JP2015183134A - Polymethine compound and uses thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide: a novel polymethine compound which is chemically stable, has high durability such as heat and light resistance, and exhibits excellent near-infrared absorption performance and visible light transmission performance; and a near-infrared cut filter and a solid imaging device that contain the compound.SOLUTION: The present invention provides a polymethine compound represented by general formula (1), a near-infrared cut filter containing the same, and a solid imaging device comprising the same. (A and B are each a benzene ring or a naphthalene ring; Lis a cyclic alkylene group; Xand Xare each a 1,1-dialkylmethylene group or the like; Rand Rare each an alkyl group or the like; Yis H or the like; n and m are each independent and respectively the percentages of WOand MoOrelative to their total amount, satisfying 0%<n<100%, 0%<m<100%, and n+m=100%.)

Description

  The present invention relates to a novel polymethine compound and use thereof. More specifically, the present invention relates to a polymethine compound that is chemically stable and excellent in durability such as heat resistance and light resistance, a near-infrared cut filter containing the polymethine compound, and a solid-state imaging device.

A solid-state imaging device such as a digital video camera, a digital camera, or a mobile phone camera is equipped with a CCD or CMOS image sensor that is a solid-state imaging device. In the solid-state image sensor, a filter that cuts near infrared rays (near infrared cut filter) for the purpose of reducing optical noise that hinders image processing and correcting the visibility so that it is natural to see with the human eye. ) Is generally provided.
As such a near-infrared cut filter, for example, a transparent resin is used as a substrate, and a transparent resin containing a dye or pigment having absorption in the near-infrared region is used. These dyes and pigments are required to be highly durable and chemically stable, such as high near-infrared absorption performance, visible transmission performance, high light resistance, and high heat resistance in consideration of the temperature of the manufacturing process. Yes.

Patent Documents 1 and 2 disclose an optical filter for a display device having a polymethine compound having a specific skeleton, which is chemically stable, near infrared absorption performance, heat ray absorption performance, visible light transmission performance, and light resistance. It is described that it is excellent. However, the polymethine compound is still insufficient in light resistance and heat resistance.
In order to improve the durability of the polymethine compound and the optical filter using the same, it has been proposed to rake the polymethine compound with a heteropolyacid or the like.
Patent Document 3 discloses a laked trivalent or tetravalent cation polymethine dye having a heteropolyacid anion such as phosphomolybdic acid, which is used in printing inks and the like.

Patent Document 4 discloses an optical filter comprising a non-rake pigment having an absorption maximum in a wavelength region of 500 to 550 nm and a lake pigment having an absorption maximum in a wavelength region of 560 to 620 nm. Examples thereof include polymethine compounds having phosphomolybdic acid or phosphotungstic acid as anions, although they are not near infrared absorptive.
Patent Document 5 proposes a near-infrared absorbing dye-containing curable composition for use in a solid-state imaging device or the like, which contains a lake dye having an absorption maximum wavelength at 700 to 1100 nm, and an alkaline earth as one type of lake dye. Cyanine dyes having cations such as metal ions are disclosed.
However, these raked polymethine compounds are still insufficient in light resistance and heat resistance, and further improvements are required.

JP 2004-69758 A JP 2004-93758 A Japanese Patent Laid-Open No. 7-3177 JP 2001-66419 A JP 2007-271745 A

  An object of the present invention is to provide a novel polymethine compound that is chemically stable, has high durability such as heat resistance and light resistance, and is excellent in near-infrared absorption performance and visible transmission performance. Moreover, it is providing the near-infrared cut filter containing this polymethine type compound, and the solid-state imaging device which comprises this near-infrared cut filter.

  As a result of intensive studies on the problems in the previous period, the present inventors have found that polymethine compounds that form an inner salt with an anion of an inorganic acid containing a mixture of phosphotungstic acid and phosphomolybdic acid have near-infrared absorption performance, visible transmission performance, and durability. As a result, the present invention has been completed.

（式（１）中、Ａ、Ｂはそれぞれ独立に置換基を有しても良いベンゼン環または置換基を有しても良いナフタレン環を表し、Ｌ_１は環状構造を形成するのに必要な置換基を有しても良いアルキレン基であり、環を構成する炭素原子の１個以上が他の原子または原子団で置換されても良く、Ｘ_１、Ｘ_２はそれぞれ独立に１，１−ジアルキルメチレン基、置換基を有しても良い１−アルキル−１−ベンジルメチレン基、置換基を有しても良い１,１−ジベンジルメチレン基または置換基を有しても良い炭素数３〜６のシクロアルカン−1,１−ジイル基を表し、Ｒ_１、Ｒ₂はそれぞれ独立に置換基を有しても良いアルキル基を表し、Ｙ_１は水素原子、ハロゲン原子、アルキルチオ基、アリールチオ基または置換アミノ基を表す。ｎ、ｍはそれぞれ独立に、Ｗ_２Ｏ_７及びＭｏ_２Ｏ_７の合計量に対するそれぞれの百分率あり、０％＜ｎ＜１００％、０％＜ｍ＜１００％、かつｎ＋ｍ＝１００％である。 That is, the present invention
(I) a polymethine compound represented by the general formula (1),

(In formula (1), A and B each independently represent a benzene ring which may have a substituent or a naphthalene ring which may have a substituent, and L ₁ is necessary to form a cyclic structure. It is an alkylene group which may have a substituent, and one or more of the carbon atoms constituting the ring may be substituted with another atom or atomic group, and X ₁ and X ₂ are each independently 1,1- Dialkylmethylene group, 1-alkyl-1-benzylmethylene group which may have a substituent, 1,1-dibenzylmethylene group which may have a substituent or 3 carbon atoms which may have a substituent To 6 cycloalkane-1,1-diyl groups, R ₁ and R ₂ each independently represents an alkyl group which may have a substituent, and Y ₁ represents a hydrogen atom, a halogen atom, an alkylthio group, an arylthio group. Represents a group or a substituted amino group, n and m are each The _stand, there are a percentage of the total amount of W 2 _{O 7} and _{Mo 2 O 7, 0% <} n <100%, which is 0% <m <100%, and n + m = 100%.

(ii) A and B are benzene rings which may have a substituent, and L ₁ is an alkylene group having 2 to 4 carbon atoms which may have a substituent necessary for forming a cyclic structure. , X ₁ and X ₂ are 1,1-dialkylmethylene groups, R ₁ and R ₂ are alkyl groups having 1 to 8 carbon atoms, Y ₁ is a halogen atom, and n is 40% to 95%. The polymethine compound of (i), wherein m is 5% to 60%.

（式(２)中、Ｄ、Ｅ、Ｆ、Ｇはそれぞれ独立に置換基を有しても良いベンゼン環を表し、Ｌ_２は環状構造を形成するのに必要な置換基を有しても良いアルキレン基であり、環を構成する炭素原子の１個以上が他の原子または原子団で置換されても良く、Ｒ_３、Ｒ_４、Ｒ_５、Ｒ_６、Ｒ_７、Ｒ_８、Ｒ_９、Ｒ_１０はそれぞれ独立に置換基を有しても良いアルキル基または置換基を有しても良いフェニル基を表し、Ｙ_２は水素原子、ハロゲン原子、アルキルチオ基、アリールチオ基または置換アミノ基を表す。ｑ、ｒはそれぞれ独立に、Ｗ_２Ｏ_７及びＭｏ_２Ｏ_７の合計量に対するそれぞれの百分率であり、０％＜ｑ＜１００％、０％＜ｒ＜１００％、かつｑ＋ｒ＝１００％である。 (Iii) a polymethine compound represented by the following general formula (2),

(In the formula (2), D, E, F and G each independently represent a benzene ring which may have a substituent, and L ₂ may have a substituent necessary to form a cyclic structure. It is a good alkylene group, and one or more of the carbon atoms constituting the ring may be substituted with other atoms or atomic groups, and R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ independently represents an alkyl group which may have a substituent or a phenyl group which may have a substituent, and Y ₂ represents a hydrogen atom, a halogen atom, an alkylthio group, an arylthio group or a substituted amino group. Q and r are each independently the percentage of the total amount of W ₂ O ₇ and Mo ₂ O ₇ , 0% <q <100%, 0% <r <100%, and q + r = 100% It is.

(Iv) D, E, F, and G are benzene rings that may have a substituent, and L ₂ may have a substituent that is necessary for forming a cyclic structure. An alkylene group, R ₄ , R ₆ , R ₈ , and R ₁₀ are alkyl groups having 1 to 8 carbon atoms, and R ₃ , R ₅ , R ₇ , and R ₉ may have a substituent. (Ii) a polymethine compound, wherein Y ₂ is a halogen atom, q is 40% to 95%, and r is 5% to 60%,
(V) a near-infrared cut filter comprising at least one polymethine compound of (i) or (ii) and / or (iii) or (iv) as a dye;
(Vi) The present invention relates to a solid-state imaging device including the near-infrared cut filter of (v).

  According to the present invention, it is possible to provide a polymethine compound that is chemically stable compared to conventional polymethine compounds, has high durability such as heat resistance and light resistance, and has excellent near-infrared absorption performance and visible transmission performance. It became. In addition, by using the polymethine compound of the present invention, the durability such as heat resistance and light resistance is high, the near-infrared absorption performance and the visible transmission performance are excellent, and the performance is deteriorated even at a high temperature particularly in the production process. It has become possible to provide a near-infrared absorption cut filter with a small amount and a solid-state imaging device including the same.

