JPWO2008038569A1 - Optical filter - Google Patents

Abstract

The present invention provides an optical filter with excellent light resistance that cuts off infrared rays and / or neon light, etc., which impede image characteristics, improves display image characteristics, and maintains the performance for a long period of time. Is an issue. The object is solved by providing an optical filter comprising an ionic conjugate of a cyclic disulfonylimide anion and a dye cation.

Description

The present invention relates to an optical filter comprising an organic dye compound. In particular, the present invention relates to an optical filter that is mounted on the surface of a display such as a plasma display television to improve image characteristics and prevent malfunction by an electronic device using a near infrared remote controller.
Background art

  With the start of high-definition television broadcasting, the demand for plasma display television receivers has increased rapidly. A plasma display is a video display device that uses gaseous plasma discharge light. It has a color purity comparable to that of a cathode ray tube, is easy to achieve full color, and has a large viewing angle, making it compatible with high-definition television broadcasting. Development and mass production are progressing as a large video display device. However, Hioki Uchiike, “The Journal of the Institute of Image Information and Television Engineers”, Volume 51, No. 4, pp. 459 to 463 (1997) and Masahei Nozaki, “Monthly Display”, Vol. 6, No. 4, 72 thru As reported on page 77 (2000), the plasma display is, in principle, a so-called “neon orange” color near the wavelength of 600 nm that is emitted when excited neon atoms return to the ground state. Light emission and unnecessary near-infrared radiation are unavoidable. When these are mixed with red light emission, there is a problem that a vivid red display with good color purity cannot be obtained or the infrared remote controller malfunctions. In addition, dyes for improving display image characteristics such as prevention of reflection of fluorescent lamps, and films and optical filters using the dyes have been studied.

  In order to solve these problems, as a countermeasure against near-infrared rays, a method of attaching a front member using a near-infrared absorber to a display part of a plasma display has been proposed. For example, Japanese Patent Laid-Open No. 9-241520 JP-A-10-128898 discloses a front member using a nickel complex-based, azo-based or anthraquinone-based organic dye compound as a near-infrared absorber, and JP-A-10-128898 discloses a heterocyclic, anthraquinone-based, dithiol-nickel. A front member using a complex organic dye compound has been proposed. Further, as a countermeasure for improving the image characteristics of the display, for example, Japanese Patent Application Laid-Open No. 2001-188121 proposes a squalium dye.

  However, many of these organic dye compounds have insufficient light resistance to environmental light such as natural light and artificial light, and thus there has been a problem that the performance of the optical filter is likely to deteriorate when used for a long period of time.

  In view of such a situation, the present invention cuts infrared and / or neon light, etc., which are obstacles to image characteristics and the like, improves the image characteristics of the display, and has excellent light resistance that maintains its performance for a long period of time. It is an object to provide an optical filter.

  As a result of intensive research and search by the present inventor, an optical filter characterized by containing an ion conjugate of a cyclic disulfonylimide anion and a dye cation has an absorption maximum in the visible to infrared region, and plasma It has been found that when used for an optical filter attached to an image display device such as a display, it effectively blocks unnecessary light radiated from the image display device. Further, it has been found that such an optical filter has excellent light resistance and maintains its performance even for a long period of time.

  That is, the present invention provides an optical filter comprising an ionic conjugate in which a cyclic disulfonylimide anion represented by the general formula 1 and a dye cation represented by the general formula 2 are ionically bonded. The above-mentioned problem is solved.

（一般式１において、Ｒ_１、Ｒ_２はそれぞれ独立に水素原子又はハロゲン原子を表す。ｎはアルキレン基の炭素原子数を表し、２〜６の整数である。）General formula 1

(In General Formula 1, R ₁ and R ₂ each independently represents a hydrogen atom or a halogen atom. N represents the number of carbon atoms of the alkylene group and is an integer of 2 to 6.)

（一般式２において、Ｙはメチン鎖を表し、そのメチン鎖は置換基及び／又は環状構造を
有していてもよい。Ｚ_１及びＺ_２は互いに同じか異なる芳香環又は複素環を表し、それらの
芳香環及び複素環は置換基を有していてもよい。）General formula 2

(In General Formula 2, Y represents a methine chain, and the methine chain may have a substituent and / or a cyclic structure. Z ₁ and Z ₂ represent the same or different aromatic rings or hetero rings, (The aromatic ring and the heterocyclic ring may have a substituent.)

  Furthermore, the present invention provides either a diimonium salt represented by the general formula 3 or an organometallic complex having a skeleton represented by the general formula 4 in addition to an ionic conjugate of a cyclic disulfonylimide anion and a dye cation. Alternatively, the above-mentioned problems can be solved by providing an optical filter containing both.

（一般式３において、Ｒ_９乃至Ｒ_１６は、それぞれ独立に、水素原子又は、適宜の置換基を表し、Ｘ⁻は対アニオンである。）General formula 3

(In General Formula 3, R _{9 to} R ₁₆ each independently represent a hydrogen atom or an appropriate substituent, and X ⁻ is a counter anion.)

（一般式４の式中Ｒ_１７乃至Ｒ_２０はそれぞれ独立に水素原子又は適宜の置換基を表し、Ｒ_１７とＲ_１８、Ｒ_１９とＲ_２０が互いに連結して芳香環を形成しても良い。Ｙ_１とＹ_２はそれぞれ酸素原子、硫黄原子、または窒素原子を表し、Ｍは金属原子又は金属イオンを表す。Formula 4

(In the general formula 4, R _{17 to} R ₂₀ each independently represents a hydrogen atom or an appropriate substituent, and R ₁₇ and R ₁₈ , R ₁₉ and R ₂₀ may be linked to each other to form an aromatic ring. Y ₁ and Y ₂ each represent an oxygen atom, a sulfur atom, or a nitrogen atom, and M represents a metal atom or a metal ion.

