WO2008038569A1

WO2008038569A1 - Optical filter

Info

Publication number: WO2008038569A1
Application number: PCT/JP2007/068276
Authority: WO
Inventors: Yasushi Aizawa; Kentaro Yano; Jun'ichiro Ihara; Masaaki Tamura; Yoji Yamaguchi
Original assignee: Kabushiki Kaisha Hayashibara Seibutsu Kagaku Kenkyujo; Japan Carlit Co., Ltd.
Priority date: 2006-09-28
Filing date: 2007-09-20
Publication date: 2008-04-03
Also published as: KR20090073147A; JPWO2008038569A1; JP5216997B2

Abstract

Disclosed is an optical filter having excellent light resistance, which can block out infrared ray and/or neon light or the like which becomes an obstacle to image properties or the like, which can improve image properties of a display, and whose properties can be maintained over a long period. Specifically disclosed is an optical filter characterized by comprising a ionic conjugate of a cyclic disulfonylimide anion with a dye cation.

Description

Specification

Optical filter technology

[0001] The present invention relates to an optical filter comprising an organic dye compound. In particular, the present invention relates to an optical filter that can be mounted on the surface of a display such as a plasma display TV to improve image characteristics and prevent malfunctions caused by electronic equipment using a near-infrared ray remote control.

Background art

[0002] 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 wide viewing angle, making it compatible with high-definition television broadcasting. Development and mass production of large-sized video display devices are underway. Tokorochi Hirai 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- As reported on page 77 (2000), the plasma display, in principle, has a so-called “neon orange color” around a wavelength of 600 nm that is emitted when excited neon atoms return to the ground state. '' And unnecessary near-infrared radiation are unavoidable, and when mixed with red light emission, a bright red display with good color purity cannot be obtained or the infrared remote control may malfunction. . In addition, pigments for improving display image characteristics, such as preventing reflection of fluorescent lamps, and films and optical filters using pigments are being 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 the display part of a plasma display has been proposed. Kaihei 9-241520 discloses a front member member using a nickel complex, azo, and anthraquinone organic dye compound as a near-infrared absorber. Also, JP-A-10-128898 discloses a heterocyclic group, Front members using anthraquinone and dithiol-uckel complex organic dye compounds have been proposed. Further, as a measure for improving the image characteristics of the display, for example, JP 2001-188121 A A squalium dye has been proposed.

[0004] However, force S, and many of these organic dye compounds are not sufficiently light resistant to ambient light such as natural light and artificial light, so that the performance of the optical filter tends to deteriorate when used for a long period of time. was there.

Disclosure of the invention

[0005] In view of such a situation, the present invention cuts infrared rays and / or neon light, etc., which hinder image characteristics and the like, improves the image characteristics of the display, and maintains its performance for a long period of time. It is an object to provide an optical filter with excellent light resistance.

[0006] As a result of diligent research and search by the present inventor, an optical filter characterized by containing an ionic conjugate of cyclic disulfonylimide anion and dye power thione is in the visible to infrared region. It has been found that it has the maximum absorption and can effectively block unnecessary light radiated from the image display device when it is used as an optical filter attached to an image display device such as a plasma display. 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 is characterized by containing an ionic conjugate in which the cyclic disulfonylimide anion represented by the general formula 1 and the dye cationic force S represented by the general formula 2 are S-ion bonded. The problem is solved by providing an optical filter.

[0008] General formula 1

[Chemical 1]

(In General Formula 1, R and R each independently represent a hydrogen atom or a halogen atom. N

1 2

Represents the number of carbon atoms of the alkylene group, and is an integer of 2 to 6. ) [0009] General formula 2

[Chemical 2]

(In General Formula 2, Y represents a methine chain, and the methine chain has a substituent and / or a cyclic structure.

You may have. Z and Z represent the same or different aromatic rings or heterocyclic rings, and

1 2

of

The aromatic ring and the heterocyclic ring may have a substituent. )

[0010] Further, the present invention provides a dimonium salt represented by the general formula 3 or a skeleton represented by the general formula 4 in addition to the ionic conjugate of the cyclic disulfonylimide anion and the dye cation. The above-mentioned problems are solved by providing an optical filter characterized in that it contains both! /, Deviated or! /, Of an organometallic complex having a hydrogen atom.

[0011] General formula 3

[Chemical 3]

(In General Formula 3, R to R are each independently a hydrogen atom or an appropriate substituent.

9 16

X_ is an anion. )

[0012] General formula 4

[Chemical 4]

(In formula (4), R 1 to R 4 each independently represents a hydrogen atom or an appropriate substituent,

17 20

R and R, R and R may be connected to each other to form an aromatic ring. Y and Y are each

17 18 19 20 1 2

Represents an oxygen atom, a sulfur atom, or a nitrogen atom, and M represents a metal atom or metal ion

[0013] The optical filter of the present invention is excellent in light resistance and does not deteriorate its light absorption ability over a long period of time, and can be used for various optical filter applications. In particular, an optical filter attached to an image display device such as a plasma display When used in a filter, it effectively blocks unwanted light radiated from image display equipment that does not impair the color purity of the three primary colors of the image in the visible light range, resulting in high-quality images with excellent contrast and image characteristics. Is obtained. In addition, even if the infrared remote control falls in the near infrared range, the infrared remote control will not malfunction due to the near infrared! /. Furthermore, since the optical filter used in the present invention is excellent in light resistance, it becomes an optical filter whose performance hardly deteriorates even when used for a long time.