（式（１）中、Ａ、Ｂはそれぞれ独立に置換基を有しても良いベンゼン環または置換基を有しても良いナフタレン環を表し、Ｌ_１は環状構造を形成するのに必要な置換基を有しても良いアルキレン基であり、環を構成する炭素原子の１個以上が他の原子または原子団で置換されても良く、Ｘ_１、Ｘ_２はそれぞれ独立に１,１−ジアルキルメチレン基、置換基を有しても良い１−アルキル−１−ベンジルメチレン基、置換基を有しても良い１,１−ジベンジルメチレン基または置換基を有しても良い炭素数３〜６のシクロアルカン−１,１−ジイル基を表し、Ｒ_１、Ｒ₂はそれぞれ独立に置換基を有しても良いアルキル基を表し、Ｙ_１は水素原子、ハロゲン原子、アルキルチオ基、アリールチオ基または置換アミノ基を表す。ｎ、ｍはそれぞれ独立に、Ｗ_２Ｏ_７及びＭｏ_２Ｏ_７の合計量に対するそれぞれの百分率あり、０％＜ｎ＜１００％、０％＜ｍ＜１００％、かつｎ＋ｍ＝１００％である。
一般式（１）で示されるポリメチン系化合物において、Ａ、Ｂはそれぞれ独立に置換基を有しても良いベンゼン環または置換基を有しても良いナフタレン環を表すが、好ましくは置換基を有しても良いベンゼン環である。 Hereinafter, the present invention will be described in detail.
[Polymethine compound of general formula (1)]
The polymethine compound of the general formula (1) will be described below.

(In formula (1), A and B each independently represent a benzene ring which may have a substituent or a naphthalene ring which may have a substituent, and L ₁ is necessary to form a cyclic structure. An alkylene group which may have a substituent, one or more of the carbon atoms constituting the ring may be substituted with another atom or atomic group, and X ₁ and X ₂ are each independently 1,1- Dialkylmethylene group, 1-alkyl-1-benzylmethylene group which may have a substituent, 1,1-dibenzylmethylene group which may have a substituent or 3 carbon atoms which may have a substituent To 6 cycloalkane-1,1-diyl groups, R ₁ and R ₂ each independently represents an alkyl group which may have a substituent, and Y ₁ represents a hydrogen atom, a halogen atom, an alkylthio group, an arylthio group. Represents a group or a substituted amino group, n and m are each The _stand, there are a percentage of the total amount of W 2 _{O 7} and _{Mo 2 O 7, 0% <} n <100%, which is 0% <m <100%, and n + m = 100%.
In the polymethine compound represented by the general formula (1), A and B each independently represent a benzene ring which may have a substituent or a naphthalene ring which may have a substituent. It is a benzene ring that may have.

Examples of the substituent include a halogen atom, a formyl group, a hydroxy group, a cyano group, a nitro group, an amino group, an alkyl group that may have a substituent, an alkoxy group that may have a substituent, and a substituent. An acyl group that may have a substituent, an alkenyl group that may have a substituent, a hydroxyalkyl group that may have a substituent, an alkoxycarbonyl group that may have a substituent, and a substituent. Alkylamino group, dialkylamino group which may have a substituent, alkoxycarbonylalkyl group which may have a substituent, alkylthio group which may have a substituent, alkylsulfonyl which may have a substituent Group, an alkylcarbonylamino group which may have a substituent, an aryl group which may have a substituent, a metallocenyl group which may have a substituent, and the like.
The substituent preferably has a halogen atom, an optionally substituted alkyl group having 1 to 8 carbon atoms, an optionally substituted alkoxy group having 1 to 8 carbon atoms, and a substituent. Or a dialkylamino group having 2 to 8 carbon atoms, an alkylthio group having 1 to 6 carbon atoms which may have a substituent, and an arylthio group which may have a substituent.
More preferably, they are a halogen atom, a C1-C8 alkyl group, and a C1-C8 alkoxy group.

Here, specific examples of the substituents A and B in the general formula (1) include halogen atoms such as fluorine atom, chlorine atom and bromine atom; formyl group; hydroxyl group; carboxyl group; cyano group; nitro group; Group;
Methyl, trifluoromethyl, ethyl, pentafluoroethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, cyclo Propyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, 1,2,2-trimethylbutyl group, 1,1,2-trimethylbutyl group, 1-ethyl-2-methylpropyl group, cyclo-hexyl group, n-heptyl Group, 2-methylhexyl group, 3-methylhexyl group, 4-methylhexyl group, 5-methylhexyl group, 2,4-dimethylpentyl group, n-octyl group, 2-ethylhexyl group, 2,5-dimethylhexyl An alkyl group having 1 to 8 carbon atoms such as a group, 2,5,5-triethylpentyl group, 2,4-dimethylhexyl group, and 2,2,4-trimethylpentyl group;
Methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, tert-butoxy group, sec-butoxy group, n-pentyloxy group, iso-pentyloxy group, n-hexyloxy group, n- An alkoxy group having 1 to 8 carbon atoms such as an octyloxy group, a methoxymethoxy group, an ethoxyethoxy group, and a 3- (iso-propyloxy) propyloxy group;
An acyl group having 2 to 7 carbon atoms such as acetyl group, propiol group, butyryl group, isobutyryl group, valeryl group, isovaleryl group, pivaloyl group, hexanoyl group, heptanoyl group;
An alkenyl group having 2 to 6 carbon atoms such as vinyl group, propenyl group, butenyl group, pentenyl group, hexenyl group, cyclopentenyl group, cyclohexenyl group;
A hydroxyalkyl group having 1 to 6 carbon atoms such as a hydroxymethyl group and a hydroxyethyl group;
Methoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group, isopropoxycarbonyl group, n-butoxycarbonyl group, tert-butoxycarbonyl group, sec-butoxycarbonyl group, n-pentyloxycarbonyl group, n-hexyloxycarbonyl group An alkoxycarbonyl group having 2 to 7 carbon atoms, such as
An alkylamino group having 1 to 6 carbon atoms such as a methylamino group, an ethylamino group, an n-propylamino group, and an n-butylamino group;
A dialkylamino group having 2 to 8 carbon atoms such as a dimethylamino group, a diethylamino group, a di-n-propylamino group, a di-n-butylamino group;
An alkoxycarbonylalkyl group having 3 to 7 carbon atoms such as a methoxycarbonylmethyl group, an ethoxycarbonylmethyl group, an n-propoxycarbonylmethyl group, an isopropoxycarbonylethyl group, a phenoxycarbonyl group;
An alkylthio group having 1 to 6 carbon atoms such as methylthio group, ethylthio group, n-propylthio group, tert-butylthio group, sec-butylthio group, n-pentylthio group, n-hexylthio group;
Phenylthio group, 2-chlorophenylthio group, 4-fluorophenylthio group,
Arylthio groups such as 4-methylphenylthio group, 2,4-dimethylphenylthio group, 2-trifluoromethylphenylthio group, 4-methoxyphenylthio group, 3-n-butoxyphenylthio group, naphthylthio group;
Methylsulfonyl group, trifluoromethylsulfonyl group, ethylsulfonyl group, pentafluoroethylsulfonyl group, n-propylsulfonyl group, isopropylsulfonyl group, n-butylsulfonyl group, tert-butylsulfonyl group, sec-butylsulfonyl group, n- An alkylsulfonyl group having 1 to 6 carbon atoms such as a pentylsulfonyl group and an n-hexylsulfonyl group;
Methylcarbonylamino group, ethylcarbonylamino group, n-propylcarbonylamino group, isopropylcarbonylamino group, n-butylcarbonylamino group, tert-butylcarbonylamino group, sec-butylcarbonylamino group, n-pentylcarbonylamino group, etc. An alkylcarbonylamino group having 2 to 6 carbon atoms;
Phenyl group, 4-methylphenyl group, 4-tert-butylphenyl group, biphenyl group, 4-trifluoromethylphenyl group, 4-methoxyphenyl group, 4-chlorophenyl group, 4-fluorophenyl group, naphthalen-1-yl Group, an aryl group such as naphthalen-2-yl group;
Examples thereof include metallocenyl groups such as a ferrocenyl group, a titanocenyl group, a chronocenyl group, and a ruthenocenyl group.

In the polymethine compound represented by the general formula (1), L ₁ is an alkylene group which may have a substituent necessary for forming a cyclic structure, and one or more carbon atoms constituting the ring are It may be substituted with other atoms or atomic groups, and those having 2 to 4 carbon atoms are preferred.
Examples of the substituent that L ₁ may have include a halogen atom, an alkylthio group, an arylthio group, an alkylamino group, and a substituted amino group, and a halogen atom is preferable.
Examples of the other atom or atomic group in which one or more carbon atoms constituting the ring may be substituted include a nitrogen atom, an oxygen atom, and a sulfur atom, and a nitrogen atom is preferable.
Examples of L ₁ include an alkylene group, and ethylene, propylene, butylene, 2-oxapropylene, 2-thiapropylene, 2-azapropylene, 2-methylpropylene, and 2-tert-butylpropylene are preferable. , Propylene and butylene are preferred.