  The optical filter of the present invention is excellent in light resistance, has a light absorption capacity that does not decrease over a long period of time, and can be used for various optical filter applications, particularly when used for an optical filter attached to a video display device such as a plasma display. In the visible light range, unnecessary light radiated from the image display device is effectively blocked without impairing the color purity of the three primary colors of the image, so that a high-quality image with excellent contrast and image characteristics can be obtained. Even in the near infrared region, the infrared remote controller does not malfunction due to near infrared rays. Furthermore, since the optical filter used in the present invention is excellent in light resistance, even if it is used for a long period of time, it becomes an optical filter whose performance is hardly lowered.

2 is a light transmission spectrum of a near-infrared thin film filter containing the compound 34 prepared in Example 1.

  The present invention is described in detail below. As described above, the present invention is an optical filter comprising an ionic conjugate of a cyclic disulfonylimide anion represented by general formula 1 and a dye cation represented by general formula 2.

General formula 1

In General Formula 1, R ₁ and R ₂ each independently represent a hydrogen atom or a halogen atom. Specific examples of the halogen atom include a fluorine atom, a bromine atom, and a chlorine atom. Among them, a fluorine atom is preferable, and a compound in which R ₁ and R ₂ are both fluorine atoms is particularly preferable. n represents the number of carbon atoms of the alkylene group and is an integer of 2 to 6, preferably 2 to 5, and more preferably 3.

General formula 2

  In General Formula 2, Y represents a methine chain. Specifically, it represents a monomethine chain or a methine chain having 1 to 12 carbon atoms in which a plurality of methine groups are bonded to each other. A methine chain of 7 is preferred.

  Such a methine chain may have a cyclic structure, and each cyclic structure includes one or more double bonds and / or heteroatoms, such as a cyclobutene ring, a cyclopentene ring, a cyclohexene ring, a benzene ring, Examples include monocyclic or condensed polycyclic rings such as a dehydrodecalin ring, a pyridine ring, a dihydropyridine ring, a tetrahydropyridine ring, a furan ring, a dihydrofuran ring, a thiophene ring, a dihydrothiophene ring, and a hexahydroquinoline ring.

  Such a methine chain and a cyclic structure may have one or more substituents without departing from the object of the present invention. Examples of the substituent in the methine chain and the cyclic structure include, for example, methyl group, ethyl group, vinyl group, propyl group, isopropyl group, isopropenyl group, 1-propenyl group, 2-propenyl group, 2-propynyl group, butyl group, Isobutyl group, sec-butyl group, tert-butyl group, 1,3-butadienyl group, 2-butenyl group, pentyl group, isopentyl group, neopentyl group, tert-pentyl group, 2-pentenyl group, 2-pentene-4- Aliphatic hydrocarbon groups such as inyl group, trifluoromethyl group, pentafluoroethyl group, heptafluoropropyl group, trichloromethyl group, pentachloroethyl group, heptachloropropyl group, tribromomethyl group, pentabromoethyl group, hepta Halogenated alkyl group such as bromopropyl group, methoxy group, trif Ether group such as olomethoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, sec-butoxy group, tert-butoxy group, pentyloxy group, phenoxy group, anilino group, o-triidino group, m-triidino group, p-triidino group, xylidino group, diphenylamino group, amino group such as p-methoxydiphenylamino group, sulfonyl group such as methylsulfonyl group, phenylsulfonyl group, arylthio group such as phenylthio group, naphthylthio group, fluoro group, chloro group , Halogen groups such as bromo group and iodo group, heterocyclic groups such as barbituric acid group, imidazolyl group and pyridyl group, alicyclic hydrocarbon groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group and cyclohexenyl group , Nitro group, cyano And hydroxy group.

Z ₁ and Z ₂ represent the same or different aromatic rings or heterocyclic rings, and these aromatic rings and heterocyclic rings may have one or more substituents. Examples of the aromatic ring in Z ₁ and Z ₂ include a benzene ring, a naphthalene ring, an azulene ring, an anthracene ring, a phenanthrene ring, and a biphenyl ring. Examples of the heterocyclic ring include a nitrogen atom, a phosphorus atom, and an oxygen atom. , A sulfur atom, a selenium atom, a tellurium atom, or the like, which contains one or more heteroatoms of Group 15 or Group 16 in the periodic table, such as an imidazoline ring, an imidazole ring, a benzimidazole ring, an α-naphthimidazole ring , Β-naphthimidazole ring, indole ring, isoindole ring, indolenine ring, isoindolenin ring, benzoindolenin ring, pyridinoindolenin ring, oxazoline ring, oxazole ring, isoxazole ring, benzoxazole ring, pyridino Oxazole ring, α-naphthoxazole ring, β-naphtho Xazole ring, selenazoline ring, selenazole ring, benzoselenazole ring, α-naphthoselenazole ring, β-naphthoselenazole ring, thiazoline ring, thiazole ring, isothiazole ring, benzothiazole ring, α-naphthothiazole ring, β- Naphthothiazole ring, tellurazoline ring, tellurazole ring, benzotelrazole ring, α-naphthotelrazole ring, β-naphthotelrazole ring, acridine ring, anthracene ring, isoquinoline ring, isopyrrole ring, imidazolane ring, indandione ring , Indazole ring, indyne ring, oxadiazole ring, carbazole ring, xanthene ring, quinazoline ring, quinoxaline ring, quinoline ring, chroman ring, cyclohexanedione ring, cyclopentanedione ring, cinnoline ring, thiodiazole ring, thioo Sazolidone ring, thiophene ring, thionaphthene ring, thiobarbituric acid ring, thiohydantoin ring, tetrazole ring, triazine ring, naphthyridine ring, piperazine ring, pyrazine ring, pyrazole ring, pyrazoline ring, pyrazolidine ring, pyrazolone ring, pyran ring, pyridine Ring, pyridazine ring, pyrimidine ring, pyrylium ring, pyrrolidine ring, pyrroline ring, pyrrole ring, phenazine ring, phenanthridine ring, phenanthroline ring, phthalazine ring, pteridine ring, furazane ring, furan ring, purine ring, benzoxazine ring, Examples thereof include a benzopyran ring, a morpholine ring, and a rhodanine ring.