Brief Description of Drawings

[0014] [FIG. 1] Light transmittance of a near-infrared thin film filter containing compound 34 prepared in Example 1 BEST MODE FOR CARRYING OUT THE INVENTION

[0015] The present invention is described in detail below. As described above, the present invention is represented by the general formula 1. An optical filter comprising a cyclic disulfonylimide anion and a dye conjugate represented by the general formula 2.

General formula 1

[Chemical 5]

In the general formula 1,! /, R and R each independently represent a hydrogen atom or a halogen atom.

1 2

Specific examples of the hydrogen atom and the rogen atom include a fluorine atom, a bromine atom, and a chlorine atom. Of these, a fluorine atom is preferred. A compound in which R and R are both fluorine atoms is particularly preferred.

1 2

Yes. 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.

[0018] General formula 2

[Chemical 6]

[0019] In the general formula 2, Y represents a methine chain, specifically, a monomethine chain force, or a methine chain having 1 to 12 carbon atoms formed by bonding a plurality of methine groups, Especially preferred are methine chains with 1 to 7 carbon atoms!

[0020] The individual methine chain may have a cyclic structure, and examples of the individual cyclic structure include one or more double bonds and / or heteroatoms such as a cyclobutene ring and a cyclopentane. Monocyclic ring such as ten ring, cyclohexene ring, benzene ring, dehydrodecalin ring, pyridine ring, dihydropyridine ring, tetrahydropyridine ring, furan ring, dihydrofuran ring, thiophene ring, dihydrothiophene ring, hexahydroquinoline ring Or a condensed polycyclic type is mentioned.

[0021] The methine chain and the 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 cyclic structure include, for example, methinole group, ethyl group, vinylinole group, propyl group, isopropyl group, isopropenyl group, 1 propenyl group, 2-propenyl group, and 2-propynyl group. , Butyl group, isobutyl group, se c butyl group, tert butyl group, 1, 3 butagenyl group, 2 butur group, pentynol group, isopentyl group, neopentyl group, tert pentyl group, 2-pentyl group, 2-pentene group 4 — Aliphatic hydrocarbon group such as ynyl group, trifluoromethyl group, pentafluoroethyl group, heptafluoropropyl group, trichloromethyl group, pentachloroethyl group, heptachloropropinole group, tribromomethinole group , Alkyl groups such as pentab mouth moletin group, heptabromo mouth pill group, methoxy group, trifluoromethoate Si group, ethoxy group, propoxy group, isopropoxy group, butoxy group, sec butoxy group, tert butoxy group, pentyloxy group, phenoxy group and other ether groups, anilino group, o triidino group, m-triidino group, p-triidino group, Amino group such as xylidino group, diphenylamino group, p-methoxydiphenylamino group, sulfonyl group such as methylsulfonyl group, phenylsulfonyl group, arylthio group such as phenylthio group, naphthylthio group, fluoro group, chloro group, bromo group Halogen groups such as iodine groups, heterocyclic groups such as barbituric acid groups, imidazolyl groups and pyridyl groups, alicyclic hydrocarbons such as cyclopropyl groups, cyclobutyl groups, cyclopentyl groups, cyclohexyl groups and cyclohexenyl groups Group, nitro group, cyano group, hydroxy group, etc. It is below.

[0022] Z and Z represent the same or different aromatic rings or heterocyclic rings,

1 2

The prime ring may have one or more substituents. Examples of aromatic rings in Z and Z