In the polymethine compound represented by the general formula (1), X ₁ and X ₂ are each independently a 1,1-dialkylmethylene group, a 1-alkyl-1-benzylmethylene group which may have a substituent, and a substituent. Represents a 1,1-dibenzylmethylene group which may have a substituent or a C3-C6 cycloalkane-1,1-diyl group which may have a substituent, preferable.

Here, specific examples of X _{1 to} X ₂ include 1,1-dimethylmethylene group, 1,1-diethylmethylene group, 1,1-di-n-propylmethylene group, 1,1-di-n-butyl. Methylene group, 1-ethyl-1-methylmethylene group, 1-methyl-1-propylmethylene group, 1-butyl-1-methylmethylene group, 1-ethyl-1-propylmethylene group, 1-ethyl-1-butyl 1,1-dialkylmethylene groups such as methylene group and 1-cyclohexylmethyl-1-methylmethylene group;
1-benzyl-1-methylmethylene group, 1-benzyl-1-ethylmethylene group, 1-benzyl-1-propylmethylene group, 1-benzyl-1-butylmethylene group, 1- (4-nitrobenzyl) -1 -Methylmethylene group, 1- (4-chlorobenzyl) -1-methylmethylene group, 1- (4-bromobenzyl) -1-methylmethylene group, 1- (4-methylbenzyl) -1-methylmethylene group, etc. 1-alkyl-1-benzylmethylene group which may have a substituent of
1,1-dibenzylmethylene group, 1,1-di (4-nitrobenzyl) methylene group, 1,1-di (4-chlorobenzyl) methylene group, 1,1-di (4-bromobenzyl) methylene group A 1,1-dibenzylmethylene group which may have a substituent such as a 1,1-di (4-methylbenzyl) methylene group;
Cyclobutane-1,1-diyl group, cyclopentane-1,1-diyl group, cyclohexyl-1,1-diyl group, 4-methylcyclohexyl-1,1-diyl group, 4-ethylcyclohexyl-1,1-diyl And a C3-C6 cycloalkane-1,1-diyl group which may have a substituent such as a 4-tert-butylcyclohexyl-1,1-diyl group.

In the polymethine compound represented by the general formula (1), R ₁ and R ₂ each independently represents an alkyl group which may have a substituent, but an alkyl group having 1 to 12 carbon atoms is preferable, and 1 carbon atom is present. An alkyl group of ˜8 is more preferred.
Examples of the substituent that R ₁ and R ₂ may have include a halogen atom, an alkoxy group, a dialkylamino group, and an alkylcarbonyl group, and a halogen atom and an alkoxy group are preferable.

Specific examples of R ₁ and R ₂ include methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, sec-butyl group, t-butyl group, and n-pentyl group. 2-methylbutyl group, 1-methylbutyl group, neo-pentyl group, 1,2-dimethylpropyl group, cyclo-pentyl group, n-hexyl group, 4-methylpentyl group, 3-methylpentyl group, 2-methylpentyl Group, 1-methylpentyl group, 3,3-dimethylbutyl group, 2,3-dimethylbutyl group, 1,3-dimethylbutyl group, 2,2-dimethylbutyl group, 1,2-dimethylbutyl group, 1, 1-dimethylbutyl group, 3-ethylbutyl group, 2-ethylbutyl group, 1-ethylbutyl group, 1,2,2-trimethylbutyl group, 1,1,2-trimethylbutyl group, 1-ethyl Ru-2-methylpropyl group, cyclo-hexyl group, n-heptyl group, 2-methylhexyl group, 3-methylhexyl group, 4-methylhexyl group, 5-methylhexyl group, 2,4-dimethylpentyl group, n-octyl group, 2-ethylhexyl group, 2,5-dimethylhexyl group, 2,5,5-triethylpentyl group, 2,4-dimethylhexyl group, 2,2,4-trimethylpentyl group, n-nonyl group 3,5,5-trimethylhexyl group, n-decyl group, 4-ethyloctyl group, 4-ethyl-4,5-dimethylhexyl group, n-undecyl group, n-dodecyl group, 1,3,5, 7-tetramethyloctyl group, 4-butyloctyl group, 6,6-diethyloctyl group, n-tridecyl group, 6-methyl-4-butyloctyl group, 6,6-diethyloctyl Group, n-tetradecyl group, n-pentadecyl group, 3,5-dimethylheptyl group, 2,6-dimethylheptyl group, 2,4-dimethylheptyl group, 2,2,5,5-tetramethylhexyl group, 1 A linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, such as -cyclo-pentyl-2,2-dimethylpropyl group, 1-cyclo-hexyl-2,2-dimethylpropyl group;
Chloromethyl group, dichloromethyl group, fluoromethyl group, trifluoromethyl group, 2,2,2-trifluoroethyl group, pentafluoroethyl group, heptafluoroisopropyl group, heptafluoro-n-propyl group, 2,2, 3,3,3-pentafluoropropyl group, nonafluoro-n-butyl group, nonafluoro-tert-butyl group, 2,2,3,3,4,4,4-heptafluorobutyl group, 2,2,3, 4,4,4-hexafluorobutyl group, perfluoroisopentyl group, 2,2,3,3,4,4,5,5-octafluoropentyl group, heptafluoro-sec-pentyl group, perfluorohexyl Groups, perfluoroisohexyl groups, perfluoroheptyl groups, perfluorooctyl groups, perfluorocyclohexyl groups, 4-trifluoromethylcyclohexyl groups and the like halogenoalkyl groups;
Alkoxyalkyl groups such as methoxyethyl group, ethoxyethyl group, iso-propyloxyethyl group, 3-methoxypropyl group, 2-methoxybutyl group;
2-dimethylaminoethyl group, 3-dimethylaminopropyl group, 4-dimethylaminobutyl group, 2-diethylaminoethyl group, 3-diethylaminopropyl group, 4-diethylaminobutyl group, 2-di-n-propylaminoethyl group, 3-di-n-propylaminopropyl group, 4-di-n-propylaminobutyl group, 2-di-n-butylaminoethyl group, 3-di-n-butylaminopropyl group, 4-di-n- A dialkylaminoalkyl group having 4 to 12 carbon atoms such as a butylaminobutyl group;
Alkyl group which may have a substituent such as an alkoxycarbonylalkyl group having 3 to 7 carbon atoms such as methoxycarbonylmethyl group, ethoxycarbonylmethyl group, n-propoxycarbonylmethyl group, isopropoxycarbonylethyl group, phenoxycarbonyl group Is mentioned.

In the polymethine compound represented by the general formula (1), Y ₁ represents a hydrogen atom, a halogen atom, an alkylthio group, an arylthio group or a substituted amino group, preferably a halogen atom, an arylthio group or a substituted amino group, More preferred.
Specific examples of Y ₁ include a hydrogen atom; a halogen atom such as a chlorine atom, a bromine atom, a fluorine atom or an iodine atom; an alkylthio group such as a methylthio group, an ethylthio group, a propylthio group or a butylthio group; a phenylthio group or a 4-chlorophenylthio group Arylthio groups such as 4-fluorophenylthio group, 4-methylphenylthio group, 2,4-dimethylphenylthio group, 4-trifluoromethylphenylthio group, 4-methoxyphenylthio group, naphthylthio group; , Substituted amino groups such as phenylamino group and diphenylamino group.
In the polymethine compound represented by the general formula (1), n and m are each independently a percentage with respect to the total amount of W ₂ O ₇ and Mo ₂ O ₇ , 0% <n <100%, 0% < m <100% and n + m = 100%, but in order for the durability of the compound to be very high, n is 40% to 95% and m is 5% to 60% N is preferably 60% to 90%, more preferably m is 10% to 40%, and most preferably n is 80% and m is 20%.
Specific examples of the polymethine compound represented by the general formula (1) of the present invention are shown in Table 1 below, but are not limited thereto.

（式（３）中、Ａ、Ｂ、Ｒ₁、Ｒ_２、Ｌ_１、Ｘ₁、Ｘ_２、Ｙ_１は前記一般式（１）におけるものと同義であり、Ｚ⁻は１価のアニオンを表す。）
一般式（３）のポリメチン系色素のアニオンであるＺ⁻としてはＦ⁻、Ｃｌ⁻、Ｂｒ⁻、Ｉ⁻、ＢｒＯ_４ ⁻、ＣｌＯ_４ ⁻、ｐ−トルエンスルホネート、ＣＨ_３ＳＯ_３ ⁻、ＢＦ_４ ⁻、ＣＨ_３ＣＯ_２ ⁻、ＣＦ_３ＣＯ_２ ⁻、ＳｂＦ_６ ⁻が好ましく、Ｃｌ⁻、Ｂｒ⁻、ＢＦ_４ ⁻がより好ましい。
一般式(３)で表されるポリメチン化合物は特許第３６０６１６５号報記載の方法を参考にして、インドレニウム系化合物とジホルミル系化合物またはジアニル系化合物を脂肪酸塩の存在下、脱水性有機酸中にて縮合させることにより製造することができる。 [Method for Producing Polymethine Compound of General Formula (1)]
Below, the manufacturing method of the polymethine type compound of General formula (1) is demonstrated.
The polymethine compound of the general formula (1) is prepared by preparing a heteropolyacid salt containing tungsten and molybdenum as essential elements in water, and then reacting the polymethine compound represented by the following general formula (3) with alcohol in the reaction solution. It can be prepared by dissolving in a water-soluble solvent such as

(In the formula (3), A, B, R ₁ , R ₂ , L ₁ , X ₁ , X ₂ , Y ₁ are as defined in the general formula (1), and Z ⁻ represents a monovalent anion. Represents.)
Z ⁻ which is an anion of the polymethine dye of the general formula (3) is F ⁻ , Cl ⁻ , Br ⁻ , I ⁻ , BrO ₄ ⁻ , ClO ₄ ⁻ , p-toluenesulfonate, CH ₃ SO ₃ ⁻ , BF _{4. ^{-, CH 3 CO 2 -,}} CF 3 CO 2 -, SbF 6 - are ^{preferred, Cl -, Br -, BF} 4 - is preferable.
The polymethine compound represented by the general formula (3) is prepared by combining an indolenium compound and a diformyl compound or a dianyl compound in a dehydrating organic acid in the presence of a fatty acid salt with reference to the method described in Japanese Patent No. 3606165. Can be produced by condensation.