Examples of the substituent in Z ₁ and Z ₂ include a methyl group, an ethyl group, a vinyl group, a propyl group, an isopropyl group, an isopropenyl group, a 1-propenyl group, a 2-propenyl group, a 2-propynyl group, a butyl group, Isobutyl group, sec-butyl group, tert-butyl group, 2-butenyl group, 1,3-butadienyl group, pentyl group, isopentyl group, neopentyl group, tert-pentyl group, 1-methylpentyl group, 2-methylpentyl group , 2-pentenyl group, 2-pentene-4-ynyl group, hexyl group, isohexyl group, 5-methylhexyl group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group and other aliphatic hydrocarbon groups, Alicyclic carbonization such as propyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cyclohexenyl group Aromatic hydrocarbon such as elementary group, phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, xylyl group, mesityl group, o-cumenyl group, m-cumenyl group, p-cumenyl group, biphenylyl group Group, methoxy group, trifluoromethoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group, pentyloxy group, phenoxy group and other ether groups, methoxycarbonyl group , Ester group such as ethoxycarbonyl group, propoxycarbonyl group, butoxycarbonyl group, acetyl group, benzoyloxy group, methylamino group, dimethylamino group, ethylamino group, diethylamino group, propylamino group, dipropylamino group, isopropylamino Group, diisopropylamino group, butyla Mino group, dibutylamino group, isobutylamino group, diisobutylamino group, sec-butylamino group, tert-butylamino group, pentylamino group, dipentylamino group, anilino group, o-triidino group, m-toluidino group, p- Amino groups such as toluidino group, xylidino group, diphenylamino group, heterocyclic groups such as quinolyl group, piperidino group, pyridyl group, morpholino group, alkylsulfonyl groups such as methylsulfonyl group, ethylsulfonyl group, trifluoromethylsulfonyl group, A halogen group such as a fluoro group, a chloro group, a bromo group, and an iodo group, a hydroxy group, a carboxyl group, a cyano group, a nitro group, and a substituent composed of a combination thereof can be mentioned.

Among the cyclic disulfonylimide anions represented by the general formula 1, particularly preferable compounds include compounds represented by the general formula 5 in which R ₁ and R ₂ in the general formula 1 are fluorine atoms.

Formula 5

In general formula 5, n represents the number of carbon atoms of the alkylene group, and represents the same value as n in general formula 1.

  Among the dye cations having the methine chain represented by the general formula 2, the cyanine dye represented by the general formula 6 can change the conjugated carbon number of the methine chain relatively easily in its synthesis, and its absorption Since the wavelength varies greatly depending on the number of conjugated carbons, it is possible to obtain a desired absorption wavelength by changing the number of conjugated carbons in the methine chain, and since it has a high molecular extinction coefficient, an optical filter Is particularly preferable in selecting a desired absorption wavelength.

General formula 6

In General Formula 6, Z ₃ and Z ₄ each represent an aromatic ring such as a benzene ring, a naphthalene ring, a pyridine ring, a quinoline ring, or a quinoxaline ring, and these aromatic rings may have one or more substituents. Examples of substituents, in Formula 2 include those similar to the substituent bonded to Z ₁ and Z _2. In the general formula 6, Z ₃ and Z ₄ may be the same as or different from each other.

A _{1 to} A ₂ in General Formula 6 represent a carbon atom or a hetero atom. Examples of the hetero atom include Group 15 in the periodic table such as a nitrogen atom, an oxygen atom, a sulfur atom, a selenium atom, and a tellurium atom. And Group 16 atoms. The carbon atom in A _{1 to} A ₂ may be an atomic group mainly composed of two carbon atoms such as an ethylene group and a vinylene group. Further, A ₁ and A ₂ in the general formula 6 may be the same or different from each other.

R ₃ and R ₄ in the general formula 6 represent an aliphatic hydrocarbon group or an aromatic hydrocarbon group. Examples of aliphatic hydrocarbon groups include, for example, methyl, ethyl, propyl, isopropyl, isopropenyl, 1-propenyl, 2-propenyl, butyl, isobutyl, sec-butyl, tert -Butyl group, 2-butenyl group, 1,3-butadienyl group, pentyl group, isopentyl group, neopentyl group, tert-pentyl group, 1-methylpentyl group, 2-methylpentyl group, 2-pentenyl group, hexyl group, Examples include an isohexyl group, a 5-methylhexyl group, a heptyl group, an octyl group, and the aromatic hydrocarbon group includes a phenyl group, an o-tolyl group, an m-tolyl group, a p-tolyl group, a xylyl group, and a mesityl group. , O-cumenyl group, m-cumenyl group, p-cumenyl group, biphenylyl group and the like, such aliphatic hydrocarbon group or Aromatic hydrocarbon group, further, the same substituents in Z ₁ and Z ₂ of Formula 2 may have one or more. Note that R ₃ and R ₄ in General Formula 6 may be the same or different from each other.

R _{5 to} R ₈ in General Formula 6 each independently represent a hydrogen atom or an appropriate substituent. Examples of the substituent include, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group, and tert-pentyl group. 1-methylpentyl group, 2-methylpentyl group, hexyl group, isohexyl group, 5-methylhexyl group, heptyl group, octyl group and other aliphatic hydrocarbon groups, phenyl group, o-tolyl group, m-tolyl group , P-tolyl group, xylyl group, mesityl group, o-cumenyl group, m-cumenyl group, p-cumenyl group, biphenylyl group and other aromatic hydrocarbon groups, trifluoromethyl group, pentafluoroethyl group, heptafluoropropyl Group, trichloromethyl group, pentachloroethyl group, heptachloropropyl group, tribromomethyl group, Halogenated alkyl groups such as interbromoethyl group and heptabromopropyl group, methoxy group, trifluoromethoxy group, ethoxy group, propoxy group, butoxy group, tert-butoxy group, pentyloxy group, phenoxy group, benzoyloxy group, etc. Ether groups, etc., and such aliphatic hydrocarbon groups, aromatic hydrocarbon groups, and ether groups further have one or more substituents similar to the substituents in Z ₁ and Z ₂ of Formula 2. It may be. In General Formula 6, when A _{1 to} A ₂ are heteroatoms, some or all of R _{5 to} R ₈ may not exist.