1 2

For example, a force such as a benzene ring, naphthalene ring, azulene ring, anthracene ring, phenanthrene ring, biphenyl ring, or a heterocyclic ring includes, for example, a nitrogen atom, phosphorus atom, oxygen atom, sulfur atom, selenium atom, tellurium To group 15 or 16 in the periodic table of atoms, etc. Comprising one or more telo atoms, such as imidazoline ring, imidazole ring, benzimidazole ring, α-naphthimidazole ring, / 3-naphthoimidazole ring, indole ring, isoindole ring, indolenine ring, isoindolenine ring, Benzoindolenin ring, pyridino indolenine ring, oxazoline ring, oxazole ring, isoxazole ring, benzoxazole ring, pyridinooxazole ring, α-naphthoxazole ring, / 3-naphthoxazole ring, selenazoline ring, selenazole ring, Benzoselenazole ring, α-naphthoselenazole ring, 0 naphthoselenazole ring, thiazoline ring, thiazole ring, isothiazole ring, benzothiazole ring, α-naphthothiazole ring, / 3-naphthothiazole ring, tellrazoline ring, tellurazole ring, benzo Lurazole ring, α-naphthotelrazole ring, β-naphthotelrazole ring, as well as atalidine ring, anthracene ring, isoquinoline ring, isopyrrole ring, imidazolano ring, indandione ring, indazole ring, indalin ring, oxadiazole ring, canolevazole ring , Xanthene ring, quinazoline ring, quinoxaline ring, quinoline ring, chroman ring, cyclohexanedione ring, cyclopentanedione ring, cinnoline ring, thiazazole ring, thixazolidone ring, thiophene ring, thianaphthene ring, thiobarbituric acid ring Thiohydantoin ring, tetrazole ring, triazine ring, naphthyridine ring, piperazine ring, pyrazine ring, pyrazole ring, pyrazoline ring, virazolidine ring, pyrazolone ring, pyran ring, pyridine ring, pyridazine ring, pyrimidine , Pyrylium ring, pyrrolidine ring, pyrroline ring, pyrrole ring, phenazine ring, phenanthridine ring, phenanthrin ring, phthalazine ring, pteridine ring, furazane ring, furan ring, purine ring, benzoxazine ring, benzopyran ring, morpholine Ring, rhodanine ring and the like.

Examples of the substituent in Ζ and Ζ include, for example, methyl group, ethyl group, bur group, propylene.

1 2

Nore group, isopropyl group, isopropenyl group, 1 propenyl group, 2-propenyl group, 2-propynyl group, butyl group, isobutyl group, sec butyl group, tert butyl group, 2-butenoyl group 1,3-Butagenyl group, pentyl group, isopentyl group, neopentyl group, tert pentyl group, 1-methylpentyl group, 2-methylpentyl group, 2-pentyl group, 2-pentene-4-ynyl group, hexyl group, isohexyl Groups, aliphatic hydrocarbon groups such as 5-methylhexyl group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cyclohexyl group Alicyclic hydrocarbon group such as senyl group, phenyl group, o tolyl group, m tolyl group, p tolyl group, xylyl group, mesityl group, o tameyl group, m tamediyl group, p tamedi Aromatic group, biphenylyl group, methoxy group, trifluoromethoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, isobutoxy group, sec butoxy group, tert butoxy group, pentyloxy group, Ether groups such as phenoxy group, methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, butoxycarbonyl group, acetyl group, benzoyloxy group and other ester groups, methylamino group, dimethylamino group, ethynoleamino group, jetylamino group, Propylamino group, dipropylamino group, isopropylamino group, diisopropylamino group Butylamino group, dibutylamino group, isobutylamino group, diisobutylamino group, sec butylamino group, tert butylamino group, pentylamino group, dipentylamino group, anilinino group, o triidino group, m toluidino group, p toluidino group, xylidino Group, amino group such as diphenylamino group, quinolyl group, piperidino group, pyridyl group, morpholino group and other heterocyclic groups, methylsulfonyl group, ethylsulfonyl group, trifluoromethylsulfonyl group and other alkylsulfonyl groups, fluoro group , Halogen groups such as chloro group, bromo group and iodine group, hydroxy group, canolepoxinole group, cyano group, nitro group, and substituents composed of combinations thereof.

[0024] Among the cyclic disulfonylimide anions represented by the general formula 1, a particularly preferable compound is R in the general formula 1.

1, compounds represented by general formula 5 in which R is a fluorine atom 2

d * o

[0025] General formula 5

[Chemical 7]

[0026] 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.

[0027] Among dye cations having a methine chain represented by the general formula 2, the cyanine dye represented by the general formula 6 can relatively easily change the conjugated carbon number of the methine chain in terms of synthesis. Since the absorption wavelength varies greatly depending on the number of conjugated carbons, it is possible to obtain the desired absorption wavelength by changing the number of conjugated carbons in the methine chain and to have a high molecular extinction coefficient. Therefore, it is particularly preferable for selecting a desired absorption wavelength in the optical filter.

[0028] General formula 6

[Chemical 8]

[0029] In general formula 6, Z and Z are benzene ring, naphthalene ring, pyridine ring, quinoline ring,

3 4

An aromatic ring such as a quinoxaline ring is represented, and these aromatic rings may have one or more substituents. Examples of the substituent are the same as the substituents bonded to Z and Z in formula 2.

1 2

The power of J is S. In general formula 6, Z and Z are the same as each other.

3 4

Can be different too.

[0030] A to A in the general formula 6 represent a carbon atom or a hetero atom,

1 2

Examples thereof include group 15 and group 16 atoms in the periodic table such as nitrogen atom, oxygen atom, sulfur atom, selenium atom and tellurium atom. In A to A

The 12 carbon atom may be an atomic group mainly composed of 2 carbon atoms such as an ethylene group or a vinylene group. Moreover, even if A and A in general formula 6 are the same,

1 2

It may be different. [0031] R and R in the general formula 6 represent an aliphatic hydrocarbon group or an aromatic hydrocarbon group.