As the heteropolyacid salt containing tungsten and molybdenum as essential elements, monovalent metal salts such as sodium, lithium and potassium are preferable because they are excellent in water solubility and can be easily raked.
The mixing ratio of the heteropoly acid salt containing tungsten element and the heteropoly acid containing molybdenum element is 40% to 95% for heteropoly acid salt containing tungsten element, and 5% to 60% for heteropoly acid containing molybdenum element. Preferably, the heteropolyacid salt containing tungsten element is 60% to 90%, the heteropolyacid containing molybdenum element is more preferably 10% to 40%, the heteropolyacid salt containing tungsten element is 80%, and the molybdenum element is contained The heteropolyacid salt is most preferably 20%.
Heteropolyacid salts containing tungsten and molybdenum as essential elements are prepared by dissolving, for example, sodium tungstate dihydrate, sodium molybdate dihydrate, and sodium phosphate dodecahydrate in water, and using hydrochloric acid. It can be produced by acidification and heating at 90 to 100 ° C. for 30 minutes to several hours after adding a small amount of zinc.

In the production of a heteropoly acid salt containing tungsten and molybdenum as essential elements, the amount of water used as a reaction solvent is sodium tungstate dihydrate, sodium molybdate dihydrate, and sodium phosphate 12 5-100 times volume is preferable with respect to the total weight of a hydrate, and 10-50 times volume is more preferable.
Next, the polymethine compound represented by the general formula (3) is dissolved in a water-soluble solvent and added to the reaction solution, and reacted.
The usage-amount of the polymethine type compound of General formula (3) is 0.5 to 1 time mole with respect to heteropolyacid salt, Preferably it is 0.8 to 1 time mole.

As the water-soluble solvent, methanol, ethanol, n-propanol, isopropanol, acetone, THF, dibrime, diethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether DMF, DMAC, DMI, DMSO are preferable, and methanol, ethanol, n-propanol, isopropanol, acetone are preferable. More preferred.
The usage-amount of a water-soluble solvent is 3-100 times capacity with respect to the weight of the polymethine type compound of General formula (3), Preferably it is 5-50 times capacity.
The reaction temperature is preferably 40-80 ° C, more preferably 50-60 ° C.
The reaction time is preferably 20 minutes to 24 hours, more preferably 1 to 5 hours.
After completion of the reaction, water can be added for dilution, and the precipitate can be collected by filtration, washed with water, further washed with the above-mentioned sex solvent and dried to obtain the desired product.

（式(２)中、Ｄ、Ｅ、Ｆ、Ｇはそれぞれ独立に置換基を有しても良いベンゼン環を表し、Ｌ_２は環状構造を形成するのに必要な置換基を有しても良いアルキレン基であり、環を構成する炭素原子の１個以上が他の原子または原子団で置換されても良く、Ｒ_３、Ｒ_４、Ｒ_５、Ｒ_６、Ｒ_７、Ｒ_８、Ｒ_９、Ｒ_１０はそれぞれ独立に置換基を有しても良いアルキル基または置換基を有しても良いフェニル基を表し、Ｙ_２は水素原子、ハロゲン原子、アルキルチオ基、アリールチオ基または置換アミノ基を表す。ｑ、ｒはそれぞれ独立に、Ｗ_２Ｏ_７及びＭｏ_２Ｏ_７の合計量に対するそれぞれの百分率であり、０％＜ｑ＜１００％、０％＜ｒ＜１００％、かつｑ＋ｒ＝１００％である。
一般式（２）で表されるポリメチン系化合物において、Ｄ、Ｅ、Ｆ，Ｇの好ましい範囲、有しても良い置換基は前記一般式（１）で表されるポリメチン系化合物のＡ、Ｂにおけるものと同じであり、具体例も同じである。 [Polymethine compound of general formula (2)]
The polymethine compound of the general formula (2) will be described below.

(In the formula (2), D, E, F and G each independently represent a benzene ring which may have a substituent, and L ₂ may have a substituent necessary to form a cyclic structure. It is a good alkylene group, and one or more of the carbon atoms constituting the ring may be substituted with other atoms or atomic groups, and R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ independently represents an alkyl group which may have a substituent or a phenyl group which may have a substituent, and Y ₂ represents a hydrogen atom, a halogen atom, an alkylthio group, an arylthio group or a substituted amino group. Q and r are each independently the percentage of the total amount of W ₂ O ₇ and Mo ₂ O ₇ , 0% <q <100%, 0% <r <100%, and q + r = 100% It is.
In the polymethine compound represented by the general formula (2), preferred ranges of D, E, F, and G, and the substituents that may be included are A and B of the polymethine compound represented by the general formula (1). The specific example is also the same.

In the polymethine compound represented by the general formula (2), the preferred ranges of L ₂ and Y ₂ , the substituents that may be present, etc. are L ₁ and Y of the polymethine compound represented by the general formula (1), respectively. ₁ and the specific example is also the same.
In the polymethine compound represented by the general formula (2), when R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ is an alkyl group, its preferred range, The substituents that may be used are the same as R ₁ and R ₂ of the polymethine compound represented by the general formula (1), and specific examples thereof are also the same.
When R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ is a phenyl group which may have a substituent, it is preferably a phenyl group having no substituent. is there. Examples of the substituent that may be included include a halogen atom, an alkyl group, and an alkoxy group.
Specific examples include phenyl group, 4-chlorophenyl group, 4-bromophenyl group, 4-fluorophenyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 2,4-dimethylphenyl group, 4-trifluoromethylphenyl group, 4-methoxyphenyl group, etc. are mentioned.

In the polymethine compound represented by the general formula (2), q and r are each independently a percentage with respect to the total amount of W ₂ O ₇ and Mo ₂ O ₇ , and 0% <q <100%, 0 % <R <100% and q + r = 100%, but in order for the compound to have very high durability, q is 40% to 95%, and r is 5% to 60%. Some are preferred, q is 60% to 90%, r is preferably 10% to 40%, more preferably q is 80%, and r is 20%.

Although the specific example of the polymethine type compound represented by General formula (2) of this invention is shown in following Table 2, it is not limited to these.

（式（４）中、Ｄ、Ｅ、Ｆ、Ｇ、Ｒ₃〜Ｒ₁₀、Ｌ₂、Ｙ_２は前記一般式（２）におけるものと同義であり、Ｚ⁻は１価のアニオンを表す。）
一般式(４)で表されるポリメチン系化合物は特開２００２―１８７８７９号報記載の方法を参考にしてインドリルエチレン化合物とジホルミル系化合物またはジアニル系化合物をアルカリ金属塩の存在下、脱水性有機酸中にて縮合させることにより製造することができる。 [Method for producing polymethine compound of general formula (2)]
Below, the manufacturing method of the polymethine type compound of General formula (2) is demonstrated.
The polymethine compound of the general formula (2) is used in the production of the polymethine compound of the general formula (1) except that the polymethine compound of the following general formula (4) is used instead of the polymethine compound of the general formula (3). Can be produced by carrying out similar methods and operations.

(In the formula (4), D, E, F, G, R _{3 to} R ₁₀ , L ₂ and Y ₂ have the same meaning as in the general formula (2), and Z ⁻ represents a monovalent anion. )
The polymethine compound represented by the general formula (4) is a dehydrating organic compound obtained by converting an indolylethylene compound and a diformyl compound or a dianyl compound in the presence of an alkali metal salt with reference to the method described in Japanese Patent Application Laid-Open No. 2002-187879. It can be produced by condensation in an acid.

