbon atoms. R ²¹ and R ²² may together form an alkylene chain of 2 to 7 carbon atoms, which may be substituted by 30 arylalkyl, nitro, sulfone or cyano group. May form a ring structure with S ⁺
R ²³ and R ²⁴ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an aromatic group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, nitro Represents a group, a cyano group or a sulfone group, wherein the hydrogen atoms of the alkyl group, the aromatic group and the arylalkyl group are each independently a hydroxyl group, a halogen atom, an alkyl group having 1 to 10 carbon atoms, An aromatic group of 20, an arylalkyl group having 7 to 30 carbon atoms, a nitro group, a sulfone group or a cyano group;
An ^q′- represents a ^q′- valent anion, q ′ represents 1 or 2, and p ′ represents a coefficient for keeping a charge neutral. )
(Wherein, R ²⁵ represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an aromatic group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, a hydroxyl group, or a nitro group. , A sulfone group or a cyano group, wherein the hydrogen atoms of the alkyl group, the aromatic group, and the arylalkyl group are each independently a hydroxyl group, a halogen atom, an alkyl group having 1 to 10 carbon atoms, and a carbon atom having 6 to 20 carbon atoms. An aromatic group, an arylalkyl group having 7 to 30 carbon atoms, a nitro group, a sulfone group or a cyano group,
R ²⁶ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aromatic group having 6 to 20 carbon atoms or an arylalkyl group having 7 to 30 carbon atoms, and the alkyl group, the aromatic group and the aryl The hydrogen atom of the alkyl group is independently a hydroxyl group, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an aromatic group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a nitro group. May be substituted with a sulfone group or a cyano group,
R ²⁷ represents an alkyl group having 1 to 10 carbon atoms, in which the constituent methylene group may be substituted with a halogen atom, -O- or -S-,
An ^{q "} -represents an anion having a valency of q", q "represents 1 or 2, and p" represents a coefficient for keeping a charge neutral. )
(Wherein, R ⁶¹ , R ⁶² , R ⁶³ , R ⁶⁴ , R ⁶⁵ , R ⁶⁶ , R ⁶⁷ , R ⁶⁸ , R ⁶⁹ and R ⁷⁰ each independently represent a hydrogen atom, a halogen atom, a carbon atom number of 1 to Represents an alkyl group having 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms or an ester group having 2 to 10 carbon atoms, and R ⁷¹ , R ⁷² , R ⁷³ , R ⁷⁴ , R ⁷⁵ , R ⁷⁶ , R ⁷⁷ and R ⁷⁸ each independently represent a hydrogen atom, a halogen atom or an alkyl group having 1 to 10 carbon atoms, R ⁸⁴ represents a group represented by hydrogen atom or the following general formula (4A), T ^- represents a monovalent anion Represents an ion.)
(Wherein, R ⁷⁹ , R ⁸⁰ , R ⁸¹ , R ⁸² and R ⁸³ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms or Represents an ester group having 2 to 10 carbon atoms.) The curable composition according to any one of claims 1 to 6 , further comprising an organic solvent. A method for curing a curable composition, comprising applying the curable composition according to claim 7 to a substrate and curing the composition with active energy rays or heating. A cured product of the curable composition according to any one of claims 1 to 7 . A wavelength cut filter comprising at least a part of the cured product according to claim 9 .