3 4

Examples of the aliphatic hydrocarbon group include, for example, methyl group, ethyl group, propyl group, isopropinole group, isopropenyl group, 1-propenyl group, 2-propenyl group, butyl group, isobutyl group, sec butyl group, tert butyl group, 2 butyr group, 1,3 butagenyl group, pentyl group, isopentyl group, neopentyl group, tert pentyl group, 1-methylpentyl group, 2 methylpentyl group, 2 penturyl group, hexyl group, iso Hexyl group, 5-methylhexyl group, heptyl group, octyl group, etc., and aromatic hydrocarbon groups such as ί, phenol group, ο 卜 linole group, m 卜 linole group, p キシ linole group, xy linole group group, Meshichinore group, o Tameniru group, _m - Tameniru group, p Tame group, etc. Bifue two drill group and the like, such an aliphatic hydrocarbon group or an aromatic hydrocarbon group, Luo, general formula 2 Z and Z

1 or 2 may have one or more substituents similar to those in 1 2. In the general formula 6, R and R may be the same or different from each other.

3 4

[0032] R to R in General Formula 6 each independently represents a hydrogen atom or an appropriate substituent.

5 8

To express. Examples of substituents include, for example, methyl group, ethyl group, propyl group, isopropinole group, butyl group, isobutyl group, sec butyl group, tert butyl group, pentyl group, isopentyl group, neopentyl group, tert pentyl group. 1-methylpentyl group, 2-methylolene pentyl 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 tamenyl group, m tamenyl group, p tamenyl group, biphenyl group and other aromatic hydrocarbon groups, trifluoromethyl group, Pentafluoroethyl group, heptafluororepinol group, trichloromethinole group, pentachloroethinole group, heptachloropropyl group, tribromomethyl group, pentabromo group Halogenated alkyl group such as til group, heptabromopropyl group, methoxy group, trifluoromethoxy group, ethoxy group, propoxy group, butoxy group, tert butoxy group, pentyloxy group, phenoxy group, benzoyl group, etc. Such aliphatic hydrocarbon group, aromatic hydrocarbon group, and ether group are further substituted with the same substituents as those in Z and Z in the general formula 2.

1 2

Or you may have two or more. In general formula 6, A to A are heteroatoms.

1 2

In some cases, some or all of R to R may not be present. [0033] R to R are bonded to Z or Z or a substituent in Z or Z to form a condensed ring.

5 8 3 4 3 4

In addition, R and R, R and R are combined to form a carbon atom, oxygen atom, and sulfur atom.

5 6 7 8

Can form 3- to 8-membered rings containing children, nitrogen atoms, etc. L represents a methine chain, and examples thereof include the same methine chain Y in general formula 2.

[0034] Examples of the ionic conjugate of the cyclic disulfonylimide anion and the dye cation used in the present invention include those represented by Chemical Formula 1 to Chemical Formula 51, for example. These ionic conjugates have, for example, optical absorption filters such as plasma displays, as neon light-absorbing dyes having an absorption maximum in the wavelength region of 550 to 620 nm, or have a maximum absorption in the near infrared region of wavelength 800 to 1200 nm. It is extremely useful as a near infrared absorbing dye. In addition, the compound used by this invention is not limited to these.

[0035] Chemical Formula 1

[Chemical 9]

[0036] Chemical Formula 2

[Chemical 10]

[0037] Chemical Formula 3 [Chemical 11]

[0038] Chemical formula 4 [Chemical 12]

Chemical formula 5

Chemical formula 6 [Chem. 14]

Chemical formula 7 [Chemical 15]

Chemical formula 8 [Chemical 16] ^F F 0.

[0043] Chemical Formula 9

[Chemical 17]

[0044] Formula 10

[Chemical 18]

[0045] Formula 11

[Chemical 19]

[0046] Chemical formula 12 [Chemical 20]

[0047] Chemical formula 13 [Chemical formula 21]

[0048] Chemical formula 14 [Chemical 22]

[0049] Chemical Formula 15

[Chemical 23]

[0050]

[0051]

[0052] Formula 18

[Chemical 26]

[0053] Chemical formula 19 [Chemical 27]

[0054] Chemical formula 20 [Chemical 28]

[0055] Formula 21

[Chemical 29]

[0056] Chemical Formula 22 [Chemical 30]

[0057] Chemical formula 23 [Chemical 31]

Chemical formula 24

[Chemical 32]

Chemical formula 25 [Chemical 33]

Chemical formula 26 [Chemical formula 34]

Chemical formula 27

[Chemical 35]

N

OS SM

[0062] Formula 28

[Chemical 36]

[0063] Chemical Formula 29

[Chemical 37]

Chemical formula 30

[Chemical 38]

[0065] Chemical formula 31 [Chemical 39]

Chemical formula 32 [Chemical 40]

[0067] Formula 33

[Chemical 41]

[0068] Chemical Formula 34 [Chemical Formula 42]

[0069] Formula 35 [Chemical 43]

Chemical formula 36

[Chemical 44]

o ss =,, / D--r o o

[0071] Chemical Formula 37

[Chemical 45]