[Near-infrared cut filter]
The near-infrared cut filter according to the present invention contains at least one polymethine compound of the general formula (1) and / or the general formula (2) as a pigment.
Hereinafter, the polymethine compound of the general formula (1) and / or the general formula (2) of the present invention may be abbreviated as “polymethine compound of the present invention”.
As an aspect of the near-infrared cut filter of the present invention,
1. An embodiment containing the polymethine compound of the present invention as a pigment in a transparent resin as a substrate,
2. A mode in which a resin film containing the polymethine compound of the present invention as a pigment is pasted on another transparent support such as glass or transparent resin,
3. A mode in which a transparent resin base material is coated with a resin coating solution containing the polymethine compound of the present invention,
4). Embodiment in which a transparent resin base material is impregnated with a solution containing the polymethine compound of the present invention,
And so on.
1. ~ 4. In any embodiment, the near-infrared cut filter of the present invention preferably contains at least one polymethine compound of the present invention as a pigment in a resin, particularly a transparent resin.
The transparent resin is not particularly limited as long as it can transmit at least light in the visible wavelength range. For example, polyester resin such as polyethylene terephthalate and polybutylene terephthalate; polyethylene, polypropylene, ethylene vinyl acetate copolymer, ethylene-acrylic copolymer Polyolefin resins such as polymers; Norbornene resins; Acrylic resins such as polyacrylate and polymethyl methacrylate; Polyurethane resins; Vinyl chloride resins: Fluorine resins; Cellulose resins; Polycarbonate resins; Fluorene polycarbonate resins; Resin; Polyamideimide resin; Polystyrene resin; Polyvinyl butyral resin; Polyvinyl acetal resin; Polyvinyl alcohol resin; Cyclic polyolefin Resins; aromatic polyether resins; polyarylate resin; polysulfone resin; polyether sulfone resins; polyparaphenylene-based resins.
In particular, polycarbonate resin, polyamide resin, polyimide resin, acrylic resin, polyester resin, polyvinyl acetal resin, polyether sulfone resin, polyether resin, cyclic olefin resin, norbornene resin, and polyether sulfone resin are preferable.
These transparent resins may be used by mixing or laminating two or more kinds.
The blending amount of the polymethine compound of the general formula (1) and / or the general formula (2) with respect to the transparent resin varies depending on the use of the near-infrared cut filter and required characteristics. In the case of a filter, the polymethine compound is preferably 0.01 to 15.0 parts by weight, more preferably 0.02 to 8.0 parts by weight, particularly preferably 0.03 to 5. 0 parts by weight. When the content of the polymethine compound is within this range, both good near-infrared absorption characteristics and high visible light transmittance can be achieved.

The method for containing the polymethine compound of the present invention in the transparent resin is not particularly limited. For example, the method of dissolving the polymethine compound of the present invention in a solvent and mixing it with the transparent resin, and then removing the solvent, the present invention. There are a method in which the polymethine compound and the transparent resin are mixed and then molded by heating and melting, and a method in which the polymethine compound of the present invention is dispersed as fine particles and mixed with the resin. Moreover, after dissolving the polymethine compound of the present invention in a solvent, the polymethine compound can be diffused and permeated into the resin by contacting a transparent resin or a molded product thereof.
Moreover, the method of polymerizing this after mixing the polymethine type compound of this invention with the monomer, prepolymer, etc. which are resin raw materials or precursors may be used. This method is suitably used when the transparent resin is a thermosetting resin, but is effective even in the case of a thermoplastic resin.
In the method of dissolving the polymethine compound of the present invention in a solvent and mixing it with a transparent resin and then removing the solvent, the solvent is preferably an organic solvent, but it is chemically reactive with the transparent resin and the polymethine compound of the present invention. It is not particularly limited as long as it is inert and has a moderately low boiling point.
In the method of mixing and molding the polymethine compound and the transparent resin of the present invention while heating and melting, they are mixed using various mixers such as a tumbler and a Henschel mixer, and this is mixed with a Banbury mixer, a heating roll, and a Brabender. A homogeneous mixture of the polymethine compound of the present invention and the transparent resin can be produced by melt-kneading with a known melt-kneader such as a single-screw kneading extruder, a twin-screw kneading extruder, or a kneader.
In the method of dispersing and mixing the polymethine compound of the present invention as fine particles, a known disperser such as a ball mill, a vibrating ball mill, a planetary ball mill, a sand mill, a colloid mill, a jet mill, or a roller mill is used to form a fine particle dispersion. I can do it. For the dispersion, it is preferable to use an appropriate medium such as water, alcohol, aliphatic hydrocarbon, aromatic hydrocarbon or the like. It is also preferable to use a dispersing surfactant. The target fine particles have an average particle size of 1000 μm or less, preferably 0.001 μm to 100 μm, more preferably 0.005 μm to 50 μm.
In the method in which the polymethine compound of the present invention is dissolved in a solvent and then the transparent resin or a molded product thereof is brought into contact to diffuse and permeate the polymethine compound into the resin, the solvent is not particularly limited. It is not preferable to decompose or alter the polymethine compound or transparent resin. Usually, liquid ketones and alcohols are often used. The concentration of the polymethine compound solution of the present invention is arbitrary depending on the purpose, but is usually in the range of about 0.01% to 30%. Diffusion conditions vary depending on the polymethine compound of the present invention, the solvent, the type of transparent resin, and the like, but are usually 25 ° C. to 200 ° C. and several minutes to 5 hours under normal pressure or pressure.

A method for polymerizing the polymethine compound of the present invention after mixing it with a resin raw material or precursor monomer or prepolymer will be described below. Here, a monomer or a prepolymer that is a resin raw material or a precursor will be described as a representative, but the monomer is not limited to the monomer.
In the step of mixing the polymethine compound of the present invention with the monomer, depending on the mixing target of the polymethine compound of the present invention, a method of making a monomer mixture after mixing with any of the monomer groups constituting the monomer mixture, the monomer mixture, and others There are a method in which a catalyst is added after mixing in a mixture consisting of the above additives, a method in which the mixture is made into a mixture consisting of a monomer mixture, a catalyst, and other additives.
In mixing the polymethine compound of the present invention with the monomer, the polymethine compound of the present invention may be directly mixed, or the polymethine compound of the present invention is previously dissolved in a low-boiling organic solvent and the organic solvent is mixed. After mixing the solution with the monomer, the organic solvent may be removed by evaporation under conditions such as heating and / or reduced pressure. Examples of the organic solvent used in this case include hexane, heptane, acetone, methyl ethyl ketone, dimethylacetamide, benzene, toluene, dichloromethane, chloroform and the like, but are chemically reactive to the monomer and the polymethine compound of the present invention. And, it is not particularly limited as long as it has a moderately low boiling point.
In mixing, it may be mixed so that the amount corresponding to the dye concentration required for the near-infrared cut filter is contained, and one of the components such as one monomer has a concentration higher than the target concentration. A master batch containing a polymethine compound may be prepared, and may be diluted by adding other components to be blended as necessary. Further, in dissolving the polymethine compound of the present invention, it can be heated within a range where there is no problem in practice in terms of deterioration of the near infrared cut filter.

Thus, this invention used for a near-infrared cut filter by polymerizing the resin raw material containing the monomer containing the polymethine compound of the present invention by a known method such as heating and irradiation with energy rays such as ultraviolet rays. A transparent resin containing the polymethine compound is obtained.
When the near infrared cut filter of the present invention is used in combination with a solid-state imaging device such as a CCD or CMOS image sensor, the thickness of the transparent resin substrate (substrate) containing the polymethine compound of the present invention is preferably 500 to It is 10 μm, more preferably 300 to 20 μm, particularly preferably 200 to 50 μm. When the thickness is within this range, the near-infrared cut filter can be reduced in size and weight, and can be suitably used for various applications such as a solid-state imaging device. In particular, when used in a lens unit such as a camera module, it is preferable because a low profile of the lens unit can be realized.
In addition, the near-infrared cut filter of the present invention has a mode in which a resin film containing the polymethine compound of the present invention as a pigment is pasted on another transparent support, or the polymethine compound of the present invention on a transparent resin substrate. In the case where the resin coating liquid is coated, the thickness of the resin layer containing the polymethine compound of the present invention is preferably about 200 to 0.01 μm, and more preferably about 50 to 0.01 μm.
The near-infrared cut filter of the present invention differs depending on its application, but when used in a camera module or the like, in the visible light region having a wavelength of 400 to 700 nm, the transparent resin substrate (substrate) containing the polymethine compound of the present invention ) Is preferably 50% or more, more preferably 65% or more, when the thickness is 100 μm.
The near-infrared cut filter of the present invention is a phthalocyanine-based compound, naphthalocyanine-based compound, diimmonium-based compound as long as it does not affect near-infrared absorption performance, visible transmission performance and durability in addition to the polymethine compound of the present invention. You may use together other near-infrared absorptive organic pigment | dyes, such as a compound, a squarylium type compound, or a croconium type compound.

（式中、Ｒ_１１〜Ｒ_２６はそれぞれ独立に、水素原子、ハロゲン原子、直鎖、分岐または環状のアルキル基、直鎖、分岐または環状のアルコキシ基、置換または非置換のアリール基、直鎖、分岐または環状のハロゲノアルキル基、直鎖、分岐または環状のハロゲノアルコキシ基、直鎖、分岐または環状のアルコキシアルキル基を表す。ただしＲ_１１〜Ｒ_２６のすべてが水素原子であることはない。Ｍ_１は２個の水素原子、２価の金属原子、または酸化金属原子を表す）
アリール基とは、例えば、フェニル基、ナフチル基などの炭素環式芳香族基、例えば、フリル基、チエニル基、ピリジル基などの複素環式芳香族基を表し、炭素環式芳香族基が好ましい。 Particularly preferred are phthalocyanine compounds represented by the following general formula (5) and naphthalocyanine compounds represented by the following general formula (6).