R _{5 to} R ₈ can be bonded to a substituent in Z ₃ or Z ₄ or Z ₃ or Z ₄ to form a condensed ring, and R ₅ and R ₆ , R ₇ and R ₈ are By bonding, a 3- to 8-membered ring containing a carbon atom, an oxygen atom, a sulfur atom, a nitrogen atom, or the like can be formed. L represents a methine chain, and examples thereof include the same methine chain Y in general formula 2.

  Examples of the ionic conjugate of a cyclic disulfonylimide anion and a dye cation used in the present invention include those represented by Chemical Formula 1 to Chemical Formula 51. These ion conjugates are, for example, neon light-absorbing dyes having an absorption maximum in the wavelength region of 550 to 620 nm in an optical filter such as a plasma display, or near absorption having a maximum absorption in the near infrared region of wavelength 800 to 1200 nm. It is extremely useful as an infrared absorbing dye. In addition, the compound used by this invention is not limited to these.

Chemical formula 1

Chemical formula 2

Chemical formula 3

Chemical formula 4

Chemical formula 5

Chemical formula 6

Chemical formula 7

Chemical formula 8

Chemical formula 9

Chemical formula 10

Formula 11

Chemical formula 12

Chemical formula 13

Chemical formula 14

Chemical formula 15

Chemical formula 16

Chemical formula 17

Chemical formula 18

Chemical formula 19

Chemical formula 20

Chemical formula 21

Chemical formula 22

Chemical formula 23

Chemical formula 24

Chemical formula 25

Chemical formula 26

Chemical formula 27

Chemical formula 28

Chemical formula 29

Chemical formula 30

Chemical formula 31

Chemical formula 32

Chemical formula 33

Chemical formula 34

Chemical formula 35

Chemical formula 36

Chemical formula 37

Chemical formula 38

Chemical formula 39

Chemical formula 40

Chemical formula 41

Chemical formula 42

Chemical formula 43

Chemical formula 44

Chemical formula 45

Chemical formula 46

Chemical formula 47

Chemical formula 48

Chemical formula 49

Chemical formula 50

Chemical formula 51

  Any of the compounds represented by Chemical Formulas 1 to 51 of the present invention can be obtained in a desired amount according to a known method or according to a known method for preparing an analogous compound. For example, FM Harmer, “Heterocyclic Compounds Cyanine Dies and Related Compounds”, John Willy and Sons. John Wiley & Sons, New York, London, 1964, and by DM Sturmer, “Heterocyclic Compound in Special Topic in Heterocyclic Chemistry” “Compounds-Special Topics in Heterocyclic Chemistry” ”, Chapter 18 , Pp. 482-515, John Willy & Sons, New York, London, 1977, “Rods Chemistry of Carbon Compounds”. 2nd, Ed. vol. IV, part B, published in 1977, Chapter 15, pages 369-422, Elsevier Science Publishing Company, New York, JP-A-6-313939 and JP-A-5-88293 It can be easily synthesized with reference to gazettes and the like.

  Furthermore, the optical filter of the present invention is capable of bringing either or both of the diimonium salt represented by the general formula 3 or the organometallic complex having a skeleton represented by the general formula 4 in addition to the organic dye compound. It can be contained as an infrared absorber or a light resistance improver.

General formula 3

Formula 4

In General Formula 3, R _{9 to} R ₁₆ each independently represent a hydrogen atom or an appropriate substituent. Examples of the substituent include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group, tert-pentyl group, 1 -Aliphatic hydrocarbon groups such as methylpentyl group, 2-methylpentyl group, hexyl group, isohexyl group, 5-methylhexyl group, heptyl group, octyl group, nonyl group, decyl group, trifluoromethyl group, pentafluoroethyl Group, heptafluoropropyl group, trichloromethyl group, pentachloroethyl group, heptachloropropyl group, tribromomethyl group, pentabromoethyl group, halogenated alkyl group such as heptabromopropyl group, cyanomethyl group, 2-cyanoethyl group, Cyanoalkyl such as 3-cyanopropyl group An aromatic hydrocarbon group such as phenyl, o-tolyl, m-tolyl, p-tolyl, xylyl, mesityl, o-cumenyl, m-cumenyl, p-cumenyl, biphenylyl, Hydroxyl group, benzyl group, phenethyl group, phenylpropyl group, finyl-α-methylpropyl group, finyl-β-methylpropyl group, phenylbutyl group, phenylpentyl group, phenyloctyl group, naphthylmethyl group, naphthylmethyl group, etc. Examples include arylalkyl groups and substituents composed of combinations of these substituents, and R _{9 to} R ₁₆ may be the same or different.

R _{9 to} R ₁₆ are not particularly limited as long as they are the above substituents, but are preferably an aliphatic hydrocarbon group having a straight chain or a side chain having 1 to 8 carbon atoms, a halogenated alkyl group, a cyanoalkyl group, A straight chain aliphatic hydrocarbon group having 2 to 6 carbon atoms is particularly preferred. Specific examples of particularly preferable ones include an ethyl group, a propyl group, a butyl group, a pentyl group, an isopropyl group, an isobutyl group, and an isopentyl group.

Furthermore, the arylalkyl group in R _{9 to} R ₁₆ is preferably a phenylalkyl group, and the phenyl group in the phenylalkyl group is further an aliphatic hydrocarbon group, a hydroxyl group, a sulfonic acid group, an alkylsulfonic acid group, a nitro group, You may have 1 type or multiple types of substituents, such as an amino group, an alkoxy group, a halogenated alkyl group, and a halogen. Of these, more preferred arylalkyl groups include phenylalkyl groups having no substituent.

  Particularly preferred examples of such a phenylalkyl group include a benzyl group and a phenethyl group.

  In the general formula 3, X is an anion for forming a salt, and an anion that keeps the general formula 3 neutral. Examples of such anions include organic acids and inorganic acids, and are not particularly limited.