[0072] Formula 38

[Chem 46]

[0073] Formula 39 [Chemical 47]

[0075]

[0076] Formula 42 [Chemical Formula 50]

[0077] Chemical Formula 43

[Chemical 51]

[0078] Formula 44

[Chemical 52]

[0079] Formula 45 [Chemical Formula 53]

[0081]

Chemical formula 48

[Chemical 56]

[0083] Chemical formula 49 [Chemical formula 57]

[0084] Formula 50 [Chemical Formula 58]

[0085] Chemical formula 51 [Chemical 59]

[0086] Any of the compounds represented by the chemical formulas 1 to 51 of the present invention can be obtained in a desired amount according to a known method for preparing a similar compound or a force by a known method. Can do. For example, FM Harmer, “Heterocyclic Com pounds and yanme uyes and Related ompounds”, Nyung Willy Zonoto 'John Wiley & Sons, New York, London, 1964, published by DM Sturmer,' Heterocyclic 'compounds, Peschanole Totubix in Heterocyclic · Heterocyclic Compoun ds—special topics in cyclic chemistry, 18 early, verses 14, pp. 482-515, John Wiley & Sons, New York, London, 1977 fi \ "Kudd's' Chemistry of Ob 'Carbon' Compounds" (Rodds Chemistry of Carbon Compounds), 2nd, Ed. Vol. IV, part B, published in 1977, No. 1 Chapter 5, pp. 369-422, Elsevier 'Science' Public 'Company' Ink (Elsevier science Publishing Company Inc., New York, JP-B-393939 and JP-A-5-88293) Can be synthesized.

[0087] Further, the optical filter of the present invention includes either a dimonium salt represented by the general formula 3 or an organometallic complex having a skeleton represented by the general formula 4, in addition to the organic dye compound. Or both can be included as near infrared absorbers or light resistance improvers.

In General Formula 3, R to R are each independently a hydrogen atom or an appropriate substitution.

9 16

Represents a group. Examples of the substituent include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, an isopentyl group, a neopentyl group, and a tert-pentyl group. 1-methylpentyl group, 2-methylenopentyl group, hexyl group, isohexyl group, 5-methylhexyl group, heptyl group, octyl group, nonyl group, decyl group and other aliphatic hydrocarbon groups, trifluoro Methyl group, pentafluoroethyl group, heptafluoropropyl group, trichloromethyl group, pentachloroethyl Nore group, halogenated alkyl group such as heptachloropropyl group, tribromomethyl group, pentabromoethyl group, heptbromopropyl group, cyanomethyl group, 2-cianoethyl group, cyanoalkyl group such as 3-cyanopropyl group, phenyl group, o —Tolyl group, m-tolyl group, p-trinole group, xylinole group, mesityl group, o-tamenyl group, m-tamenyl group, p-tamenyl group, biphenylsilyl group and other aromatic hydrocarbon groups , Hydroxyl group, benzyl group, phenethyl group, phenylpropyl group, fininole α-methylpropyl group, fininole β-methyl propyl group, phenylbutyl group, phenylpentyl group, phenyloctyl group, naphthylmethyl group, naphthylmethyl group, etc. Examples include reel alkyl groups and substituents that can combine these substituents. Are, R to R may be different and the same.

9 16

[0091] R to R are not particularly limited as long as they are the above substituents.

9 16

A straight-chain aliphatic hydrocarbon group having 2 to 6 carbon atoms, such as an aliphatic hydrocarbon group having a chain or a side chain, a halogenated alkyl group, or a cyanoalkyl group, is particularly preferred. Specific examples of particularly preferable ones include ethyl group, propyl group, butyl group, pentyl group, isopropyl group, isobutyl group and isopentyl group.

[0092] Further, the arylalkyl group in R to R is preferably a phenylalkyl group.

9 16

Further, the phenyl group in the phenylalkyl group further includes an aliphatic hydrocarbon group, a hydroxyl group, a sulfonic acid group, an alkylsulfonic acid group, a nitro group, an amino group, an alkoxy group, a halogenated alkyl group, and a halogen. Has one or more substituents! /, May! /. Of these, more preferred arylalkyl groups include phenylalkyl groups having no substituent.

[0093] Such a phenylalkyl group is particularly preferred! /, And examples thereof include a benzyl group and a phenethylol group.

[0094] In general formula 3, X is an anion for forming a salt, and is an anion that keeps general formula 3 neutral. Such anions include, for example, organic acids and inorganic acids, and are not particularly limited.

[0095] In the general formula 4, R 1 to R 4 are each independently a hydrogen atom or an aliphatic hydrocarbon group.

17 20

Represents an aromatic hydrocarbon group or cyano group, and R and R, R and R are connected to each other to form an aromatic ring

17 18 19 20

Can form the power. Such aromatic rings include benzene rings or naphthalene rings. The benzene ring or naphthalene ring may have a substituent, and examples of the substituent include the same substituents as Z and Z in formula 2.