(In the formula, each of R _{11 to} R ₂₆ is independently a hydrogen atom, a halogen atom, a linear, branched or cyclic alkyl group, a linear, branched or cyclic alkoxy group, a substituted or unsubstituted aryl group, and a linear chain. Represents a branched or cyclic halogenoalkyl group, a linear, branched or cyclic halogenoalkoxy group, a linear, branched or cyclic alkoxyalkyl group, provided that not all of R _{11 to} R ₂₆ are hydrogen atoms. M ₁ represents two hydrogen atoms, a divalent metal atom, or a metal oxide atom)
The aryl group represents, for example, a carbocyclic aromatic group such as a phenyl group or a naphthyl group, for example, a heterocyclic aromatic group such as a furyl group, a thienyl group or a pyridyl group, and a carbocyclic aromatic group is preferable. .

（式中、Ｒ_２７〜Ｒ_５０はそれぞれ独立に、水素原子、フッ素原子、シアノ基、直鎖、分岐または環状のアルキル基、直鎖、分岐または環状のアルコキシ基、置換または非置換のアリール基、直鎖、分岐または環状のハロゲノアルキル基、直鎖、分岐または環状のハロゲノアルコキシ基、直鎖、分岐または環状のアルコキシアルキル基を表す。ただしＲ_２７〜Ｒ_５０のすべてが水素原子であることはない。Ｍ_２は２個の水素原子、２価の金属原子、または酸化金属原子を表す） In the compound represented by the general formula (5), R _{11 to} R ₂₆ are each independently a hydrogen atom, a fluorine atom, a bromine atom, a chlorine atom, a linear, branched or cyclic alkyl group having 1 to 24 carbon atoms, C1-C24 linear, branched or cyclic alkoxy group, C4-C30 substituted or unsubstituted aryl group, C1-C24 linear, branched or cyclic halogenoalkyl group, C1 A linear, branched or cyclic halogenoalkoxy group having ˜24 or a linear, branched or cyclic alkoxyalkyl group having 2 to 24 carbon atoms is preferable.

Wherein R _{27 to} R ₅₀ are each independently a hydrogen atom, a fluorine atom, a cyano group, a linear, branched or cyclic alkyl group, a linear, branched or cyclic alkoxy group, a substituted or unsubstituted aryl group Represents a linear, branched or cyclic halogenoalkyl group, a linear, branched or cyclic halogenoalkoxy group, a linear, branched or cyclic alkoxyalkyl group, provided that all of R _{27 to} R ₅₀ are hydrogen atoms. M ₂ represents two hydrogen atoms, a divalent metal atom, or a metal oxide atom)

In the compound represented by the general formula (6), R _{27 to} R ₅₀ are each independently a hydrogen atom, a fluorine atom, a cyano group, a linear, branched or cyclic alkyl group having 1 to 24 carbon atoms, or 1 carbon atom. -24 linear, branched or cyclic alkoxy group, substituted or unsubstituted aryl group having 4 to 30 carbon atoms, linear, branched or cyclic halogenoalkyl group having 1 to 24 carbon atoms, 1 to 24 carbon atoms A linear, branched or cyclic halogenoalkoxy group and a linear, branched or cyclic alkoxyalkyl group having 2 to 24 carbon atoms are preferred.
The near-infrared cut filter of this invention can mix | blend a well-known ultraviolet absorber, an infrared absorber, and various resin additives as needed. Various resin additives include phenolic antioxidants, mold release agents, dyes and pigments, phosphorus thermal stabilizers, thermal polymerization inhibitors, weather resistance improvers, antistatic agents, antifogging agents, lubricants and antiblocking agents, Examples include flame retardants, fluidity improvers, plasticizers, dispersants, and antibacterial agents.
As the ultraviolet absorber, benzophenone compounds, benzotriazole compounds, triazine compounds, benzoate compounds, hindered amine compounds, and the like can be used. In particular, benzophenone compounds and benzotriazole compounds are preferred.
The addition amount of these various resin additives is appropriately selected according to the desired properties, but is usually 0.01 to 5.0 parts by weight, preferably 0.05 to 100 parts by weight of the transparent resin. -2.0 parts by weight.
The near-infrared cut filter of the present invention is provided with a functional film such as an antireflection film, a hard coat film, an antistatic film, a dielectric multilayer film, and a near-infrared reflection film on the surface, as long as the effects of the present invention are not impaired. Also good. Further, surface treatment such as corona treatment or plasma treatment may be performed.
The near infrared cut filter of the present invention efficiently cuts near infrared rays in the range of 600 nm to 1000 nm, particularly in the range of 750 nm to 1000 nm.
Moreover, the near-infrared cut filter of the present invention is also useful as a heat ray cut filter mounted on a window or the like of an automobile or a building.

[Solid-state imaging device]
The solid-state imaging device of the present invention includes the near-infrared cut filter of the present invention.
Here, the solid-state imaging device is an image sensor including a solid-state imaging device such as a CCD or a CMOS, and can be used specifically for applications such as a digital still camera, a mobile phone camera, and a digital video camera. Since the solid-state imaging device uses a silicon photodiode having sensitivity to near infrared rays in the light receiving portion thereof, it is necessary to perform visibility correction, and it is effective to use a near infrared cut filter.
The near-infrared cut filter of the present invention is disposed, for example, between an imaging lens and a solid-state imaging device in a solid-state imaging device such as a digital still camera, a mobile phone camera, or a digital video camera. In the automatic exposure meter, for example, it is arranged in front of the light receiving element.
In a solid-state imaging device, a near-infrared cut filter may be disposed at a position away from the front surface of the solid-state imaging device, or may be directly attached to a solid-state imaging device or a package of the solid-state imaging device. The cover for protecting the light may be a near infrared cut filter. Further, it may be directly attached to a low-pass filter using a crystal such as quartz or lithium niobate for reducing moire or false color.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these.

得られた化合物は、下記の分析結果より目的の化合物であることを確認した。
・ＭＳ（ＥＳＩ）（ｍ／ｚ）：４８３（＋）、７２８（−）４価、３２０（−）４価
・元素分析値： 実測値（Ｃ：３４．０３％、Ｈ：３．３１％、Ｎ：２．４５％）；理論値（Ｃ：３３．９９％、Ｈ：３．２８％、Ｎ：２．４８％）
このようにして得られた化合物のジメチルアセトアミド（ＤＭＡＣ）溶液は７８７ｎｍに極大吸収を示し、グラム吸光係数は１７２９００ｇ/ｍＬ・ｃｍであった。 Example 1 Production of Specific Example Compound (1) -1 Sodium tungstate dihydrate 3.08 g, sodium molybdate dihydrate 0.57 g, sodium phosphate dodecahydrate 0.18 g The product was dissolved in 30 mL of water, acidified with hydrochloric acid, 0.1 g of zinc powder was added, and the mixture was stirred at 90-95 ° C. for 1 hour.
After cooling to 70 ° C. or lower, a solution prepared by dissolving 2.2 g of the following polymethine compound (a) in 20 mL of methanol was added and stirred at 50 to 60 ° C. for 1 hour. After cooling, 50 mL of water was added, and the precipitate was collected by filtration and washed with water. Further, it was washed with 80 mL of methanol and dried to obtain 4.2 g of a green powder.

The obtained compound was confirmed to be the target compound from the following analysis results.
MS (ESI) (m / z): 483 (+), 728 (-) tetravalent, 320 (-) tetravalent Elemental analysis values: Measured values (C: 34.03%, H: 3.31% , N: 2.45%); theoretical value (C: 33.99%, H: 3.28%, N: 2.48%)
A dimethylacetamide (DMAC) solution of the compound thus obtained showed a maximum absorption at 787 nm, and the gram extinction coefficient was 172900 g / mL · cm.

得られた化合物は、下記の分析結果より目的の化合物であることを確認した。
・ＭＳ（ＥＳＩ）（ｍ／ｚ）：６５９（＋）、７２８（−）４価、３２０（−）４価
・元素分析値： 実測値（Ｃ：３６．８１％、Ｈ：１．０９％、Ｎ：２．０９％）；理論値（Ｃ：３６．７６％、Ｈ：１．０６％、Ｎ：２．１４％）
このようにして得られた化合物のＤＭＡＣ溶液は８２６．５ｎｍに極大吸収を示し、グラム吸光係数は６３２００ｇ/ｍＬ・ｃｍであった。 Example 2 Production of Specific Example Compound (1) -5 Sodium tungstate dihydrate 3.08 g, sodium molybdate dihydrate 0.57 g, sodium phosphate dodecahydrate 0.18 g The mixture was dissolved in 30 mL of water, acidified with hydrochloric acid, 0.1 g of zinc powder was added, and the mixture was stirred at 90-95 ° C. for 1 hour.
After cooling to 70 ° C. or lower, a solution prepared by dissolving 2.91 g of the following polymethine compound (b) in 20 mL of acetone was added and stirred at 50 to 60 ° C. for 1 hour. After cooling, 50 mL of water was added, and the precipitate was collected by filtration and washed with water. Further, it was washed with 80 mL of acetone and dried to obtain 4.1 g of a blackish brown powder.

The obtained compound was confirmed to be the target compound from the following analysis results.
-MS (ESI) (m / z): 659 (+), 728 (-) tetravalent, 320 (-) tetravalent-Elemental analysis value: Measured value (C: 36.81%, H: 1.09% , N: 2.09%); theoretical value (C: 36.76%, H: 1.06%, N: 2.14%)
The DMAC solution of the compound thus obtained showed a maximum absorption at 826.5 nm, and the gram extinction coefficient was 63200 g / mL · cm.