In the general formula 4, R _{17 to} R ₂₀ each independently represent a hydrogen atom, an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a cyano group, and R ₁₇ and R ₁₈ , R ₁₉ and R ₂₀ are connected to each other. Can form an aromatic ring. Examples of such an aromatic ring include a benzene ring or a naphthalene ring, and the benzene ring or naphthalene ring may have a substituent. Examples of the substituent include, for example, Z ₁ and Z ₂ in the general formula 2 The same thing as a substituent is mentioned.

Examples of the aliphatic hydrocarbon group and aromatic hydrocarbon group for R _{17 to} R ₂₀ include the same aliphatic hydrocarbon groups and aromatic hydrocarbon groups for R _{9 to} R ₁₆ in the general formula 3.

Y ₁ and Y ₂ each independently represent an oxygen atom, a sulfur atom or a nitrogen atom, and a sulfur atom is particularly preferred. M represents a metal atom or metal ion, usually scandium, yttrium, titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, technetium, rhenium, iron, ruthenium, osmium, cobalt, rhodium, Transition metals of Groups 3 to 12 in the periodic table such as iridium, nickel, palladium, platinum, copper, silver, gold, zinc, cadmium, mercury, etc. are selected. Of these, manufacturing costs and ease of handling are selected. Thus, cobalt, nickel and copper of Groups 9 to 11 in the periodic table are preferable.

  When M is a metal ion, the organometallic complex having a skeleton represented by the general formula 4 has a cationic counter ion to keep the organometallic complex neutral. Examples of cationic counter ions include quaternary ammonium salts such as tetramethylammonium, tetraethylammonium, tetrabutylammonium, octyltriethylammonium, phenyltrimethylammonium, triphenylbutylammonium, triphenylbenzylammonium, tetraphenylammonium, tetra There can be mentioned quaternary phosphonium salts such as methylphosphonium, tetraethylphosphonium, tetrabutylphosphonium, octyltriethylphosphonium, phenyltrimethylphosphonium, triphenylbutylphosphonium, triphenylbenzylphosphonium, tetraphenylphosphonium.

  Examples of the diimonium salt include those represented by chemical formulas 52 to 56, and examples of the organometallic complex include those represented by chemical formulas 57 to 62.

Chemical formula 52

Chemical formula 53

Chemical formula 54

Chemical formula 55

Formula 56

Chemical formula 57

Chemical formula 58

Chemical formula 59

Chemical formula 60

Chemical formula 61

Chemical formula 62

  Any of the above dimonium salt and organometallic complex can be obtained in a desired amount according to a known method or according to a known method for preparing an analogous compound. The diimonium salt can be produced, for example, with reference to Japanese Patent Application Laid-Open No. 2005-325292, and the organometallic complex can be produced by “organometallic compound synthesis method and utilization method”, supervised by Akio Yamada, Tokyo Chemical Dojin, (1991 Issue).

Now, the optical filter of the present invention containing such an ion conjugate of a cyclic disulfonylimide anion and a dye cation will be described. At least the member used for the optical filter of the present invention is a transparent base material that is the main component of the member used. And an ionic conjugate of a cyclic disulfonylimide anion as a light absorber and a dye cation. As the light absorber, in addition to an ionic conjugate of a cyclic disulfonylimide anion and a dye cation, a diimonium salt, an organometallic complex, or the like can be used in combination. The “light absorber” as used in the present invention is used for such a member and substantially blocks unnecessary light emitted from the image display device or natural light, particularly light in the near infrared region. A light-absorbing organic compound or a composition containing a light-absorbing organic compound is meant. In the optical filter of the present invention, the content of the light-absorbing organic compound is usually in the range of 1 to 1000 mg / m ² , preferably 5 to 100 mg / m ² per unit area of the optical filter.

  As the transparent substrate, in the entire visible region, the light transmittance is 50% or more, preferably 70% or more, for example, ABS resin, polyacrylic acid resin, polyacrylic acid ester resin, polyarylate resin, polyester resin, Polyether sulfone resin, polyvinyl chloride resin, polyolefin resin, polycarbonate resin, polyvinyl acetate resin, polystyrene resin, polymethacrylic acid resin, polymethacrylic acid ester resin, and glass, ceramic, etc. These are used in combination as appropriate. Among these, in terms of light transmittance and mechanical strength, polyacrylic acid resin, polyacrylic ester resin, polyarylate resin, polyester resin, polyethersulfone resin, polyolefin resin, polycarbonate resin, polymethacrylic acid resin, Polymethacrylate resins are particularly preferred.

  The optical filter of the present invention may be formed into a film, a sheet, a panel, or the like according to the shape of the use part after mixing the light absorber with the transparent substrate, or the use part Depending on the shape of the film, it can be produced by adhering a light absorbent to one or both sides of a transparent substrate that has been formed into a film, sheet, panel, etc., and forming a light shielding layer with the light absorbent. it can. The thickness of the transparent base material after molding is preferably 0.1 μm to 10 mm, more preferably 0.5 μm to 100 μm, although it depends on the material of the transparent base material and the area of the used part. Depending on the situation of use, instead of directly attaching the transparent base material to the use part, the transparent base material may be temporarily bonded to a glass plate or the like according to the shape of the use part, and the glass plate may be attached to the use part. . In such a case, the transparent base material is formed into a relatively thin film, for example, a film or a sheet, and an adhesive layer or the like for bonding the transparent base material to a glass plate is formed on one surface thereof.

  In the former method of mixing the light absorber with the transparent substrate, for example, the resin and the light absorber, which are transparent substrates, are melt-kneaded, and if necessary, once formed into a pellet, etc., then extrusion molding, It is molded according to the shape of the display part in the video display device by a method such as injection molding or press molding, or the raw material monomer of the transparent base material and the light absorber are mixed and injected according to the shape of the display part. Mold polymerization.