1 2

[0096] Examples of the aliphatic hydrocarbon group and the aromatic hydrocarbon group in R 1 to R 4 include ones

17 20

The same as the aliphatic hydrocarbon group and aromatic hydrocarbon group in R to R in the general formula 3 are listed.

9 16

I can get lost.

[0097] Y and Y each independently represent an oxygen atom, a sulfur atom or a nitrogen atom, particularly sulfur

1 2

Atoms are preferred. M represents a metal atom or metal ion. Group 3 to group 12 transition metals in the periodic table, such as cobalt, rhodium, iridium, nickel, noradium, platinum, copper, silver, gold, zinc, force domes, mercury, etc., are selected. From the viewpoint of production cost and ease of handling, Group 9 to Group 11 cobalt, Nikkenore and copper in the periodic table are preferred.

[0098] 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 counterions include tetramethylammonium, tetraethylammonium, tetrabutylammonium, octyltriethylammonium, phenyltrimethylammonium, triphenylenorebutinoleammonium, trifium. Quaternary ammonium salts such as Enenorependinoleanmonium, Tetraphenylenomonium, Tetramethylphosphonium, Tetraethylphosphonium, Tetrabutinorephosphonium, Octinoretrechinorephosphonium, Hue Examples include quaternary phosphonium salts such as ninoretrimethinorephosphonium, triphenenolebutinorephosphonium, triphenenolevenorephosphonium and tetraphenylphosphonium.

[0099] Examples of the dimonium salt include those represented by the chemical formulas 52 to 56, and examples of the organic metal complex include those represented by the chemical formulas 57 to 62.

[0100] Formula 52

[Chemical 62]

[0101] Formula 53 [Chemical 63]

[0102] Formula 54 [Chemical 64]

[0103] Formula 55

[Chemical 65]

[0105] Chemical formula 57 [Chemical 67]

[0106] Formula 58

[Chemical 68]

[0107] Formula 59

[Chem 69]

[0108] Formula 60

[Chemical 70]

(C ₄ H ₉ ) ₄ N

[0109] Formula 61

[Chemical 71]

Chemical formula 62

[Chemical 72]

[0111] Each 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 dimoyuum 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, Year issue).

[0112] Now, the optical filter of the present invention containing an ion conjugate of the cyclic disulfonylimide anion and the dye cation will be described. At least the member used for the optical filter of the present invention is a member used. And a 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 dimonium salt, an organometallic complex, or the like can be used in combination. The “light absorber” in the present invention means that unnecessary light emitted from a video display device or natural light, particularly light in the near infrared region, is substantially used by being used for such a member. It means a composition containing a light-absorbing organic compound or a light-absorbing organic compound that is blocked. In the optical filter of the present invention, the content of the light-absorbing organic compound is usually in a range of! To 1000 mg / m ² , preferably 5 to 100 mg / m, per unit area of the optical filter. .

[0113] The transparent substrate has a light transmittance of 50% or more, preferably 70% or more in the entire visible region, for example, ABS resin, polyacrylic acid resin, polyacrylic acid ester resin, polyarylate resin, Examples include polyester resin, polyethersulfone resin, polychlorinated bur resin, polyolefin resin, polycarbonate resin, polyacetic acid bur resin, polystyrene resin, polymethacrylic acid resin, polymethacrylic ester resin, and glass and ceramic. If necessary, these are used in appropriate combination. Of these In terms of light transmittance and mechanical strength, polyacrylic acid resin, polyacrylic acid ester resin, polyarylate resin, polyester resin, polyethersulfone resin, polyolefin resin, polycarbonate resin, polymethacrylic acid resin, polymethacrylic acid An ester resin is particularly preferred.

[0114] The optical filter according to the present invention has the ability to form, for example, a film shape, a sheet shape, a panel shape, etc. according to the shape of the use portion after the light absorber is mixed into the transparent substrate. Depending on the shape of the part to be used, a light absorber is adhered to one or both sides of a transparent substrate that has been formed into a film, sheet, panel, etc. It is possible to manufacture by forming S. The thickness of the transparent base material after molding is preferably 0.5; 1 m to 10 mm, although it depends on the material of the transparent base material and the area of the used part. Is more preferable. Depending on the situation of use, instead of attaching the transparent base material directly 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 to be relatively thin, for example, in the form of a film or a sheet, and an adhesive layer or the like for bonding the transparent base material to the glass plate is formed on one side thereof. .

[0115] In the former method of mixing the light absorber with the transparent substrate, for example, the resin that is the transparent substrate and the light absorber are melt-kneaded and, if necessary, once formed into a pellet or the like, Shape according to the shape of the display part in the video display device by methods such as extrusion molding, injection molding, press molding, etc., or mix the raw material monomer of the transparent substrate and the light absorber and shape the display part Depending on the type, cast polymerization is performed.