得られた化合物は、下記の分析結果より目的の化合物であることを確認した。
・ＭＳ（ＥＳＩ）（ｍ／ｚ）：１０７１（＋）、７２８（−）４価、３２０（−）４価
・元素分析値： 実測値（Ｃ：５３．１１％、Ｈ：１．０７％、Ｎ：３．２２％）；理論値（Ｃ：５３．０８％、Ｈ：１．０４％、Ｎ：３．２６％）
このようにして得られた化合物のＤＭＡＣ溶液は１０１２ｎｍに極大吸収を示し、グラム吸光係数は４７５００ｇ/ｍＬ・ｃｍであった。 [Example 3] Production of specific example compound (2) -1 In the same manner as in Example 2, except that 4.52 g of the following polymethine compound (c) was used instead of 2.91 g of the polymethine compound (b) in Example 2. As a result, 4.95 g of black powder was obtained.

The obtained compound was confirmed to be the target compound from the following analysis results.
-MS (ESI) (m / z): 1071 (+), 728 (-) tetravalent, 320 (-) tetravalent-Elemental analysis values: Measured values (C: 53.11%, H: 1.07% , N: 3.22%); theoretical value (C: 53.08%, H: 1.04%, N: 3.26%)
The DMAC solution of the compound thus obtained showed a maximum absorption at 1012 nm, and the gram extinction coefficient was 47500 g / mL · cm.

１２モリブデン（ＩＶ）リン酸ｎ水和物４．６５ｇ、メタノール４０ｍＬ、水２０ｍＬを５０-５５℃で1時間撹拌した。
次いでポリメチン化合物（ａ）１．５５ｇをメタノール４０ｍＬに溶解したものを加え、同温で1時間撹拌した。反応混合物からメタノールを留去して残渣に水１００ｍＬを加え、沈殿物をろ取、水洗した。更にメタノール８０ｍＬで洗浄して乾燥して緑色粉末３．３ｇを得た。
得られた化合物は、下記の分析結果より目的の化合物であることを確認した。
・ＭＳ（ＥＳＩ）（ｍ／ｚ）：４８３（＋）、６０７（−）３価
・元素分析値： 実測値（Ｃ：３５．２５％、Ｈ：３．３７％、Ｎ：２．５３％）；理論値（Ｃ：３５．２１％、Ｈ：３．３３％、Ｎ：２．５７％）
このようにして得られた化合物のジメチルアセトアミド（ＤＭＡＣ）溶液は７８７ｎｍに極大吸収を示し、グラム吸光係数は８２０００ｇ/ｍＬ・ｃｍであった。
なお、化合物（ｒ-１）は、特開平７−３１７７号公報で開示されているポリメチン化合物のアニオンを有する化合物である。 [Comparative Synthesis Example 1] Production of polymethine lake compound (r-1)

4.65 g of 12 molybdenum (IV) phosphoric acid n hydrate, 40 mL of methanol, and 20 mL of water were stirred at 50-55 ° C. for 1 hour.
Next, 1.55 g of polymethine compound (a) dissolved in 40 mL of methanol was added and stirred at the same temperature for 1 hour. Methanol was distilled off from the reaction mixture, 100 mL of water was added to the residue, and the precipitate was collected by filtration and washed with water. Further, it was washed with 80 mL of methanol and dried to obtain 3.3 g of a green powder.
The obtained compound was confirmed to be the target compound from the following analysis results.
-MS (ESI) (m / z): 483 (+), 607 (-) trivalent-Elemental analysis value: Measured value (C: 35.25%, H: 3.37%, N: 2.53%) ); Theoretical value (C: 35.21%, H: 3.33%, N: 2.57%)
A dimethylacetamide (DMAC) solution of the compound thus obtained showed a maximum absorption at 787 nm, and the gram extinction coefficient was 82000 g / mL · cm.
The compound (r-1) is a compound having an anion of a polymethine compound disclosed in JP-A-7-3177.

タングステン酸ナトリウム・二水和物９．１ｇ、リン酸１２．８ｇ、水４６ｍＬを９５−１００℃で７時間撹拌し、冷却後、臭素水１滴を添加した。
次いでポリメチン化合物（ａ）４．９ｇをメタノール８０ｍＬに溶解したものを加え、８０−８５℃で1時間撹拌した。水３０ｍＬを添加し、室温まで冷却、沈殿物をろ取、水洗した。更にメタノール１００ｍＬで洗浄し、乾燥して黒紫色粉末３．３ｇを得た。
得られた化合物は、下記の分析結果より目的の化合物であることを確認した。
・ＭＳ（ＥＳＩ）（ｍ／ｚ）：４８３（＋）、３３７１（−）
・元素分析値： 実測値（Ｃ：１０．０１％、Ｈ：０．９８％、Ｎ：０．７０％）；理論値（Ｃ：９．９７％、Ｈ：０．９４％、Ｎ：０．７３％）
このようにして得られた化合物のジメチルアセトアミド（ＤＭＡＣ）溶液は７８７ｎｍに極大吸収を示し、グラム吸光係数は１５０６００ｇ/ｍＬ・ｃｍであった。
なお、化合物（ｒ-２）は、特開平７−３１７７号公報で開示されているポリメチン化合物のアニオンを有する化合物である。 [Comparative Synthesis Example 2] Production of polymethine lake compound (r-2)

9.1 g of sodium tungstate dihydrate, 12.8 g of phosphoric acid, and 46 mL of water were stirred at 95-100 ° C. for 7 hours, and after cooling, 1 drop of bromine water was added.
Subsequently, what melt | dissolved 4.9 g of polymethine compounds (a) in 80 mL of methanol was added, and it stirred at 80-85 degreeC for 1 hour. 30 mL of water was added and cooled to room temperature, and the precipitate was collected by filtration and washed with water. Further, it was washed with 100 mL of methanol and dried to obtain 3.3 g of a black purple powder.
The obtained compound was confirmed to be the target compound from the following analysis results.
MS (ESI) (m / z): 483 (+), 3371 (-)
Elemental analysis values: measured values (C: 0.01%, H: 0.98%, N: 0.70%); theoretical values (C: 9.97%, H: 0.94%, N: 0) .73%)
A dimethylacetamide (DMAC) solution of the compound thus obtained showed a maximum absorption at 787 nm, and the gram extinction coefficient was 150600 g / mL · cm.
The compound (r-2) is a compound having an anion of a polymethine compound disclosed in JP-A-7-3177.

タングステン酸ナトリウム・二水和物４．５５ｇ、リン酸６．４ｇ、水２３ｍＬを９５−１００℃で７時間撹拌し、冷却後、臭素水１滴を添加した。
次いでポリメチン化合物（ｃ）５．０ｇをアセトン４０ｍＬに溶解したものを加え、８０−８５℃で1時間撹拌した。水１５ｍＬを添加し、室温まで冷却、沈殿物をろ取、水洗した。更にアセトン５０ｍＬで洗浄し、乾燥して黒色粉末５．５ｇを得た。
得られた化合物は、下記の分析結果より目的の化合物であることを確認した。
・ＭＳ（ＥＳＩ）（ｍ／ｚ）：１０７１（＋）、３３７１（−）
・元素分析値： 実測値（Ｃ：２０．５８％、Ｈ：１．５６％、Ｎ：０．７０％）；理論値（Ｃ：２０．５４％、Ｈ：１．５４％、Ｎ：０．６９％）
このようにして得られた化合物のジメチルアセトアミド（ＤＭＡＣ）溶液は１０１１ｎｍに極大吸収を示し、グラム吸光係数は５９９００ｇ/ｍＬ・ｃｍであった。
なお、化合物（ｒ-３）は、特開平７−３１７７号公報で開示されているポリメチン化合物のアニオンを有する化合物である。 [Comparative Synthesis Example 3] Production of polymethine lake compound (r-3)

4.55 g of sodium tungstate dihydrate, 6.4 g of phosphoric acid, and 23 mL of water were stirred at 95-100 ° C. for 7 hours, and after cooling, 1 drop of bromine water was added.
Subsequently, 5.0 g of polymethine compound (c) dissolved in 40 mL of acetone was added, and the mixture was stirred at 80 to 85 ° C. for 1 hour. Water (15 mL) was added, and the mixture was cooled to room temperature. The precipitate was collected by filtration and washed with water. Further, it was washed with 50 mL of acetone and dried to obtain 5.5 g of a black powder.
The obtained compound was confirmed to be the target compound from the following analysis results.
MS (ESI) (m / z): 1071 (+), 3371 (-)
Elemental analysis values: Measured values (C: 20.58%, H: 1.56%, N: 0.70%); theoretical values (C: 20.54%, H: 1.54%, N: 0 .69%)
A dimethylacetamide (DMAC) solution of the compound thus obtained showed a maximum absorption at 1011 nm, and the gram extinction coefficient was 59900 g / mL · cm.
The compound (r-3) is a compound having an anion of a polymethine compound disclosed in JP-A-7-3177.

[Example 4] Manufacture of near-infrared cut filter A 110% T B-NP (polyamide acid varnish 20% DMAC solution) manufactured by Mitsui Chemicals was further diluted with DMAC to prepare a 7% DMAC solution of polyamide acid varnish. A specific example compound (1) -1 (77 mg) and the 7% polyamic acid varnish DMAC solution (10 g) were treated with an ultrasonic vibration device for 20 minutes and dissolved to prepare a coating solution.
This coating solution was applied onto a glass plate and heated at 150 ° C. for 3 hours to form a polyimide resin film. The resin film was peeled from the glass plate to obtain a polyimide film (thickness 21 μm) containing the specific example compound (1) -1.