  On the other hand, in the latter method of providing a light absorber layer in close contact with a transparent substrate, for example, if necessary, a binder is allowed to coexist and the light absorber is, for example, chloroform, cyclohexanone, ethyl methyl ketone, Dissolve or disperse in an appropriate organic solvent such as ketones such as isopropyl methyl ketone, ethers such as halogenated hydrocarbons, ethylene glycol monopropyl ether, and esters, depending on the shape of the used part, for example Apply directly to one or both sides of a transparent substrate that has been formed into a film, sheet, panel, etc., or apply a solution or dispersion prepared in the same way to the same material as on a transparent substrate. Once applied to the film or sheet, the transparent substrate that has been formed according to the shape of the use part of the film or sheet It is stuck to the surface or both sides.

  Examples of the binder include ethylene-vinyl acetate copolymer resin, ethylene-vinyl alcohol copolymer resin, cellulose acetate resin, vinyl acetate resin, cellulose resin, nylon, phenol resin, phenoxy resin, polyester resin, and polyethyl methacrylate. Examples thereof include resins, polycarbonate resins, polystyrene resins, polysulfone resins, polyvinyl butyral resins, polymethyl methacrylate resins, and the like, and these are used in combination as appropriate. Such a binder is usually used in an amount of 10 to 1,000 times, preferably 50 to 500 times by weight with respect to the light absorber of the present invention. When the light absorber is applied as a dispersion, the solid light absorber is dispersed as fine particles having a particle diameter of 0.1 to 10 μm, preferably 0.5 to 5 μm.

  In order to apply a solution or dispersion containing a light absorber to a transparent substrate, etc., it is widely used in the field, for example, dipping method, flow coating method, spray method, bar coating method, gravure coating method, roll coating method The blade coating method, the air knife coating method, and the like are applied, and these are applied in combination as appropriate.

  The optical filter of the present invention includes an ion conjugate of a cyclic disulfonylimide anion and a dye cation, or an ion conjugate of a cyclic disulfonylimide anion and a dye cation, and diimonium without departing from the object of the invention. For example, an aminium salt compound, an amino compound, an aminothiol nickel complex compound, an anthraquinone compound, an imonium compound, a cyanine compound, and triallyl, which are widely used in the art, together with a light absorber composed of a salt or an organometallic complex. Methane compounds, naphthoquinone compounds, nitroso compounds and their metal salts, phthalocyanine compounds, carbon black, indium tin oxide, near-infrared absorbers containing antimony tin oxide, benzotriazole compounds, benzophenone compounds, hydroxy Ultraviolet absorbers containing benzoate compounds, titanium oxide, zinc oxide, cerium oxide, iron oxide, barium sulfate, etc., as well as antioxidants, flame retardants, stabilizers, lubricants, antistatic agents, heat aging inhibitors One or a plurality of release agents may be included. An ionic conjugate of a cyclic disulfonylimide anion and a dye cation of the present invention, or an ion conjugate of such a cyclic disulfonylimide anion and a dye cation, and a light absorber containing a diimonium salt or an organometallic complex, When used in combination with near-infrared absorbers and ultraviolet absorbers as described above, the light resistance of the organic dye compound contained in the light absorber is remarkably improved, and it is faded, denatured and decomposed by ambient light such as natural light and artificial light. Is effectively suppressed.

  Further, the optical filter of the present invention is used in this field as needed, for example, silver, silver-palladium alloy, indium oxide, indium oxide-tin oxide mixture (ITO), zinc oxide, etc. It is not prohibited to use in combination with one or more of an anti-reflective agent containing an agent, metal oxide, metal fluoride, metal silicide, metal boride, metal carbide, metal nitride, metal sulfide and the like. These materials are usually formed as a layer independent of the light shielding layer containing the light absorber on the transparent substrate by a method such as vacuum deposition, sputtering, ion plating, or ion beam assist. Alternatively, one or more of an ultraviolet blocking layer, an electromagnetic wave blocking layer, an antireflection layer, etc. are formed on a film or sheet of the same material as in the transparent substrate, and the film or sheet is bonded to the transparent substrate. .

  Furthermore, the optical filter of the present invention attaches a non-glare layer for suppressing glare and widening the viewing angle, a hard coat layer for protecting the surface, and an optical filter to an image display device or a glass plate, if necessary. It does not prevent providing one or more, such as a pressure-sensitive adhesive layer.

  The optical filter of the present invention thus obtained comprises an ionic conjugate of a cyclic disulfonylimide anion and a dye cation, or an ionic conjugate of a cyclic disulfonylimide anion and a dye cation, and a diimonium salt or an organometallic complex. By selecting an ionic conjugate having an appropriate absorption range according to the wavelength of light to be blocked, a light absorber containing no waste in the near infrared region without impairing the color purity of the three primary colors of light. Light, especially infrared light and / or neon light in plasma displays, is selectively blocked, and the three primary colors of light are reproduced well in the visible light range, resulting in high-quality images with excellent contrast and color reproducibility. Moreover, the infrared remote controller does not malfunction due to near infrared rays. Examples of the image display device to which the optical filter of the present invention can be applied include, for example, a direct-view television using a cathode ray tube, a television using a plasma display, an electroluminescent display, a non-light emitting panel using a liquid crystal display, and the like. TVs, rear projection TVs with built-in liquid crystal projectors, and the like. Among these, the optical filter of the present invention can be applied to a light-emitting panel type television using a plasma display, an electroluminescence display, or the like that easily radiates unnecessary light in principle.

Hereinafter, embodiments of the present invention will be described based on experimental examples and examples.