[0116] 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 light absorber can be used together with, for example, black mouth form, Dissolves in organic solvents such as cyclohexanone, ethyl methyl ketone, isopropyl methyl ketone and other ketones, halogenated hydrocarbons, ether glycols such as ethylene glycol monopropyl ether, and esters. Depending on the shape of the used part, it can be dispersed and applied directly to one or both sides of a transparent substrate that has been formed into a film, sheet, panel, etc. Once the dispersion is applied to a film or sheet of the same material as on the transparent substrate, A sheet or sheet is bonded to one or both sides of a transparent base material that has been molded according to the shape of the part to be used.

[0117] Examples of the noder include ethylene monoacetate copolymer resin, ethylene monovinyl alcohol copolymer resin, cellulose acetate resin, acetate resin, cellulose resin, nylon, phenol resin, phenoxy resin, and polyester. Examples thereof include resins, polyethylene methacrylate resins, polycarbonate resins, polystyrene resins, polysulfone resins, polyvinyl butyral resins, polymethyl methacrylate resins, and the like, and these are used in combination as necessary. Such binder is usually used in a weight ratio of 10 to 1,000 times, preferably 50 to 500 times, 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 Hm, preferably 0.5 to 5 Hm.

[0118] In order to apply a solution or dispersion containing a light absorber to a transparent substrate or the like, it is widely used in the field, for example, dating method, flow coating method, spray method, bar coating method, gravure coating method. A roll coating method, a blade coating method, an air knife coating method, and the like are applied, and these are applied in appropriate combinations as necessary.

[0119] The optical filter of the present invention includes 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, without departing from the object of the present invention. And dimonium salt or a light absorber composed of an organometallic complex, and widely used in the art, such as an ammium salt compound, an amino compound, an aminothiol nickel complex compound, an anthraquinone compound, an immuumum Compounds, cyanine compounds, triallylmethane compounds, naphthoquinone compounds, nitroso compounds and their metal salts, phthalocyanine compounds, carbon black, indium tin oxide, antimony tin oxide, benzotriazo Compounds, benzophenone compounds, UV absorbers containing droxybenzoate compounds, titanium oxide, zinc oxide, cerium oxide, iron oxide, barium sulfate, etc., as well as antioxidants, flame retardants, stabilizers, lubricants, antistatic agents, heat resistance One or more of an anti-aging agent and a release agent may be contained. An ionic conjugate of the cyclic disulfonylimide anion and dye power thione of the present invention, or such a cyclic disulfonylimide anion and dye catho When combined with a near-infrared absorber or ultraviolet absorber as described above, a light absorber containing an ionic conjugate with diamine and a dimonium salt or an organometallic complex is used as an organic dye compound contained in the light absorber. Light resistance is remarkably improved, and it effectively suppresses fading, denaturation and decomposition by ambient light such as natural light and artificial light.

[0120] Further, the optical filter of the present invention may be used in the field as needed, for example, silver, silver palladium alloy, indium oxide, indium oxide tin oxide mixture (ITO), zinc oxide, etc. Prevents use with one or more anti-reflective agents including electromagnetic wave blocking agents, metal oxides, metal fluorides, metal silicides, metal borides, metal carbides, metal nitrides, metal sulfides, etc. Absent. 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. Or, 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 that on the transparent substrate, and the film or sheet is formed as a transparent substrate. Paste to.

[0121] Furthermore, the optical filter according to the present invention displays, as necessary, a non-glare layer for suppressing glare and a wide viewing angle, a hard coat layer for protecting the surface, and an optical filter. It does not interfere with the provision of one or more adhesive layers for attachment to equipment or glass plates.

[0122] The thus obtained optical filter of the present invention 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. In addition, in light absorbers containing dimoyuum salts or organometallic complexes, the color purity of the three primary colors of light is impaired by selecting an ionic conjugate having an appropriate absorption range according to the wavelength of light to be blocked. It selectively blocks unwanted light in the near-infrared region, especially infrared light and / or neon light in the plasma display, and reproduces the three primary colors of light well in the visible light region. High-quality images with excellent reproducibility can be obtained, and the infrared remote control does not malfunction due to near infrared rays. Image display devices 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 plasma display, and an electroluminescence display. For example, a light-emitting panel television using a display, a non-light-emitting panel television using a liquid crystal display, and a rear projection television with a built-in liquid crystal projector. Among these, the optical filter of the present invention can be applied very advantageously 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.

[0124] Experimental example 1: Photostability of near-infrared absorbing dyes

Regarding the ionic conjugate of the cyclic disulfonylimide anion and the dye cation contained in the optical filter of the present invention, the light stability of the ionic conjugate alone under thin film conditions was 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 dye, 0.1% by mass of the dye and polymethyl metatalylate (trade name “PMMA”) , sigma-Aldrich production) 2.5 weight ^_0/0 methyl Echiruketon (hereinafter, were dissolved in say.) as "MEK". Thereafter, a thin film filter was formed on a polycarbonate substrate by spin coating. The thin film absorption at that time was measured, and the absorbance (initial absorbance) of the dye at the maximum absorption wavelength (λ max) was measured. After that, using the product name “Cenon Weather Meter XL-75” (manufactured by Suga Test Instruments Co., Ltd.) Measurement conditions: 180 W / m ² Inside temperature: 15 ° C Humidity: 60% exposure for a predetermined time (300 Kj / m ² ), the absorbance (absorbance after irradiation) at the absorption maximum wavelength (λ max) (λ max of chemical formula 34 is 947 nm, max of chemical formula 37 is 865 nm) is measured, and the absorption maximum wavelength is measured. The value of “absorbance after irradiation / initial absorbance” expressed as 100 fraction was determined as the dye residual ratio. The results are shown in Table 1. In addition, Fig. 1 shows the light transmission spectrum of an optical filter containing an ion conjugate represented by Chemical Formula 34.