[Example 5] Production of near-infrared cut filter In Example 4, the same operation as in Example 4 was performed except that 77 mg of the specific compound (1) -5 was used instead of the specific compound (1) -1. A near-infrared cut filter was manufactured.

[Example 6] Production of near-infrared cut filter In Example 4, the same operation as in Example 4 was performed, except that 77 mg of the specific compound (1) -8 was used instead of the specific compound (1) -1. A near-infrared cut filter was manufactured.

[Example 7] Production of near-infrared cut filter In Example 4, the same operation as in Example 4 was performed except that 77 mg of the specific compound (1) -11 was used instead of the specific compound (1) -1. A near-infrared cut filter was manufactured.

[Example 8] Production of near-infrared cut filter In Example 4, the same operation as in Example 4 was performed, except that 77 mg of the specific compound (1) -20 was used instead of the specific compound (1) -1. A near-infrared cut filter was manufactured.

[Example 9] Production of near-infrared cut filter In Example 4, the same operation as in Example 4 was carried out except that 77 mg of the specific compound (2) -1 was used instead of the specific compound (1) -1. A near-infrared cut filter was manufactured.

[Example 10] Production of near-infrared cut filter In Example 4, the same operation as in Example 4 was performed, except that 77 mg of the specific compound (2) -3 was used instead of the specific compound (1) -1. A near-infrared cut filter was manufactured.

[Example 11] Production of near-infrared cut filter 100 g of cyclic olefin resin (Zeonor 1020R, manufactured by Nippon Zeon Co., Ltd.), 0.1 g of specific example compound (1) -1 and 400 g of DMAC were added, and the resin concentration was A 20% by weight solution was obtained.
The obtained solution was cast on a smooth glass plate, dried at 60 ° C. for 8 hours, and at 80 ° C. for 8 hours, and then peeled off from the glass plate. The peeled coating film was further dried under reduced pressure at 100 ° C. for 24 hours to produce a substrate having a thickness of 0.1 mm, a length of 60 mm, and a width of 60 mm. Subsequently, a dielectric multilayer film (silica layer (SiO ₂ : film thickness 83 to 199 nm) and a titania layer (TiO ₂ : film thickness 101 to 101 nm) reflecting near infrared rays at a deposition temperature of 100 ° C. on one side of the obtained substrate. And a dielectric multilayer film [silica layer (SiO ₂ : film thickness) reflecting near infrared rays at a deposition temperature of 100 ° C. on the other surface of the substrate. 77 to 189 nm) and titania layers (TiO ₂ : film thickness 84 to 118 nm) are formed alternately to form a near infrared cut filter filter having a thickness of 0.105 mm.

[Example 12] Production of near-infrared cut filter In Example 11, the same operation as in Example 11 except that 0.1 g of the specific compound (1) -5 was used instead of the specific compound (1) -1. A near-infrared cut filter was manufactured.

[Example 13] Production of near-infrared cut filter The same operation as in Example 11 except that 0.1 g of the specific example compound (2) -1 was used instead of the specific example compound (1) -1 in Example 11. A near-infrared cut filter was manufactured.

[Comparative Example 1] Production of near-infrared cut filter In Example 4, the same procedure as in Example 4 was performed, except that 77 mg of the polymethine lake compound (r-1) was used instead of the specific example compound (1) -1. A near-infrared cut filter was manufactured.

[Comparative Example 2] Production of near-infrared cut filter In Example 4, the same procedure as in Example 4 was performed, except that 77 mg of polymethine lake compound (r-2) was used instead of the specific example compound (1) -1. A near-infrared cut filter was manufactured.

[Comparative Example 3] Production of near-infrared cut filter In Example 4, the same operation as in Example 4 was performed, except that 77 mg of polymethine lake compound (r) -3 was used instead of specific example compound (1) -1. A near-infrared cut filter was manufactured.

[Comparative Example 4] Production of near-infrared cut filter The same operation as in Example 4 was performed except that 77 mg of the following naphthalocyanine (r-4) was used instead of the specific example compound (1) -1 in Example 4. A near-infrared cut filter was manufactured.

[Performance of near infrared cut filter]
The performance of the near-infrared cut filters manufactured in the examples and comparative examples were evaluated and compared by the following methods. For the transmittance measurement, a spectrophotometer (U-4100) manufactured by Hitachi High-Technology Corporation was used.

(Near-infrared cut performance)
Measure the transmittance at a wavelength of 750 to 820 nm or 990 to 1010 nm,
◎ If the transmittance is less than 10%
○ in the case of 10% or more and less than 20%
When it was 20% or more, it was set as x.
The results are shown in Table 3.

(Evaluation of visible light transmission performance)
The transmittance at a wavelength of 400 nm to 600 nm was measured. When the average transmittance was 80% or more, ◎, when 75% or more and less than 80%, ○, and when it was less than 75%, ×. The results are shown in Table 3.

(Durability evaluation)
-Light resistance test Using a xenon weathering device (Suntest XLS + II type manufactured by ATLAS), the test object is a xenon lamp at a black standard temperature of 65 ° C and a chamber temperature of 45 ° C with an irradiance of 550 W / m ² Irradiated for hours. Measure the minimum value of transmittance from 750 nm to 1010 nm of each sample before and after irradiation,
The rate of change before and after the test is less than 5%.
○ 5% or more and less than 10%
Those with 10% or more were marked with ×.
Rate of change in transmittance after 300 hours of light resistance test =
(Transmittance after 300 hours of light resistance test-transmittance before test) / transmittance before test Table 4 shows the results.

-Heat resistance test After the test object was exposed to the conditions of 200 ° C and 20% RH for 3 hours, the minimum transmittance from 750 nm to 1010 nm of each sample was measured,
The rate of change before and after the test is less than 5%.
○ 5% or more and less than 10%
Those with 10% or more were marked with ×.
Permeability change rate in 3 hours of heat test =
(Transmittance after 3 hours of light resistance test-transmittance before test) / transmittance before test Table 4 shows the results.

The polymethine compound of the present invention is chemically stable, has high durability such as heat resistance and light resistance, and is excellent in near infrared absorption performance and visible transmission performance. It has become possible to provide a near-infrared cut filter excellent in absorption performance and visible transmission performance, and a solid-state imaging device including the same.

Claims (6)

A polymethine compound represented by the following general formula (1).

(In Formula (1), A and B each independently represent a benzene ring which may have a substituent or a naphthalene ring which may have a substituent, and L ₁ is necessary to form a cyclic structure. An alkylene group which may have a substituent, one or more of the carbon atoms constituting the ring may be substituted with another atom or atomic group, and X ₁ and X ₂ are each independently 1,1- Dialkylmethylene group, 1-alkyl-1-benzylmethylene group which may have a substituent, 1,1-dibenzylmethylene group which may have a substituent or 3 carbon atoms which may have a substituent To 6 cycloalkane-1,1-diyl groups, R ₁ and R ₂ each independently represents an alkyl group which may have a substituent, and Y ₁ represents a hydrogen atom, a halogen atom, an alkylthio group, an arylthio group. Represents a group or a substituted amino group, n and m are independent of each other; There each percentage to the total amount of _W 2 _{O 7} and _{Mo 2 O 7, 0% <} n <100%, which is 0% <m <100%, and n + m = 100%. A and B are benzene rings which may have a substituent, L ₁ is an alkylene group having 2 to 4 carbon atoms which may have a substituent necessary to form a cyclic structure, and X ₁ X ₂ is a 1,1-dialkylmethylene group, R ₁ and R ₂ are alkyl groups having 1 to 8 carbon atoms, Y ₁ is a halogen atom, n is 40% to 95%, m The polymethine compound according to claim 1, wherein is 5% to 60%. A polymethine compound represented by the following general formula (2).

(In Formula (2), D, E, F, and G each independently represent a benzene ring that may have a substituent, and L ₂ may have a substituent necessary to form a cyclic structure. It is a good alkylene group, and one or more of the carbon atoms constituting the ring may be substituted with other atoms or atomic groups, and R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ independently represents an alkyl group which may have a substituent or a phenyl group which may have a substituent, and Y ₂ represents a hydrogen atom, a halogen atom, an alkylthio group, an arylthio group or a substituted amino group. Q and r are each independently the percentage of the total amount of W ₂ O ₇ and Mo ₂ O ₇ , 0% <q <100%, 0% <r <100%, and q + r = 100% It is. D, E, F and G are benzene rings which may have a substituent, and L ₂ is an alkylene group having 2 to 4 carbon atoms which may have a substituent necessary for forming a cyclic structure. R ₄ , R ₆ , R ₈ , and R ₁₀ are alkyl groups having 1 to 8 carbon atoms, and R ₃ , R ₅ , R ₇ , and R ₉ are phenyl groups that may have a substituent, The polymethine compound according to claim 3, wherein Y ₂ is a halogen atom, q is 40% to 95%, and r is 5% to 60%. A near-infrared cut filter comprising at least one polymethine compound according to claim 1 or 2 and / or claim 3 or 4 as a dye. A solid-state imaging device comprising the near infrared cut filter according to claim 5.