Experimental Example 1: Light Stability of Near-Infrared Absorbing Dye With respect to an ionic conjugate of a cyclic disulfonylimide anion and a dye cation contained in the optical filter of the present invention, the light stability of the ionic conjugate alone under thin film conditions Examined. Using the chemical formula 34, the chemical formula 37, which are the ionic conjugates of the present invention, and the chemical formula 63, the chemical formula 64, which are comparative compounds, for each pigment, 0.1% by mass of the pigment and polymethylmethacrylate (trade name “PMMA”, 2.5% by mass (manufactured by Sigma Aldrich) was dissolved in methyl ethyl ketone (hereinafter referred to as “MEK”). Thereafter, a thin film filter was formed on the polycarbonate substrate by spin coating. The thin film absorption at that time was measured, and the absorbance (initial absorbance) of the dye at the absorption maximum wavelength (λmax) was measured. Then, using the trade name “Cenon Weather Meter XL-75” (manufactured by Suga Test Instruments Co., Ltd.), measurement conditions: 180 W / m ² temperature in the tank: 15 ° C., humidity: 60% exposure for a predetermined time (300 KJ / m ² ), the absorbance (absorbance after irradiation) at the absorption maximum wavelength (λmax) (λmax in chemical formula 34 is 947 nm and λmax in chemical formula 37 is 865 nm) is measured, and “absorbance after irradiation / The value of the “initial absorbance” expressed as 100 fraction was determined as the dye residual ratio. The results are shown in Table 1. Further, FIG. 1 shows a light transmission spectrum of an optical filter containing an ionic conjugate represented by the chemical formula 34.

Chemical formula 63 (Comparative compound 1)

Chemical formula 64 (Comparative Compound 2)

  From the results shown in Table 1, the ionic conjugate contained in the optical filter of the present invention showed an improvement of about 10% in stability compared with the comparative example conventionally used as a near infrared absorbing material. The ionic conjugate contained in the optical filter of the present invention is superior to the materials used in the past, and an improvement in light resistance of about 10% is confirmed. When used in an optical filter, it is effective in light stability. I understand.

Experimental Example 2: Light stability of near-infrared absorbing dye Combined use of organometallic complex The ionic conjugate of the cyclic disulfonylimide anion and the dye cation contained in the optical filter of the present invention contains an ionic conjugate and an organometallic complex. The light stability of the light absorber under thin film conditions was investigated. The dithiol metal complex represented by the chemical formula 34, the chemical formula 37, which is the ionic conjugate of the present invention, and the chemical formula 63, which is the comparative compound, and the chemical formula 64. 0.1% by mass and 2.5% by mass of polymethyl methacrylate (trade name “PMMA”, manufactured by Sigma-Aldrich) were dissolved in MEK. Thereafter, a thin film filter was formed on the polycarbonate substrate by spin coating. The thin film absorption at that time was measured, and the absorbance (initial absorbance) of the dye at the absorption maximum wavelength (λmax) (λmax in Chemical Formula 34 was 947 nm and λmax in Chemical Formula 37 was 865 nm) was measured. Then, using “Cenon Weather Meter XL-75” (manufactured by Suga Test Instruments), exposure for a predetermined time (300 KJ / m ² , 600 KJ /) under measurement conditions: 180 W / m ² temperature in the tank: 15 ° C. humidity: 60% m ² , 1200 KJ / m ² ), the absorbance at λmax (absorbance after irradiation) was measured, and the value of “absorbance after irradiation / initial absorbance” at the absorption maximum wavelength was expressed as a fraction of 100 Calculated as a rate. The results are shown in Table 2.

From the results of Table 2, when combined organometallic complexes Formula 57, when 300 kJ / ^{m 2} light irradiation, as compared with the comparative example, although a large difference is not for light stability, 600 kJ / ^{m 2} when irradiated with light In about 6%, 1200 KJ / m ² light irradiation, about 10% improvement in light stability is confirmed, and as the light irradiation time becomes longer (light irradiation amount increases), It was confirmed that a thin film filter using an ionic conjugate and an organometallic complex in combination has superior light stability compared to the comparative example, and the optical filter containing the dye of the present invention and the organometallic complex is the conventional example of the comparative example. It was confirmed that the filter was more stable to light for a longer period of time than an optical filter containing a dye.

Experimental Example 3: Photostability of near-infrared absorbing dye Combined use with dimonium salt Regarding an ionic conjugate of a cyclic disulfonylimide anion and a pigment cation contained in the optical filter of the present invention, light absorption containing an ionic conjugate and a diimonium salt The photostability of the agent under thin film conditions was investigated. Using the chemical formula 34 and chemical formula 37 which are ionic conjugates of the present invention and the chemical formula 63 and chemical formula 64 which are comparative compounds, for each dye, 0.1% by weight of the dye, and a diimonium salt represented by the chemical formula 53 6% by mass and 2.5% by mass of polymethyl methacrylate (trade name “PMMA”, manufactured by Sigma-Aldrich) were dissolved in MEK. Thereafter, a thin film filter was formed on the polycarbonate substrate by spin coating. The thin film absorption at that time was measured, and the absorbance (initial absorbance) of the dye at the absorption maximum wavelength (λmax) (λmax in Chemical Formula 34 was 947 nm and λmax in Chemical Formula 37 was 865 nm) was measured. Then, using “Cenon Weather Meter XL-75” (manufactured by Suga Test Instruments), measurement conditions: 180 W / m ² temperature in tank: 15 ° C. humidity: 60% exposure for a predetermined time (600 KJ / m ² , 2400 KJ / After performing m ² ), the absorbance at λmax (absorbance after irradiation) was measured, and the value of “absorbance after irradiation / initial absorbance” at the absorption maximum wavelength expressed in 100 fractions was determined as the dye residual ratio. The results are shown in Table 3.

The results in Table 3, when used in combination diimmonium salt represented by Chemical Formula 53, when 600 kJ / ^{m 2} light irradiation, as compared with the comparative example, although a large difference is not seen in the light stability, 2400KJ / ^{m 2} Light When irradiated, a light stability of about 9% was confirmed. The thin film filter using the ionic conjugate of the present invention and the diimmonium salt is more stable to light as the light irradiation time becomes longer (the amount of light irradiation increases) compared to the comparative example. It was shown in It was confirmed that the optical filter containing the ionic conjugate of the present invention and the diimonium salt is more stable to light for a longer period than the optical filter containing the conventional dye of the comparative example.

Example 1: Optical filter 100 parts by mass of a 20% by weight toluene solution of a saturated copolyester resin (trade name “Byron 200” manufactured by Toyobo Co., Ltd.) and 0.5 of an ion conjugate represented by Chemical Formula 37 After mixing with the mass% cyclohexanone solution, toluene was added to adjust the concentration of the polyester resin to 9 mass%. Next, using a bar coater, this solution is uniformly applied to one side of a polyethylene terephthalate film (trade name “T100E”, manufactured by Diafoil Hoechst Co., Ltd., thickness 100 μm) and dried to provide a coating having a thickness of 4 μm. An optical filter having a film was prepared.

  Any of the optical filters of this example that effectively blocks unnecessary light radiated from the image display device without impairing the color purity of the three primary colors of the image can be advantageously applied to an image display device such as a plasma display.

Example 2: Optical filter 100 parts by mass of a 20% by weight toluene solution of a saturated copolyester resin (trade name “Byron 200” manufactured by Toyobo Co., Ltd.) and 0.5 of an ionic conjugate represented by Chemical Formula 37 After mixing with the mass% cyclohexanone solution, 0.66 mass% of diimonium represented by Chemical Formula 52 was added, and toluene was added to adjust the concentration of the polyester resin to 9 mass%. Next, using a bar coater, this solution is uniformly applied to one side of a polyethylene terephthalate film (trade name “T100E”, manufactured by Diafoil Hoechst Co., Ltd., thickness 100 μm) and dried to provide a coating having a thickness of 4 μm. An optical filter having a film was prepared.

  All of the optical filters of this example that effectively block unwanted light radiated from the video display device without impairing the color purity of the three primary colors of the video can be advantageously applied to video display devices such as plasma displays. It became possible to create optical filters with improved light resistance.

Example 3: Optical filter 100 parts by mass of a 20% by weight toluene solution of a saturated copolyester resin (trade name “Byron 200” manufactured by Toyobo Co., Ltd.) and 0.5 of an ionic conjugate represented by Chemical Formula 37 After mixing with the mass% cyclohexanone solution, 0.2 mass% of the dithiol metal complex represented by Chemical Formula 57 was added, and toluene was added to adjust the concentration of the polyester resin to 9 mass%. Next, using a bar coater, this solution is uniformly applied to one side of a polyethylene terephthalate film (trade name “T100E”, manufactured by Diafoil Hoechst Co., Ltd., thickness 100 μm) and dried to provide a coating having a thickness of 4 μm. An optical filter having a film was prepared.

All of the optical filters of this example that effectively block unwanted light radiated from the video display device without impairing the color purity of the three primary colors of the video can be advantageously applied to video display devices such as plasma displays. It became possible to create optical filters with improved light resistance.
Industrial applicability

  As described above, the optical filter of the present invention is excellent in light resistance, has a light absorption capability that does not decrease over a long period of time, and can be used for various optical filter applications. For example, an optical filter attached to a video display device such as a plasma display. When used in a filter, it effectively blocks unwanted light radiated from the video display device without losing the color purity of the three primary colors of the image in the visible light range, resulting in high image quality with excellent contrast and color reproducibility. An image can be obtained, and the infrared remote controller does not malfunction due to near infrared rays even in the near infrared region.

  It can be said that this invention having such remarkable effects is a very significant invention that contributes to the world.

Claims (4)

An optical filter comprising an ionic conjugate of a cyclic disulfonylimide anion represented by General Formula 1 and a dye cation represented by General Formula 2.
General formula 1:

(In General Formula 1, R ₁ and R ₂ each independently represents a hydrogen atom or a halogen atom. N represents the number of carbon atoms of the alkylene group and is an integer of 2 to 6.)
General formula 2:

(In General Formula 2, Y represents a methine chain, and the methine chain may have a substituent and / or a cyclic structure. Z ₁ and Z ₂ represent the same or different aromatic rings or hetero rings, (The aromatic ring and the heterocyclic ring may have a substituent.) The optical filter according to claim 1, wherein the cyclic disulfonylimide anion is a cyclic disulfonylimide anion represented by the general formula 5, and the dye cation is a dye cation represented by the general formula 6.
General formula 5:

(In General Formula 5, n represents the number of carbon atoms of the alkylene group and is an integer of 2 to 6.)
General formula 6:

(In General Formula 6, Z ₃ and Z ₄ represent the same or different aromatic rings or heterocyclic rings, and these aromatic rings or heterocyclic rings may have a substituent. A ₁ and A ₂ are respectively Independently, it represents a carbon atom or a hetero atom, R ₃ and R ₄ represent an aliphatic hydrocarbon group or an aromatic hydrocarbon group, and the aliphatic hydrocarbon group or the aromatic hydrocarbon group has a substituent. R _{5 to} R ₈ each independently represents a hydrogen atom or an appropriate substituent, and when A ₁ and A ₂ are heteroatoms, a part or all of R _{5 to} R ₈ are present. R _{5 to} R ₈ can be bonded to a substituent in Z ₃ or Z ₄ or Z ₃ or Z ₄ to form a condensed ring, and R ₅ and R ₆ , R ₇ and R ₈ can be combined. Can combine to form a 3- to 8-membered ring, L is a methine chain It represents, the methine chain may have a substituent and / or a cyclic group. The optical filter according to claim 1, wherein the cyclic disulfonylimide anion is an anion represented by Chemical Formula 65.
Chemical formula 65:

The optical filter according to any one of claims 1 to 3, comprising either a diimonium salt represented by the general formula 3 or an organometallic complex having a skeleton represented by the general formula 4, or both.
General formula 3:

(In General Formula 3, R _{9 to} R ₁₆ each independently represent a hydrogen atom or an appropriate substituent, and X ⁻ is a counter anion.)
General formula 4:

(In the general formula 4, R _{17 to} R ₂₀ each independently represents a hydrogen atom or an appropriate substituent, and R ₁₇ and R ₁₈ , R ₁₉ and R ₂₀ may be linked to each other to form an aromatic ring. Y ₁ and Y ₂ each represents an oxygen atom, a sulfur atom, or a nitrogen atom, and M represents a metal atom or a metal ion.)

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