[0125] Formula 63 (Comparative Compound 1)

[Chemical 73]

[0127] [Table 1]

[0128] From the results of Table 1, the stability of the ionic conjugate contained in the optical filter of the present invention was improved by about 10% 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 materials used in the past, and an improvement in light resistance of about 10% has been confirmed. When used in an optical filter, the light stability is improved! / It turns out that it is effective.

[0129] Experimental Example 2: Photostability of near-infrared absorbing dyes Combined use of organometallic complexes The light-absorbing agent containing the ionic conjugate and the organometallic complex is used under the thin film conditions for the ionic conjugate of the cyclic disulfonylimide anion and the dye catalyst contained in the optical filter of the present invention. Stability was examined. The dithiol metal represented by chemical formula 34, chemical formula 37, which is an ionic conjugate of the present invention, and chemical formula 63, chemical formula 64, which are comparative compounds, each of which is represented by 0.1% by weight of a dye and chemical formula 57 complex 0.1 wt%, polymethyl methacrylate Tari rate (trade name "PMMA", sigma-Aldrich manufacturing) a 2.5 mass ^_0/0 were dissolved in MEK. Thereafter, a thin film filter was formed on a polycarbonate substrate by spin coating. The absorption of the thin film at that time was measured, and the absorbance (initial absorbance) of the dye was measured at the absorption maximum wavelength (λ max) (λ max in chemical formula 34 was 947 nm and λ max in chemical formula 37 was 865 nm). Then, using “Cenon Weather Meter XL-75” (manufactured by Suga Test Instruments), measurement conditions: 180 W / m ² temperature inside the tank: 15 ° C humidity: 60% exposure for a predetermined time (300 Kj / m ² , 600 Kj / m ² , 1200 Kj / m ² ) Measured at λ max ο Absorption τ 6 degrees (absorbance after irradiation), and measured the value of “absorbance after irradiation / initial absorbance” at the absorption maximum wavelength for 100 minutes. The ratio expressed as a percentage was determined as the dye residual ratio. The results are shown in Table 2.

[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 to about 6% when 1200Kj / m ² light irradiation was confirmed improvement of approximately 10% of the light stability, as the light exposure time becomes longer (the amount of light irradiation is increased), the onset Ming It was confirmed that the thin-film filter using both the ion conjugate of the present invention and the organometallic complex was superior in light stability compared to the comparative example, and the optical filter containing the dye of the present invention and the organometallic complex was compared. Compared to the optical filter containing the conventional dye of the example, it was confirmed that it was more stable to light for a longer period of time. [0132] Experimental Example 3: Photostability of near-infrared absorbing dyes with dimoyuum salt

An ion conjugate of a cyclic disulfonylimide anion and a dye catalyst contained in the optical filter of the present invention! / And a thin film condition of a light absorber containing the ion conjugate and a dimonium salt. The photostability of was investigated. Using the chemical formula 34, chemical formula 37, which is an ionic conjugate of the present invention, and chemical formula 63, chemical formula 64, which are comparative compounds, for each dye, 0.1% by mass of the dye and dimethyl compounds represented by the chemical formula 53 are used. 0.6% by mass of mel salt and 2.5% by mass of polymethylmethacrylate (trade name “PMMA”, manufactured by Sigma Aldrich) were dissolved in MEK. Thereafter, a thin film filter was formed on a polycarbonate substrate by spin coating. The absorption of the thin film at that time was measured, and the absorbance (initial absorbance) of the dye at the absorption maximum wavelength (λ max) (λ max in chemical formula 34 was 947 nm and λ max in chemical formula 37 was 865 nm) was measured. Then, using “Cenon Weather Meter XL-75” (manufactured by Suga Test Instruments), measurement conditions: 180W / m ^{2 In-} vessel temperature: 15 ° C Humidity: 60% exposure for a predetermined time (600KJ / m ² , 2400Kj / m ² ), the absorbance at max (absorbance after irradiation) is measured, and the value of “absorbance after irradiation / initial absorbance” at the maximum absorption wavelength is expressed as a percentage of dye remaining. Asked. The results are shown in Table 3.

[0133] [Table 3]

[0134] From the results in Table 3, when the dimonium salt represented by Chemical Formula 53 is used in combination, there is no significant difference in photostability when compared with the comparative example when irradiated with 600 KJ / 1 ^ light. , when 2400Kj / m ² light irradiation, approximately 9% of the light stability was confirmed. The thin film filter using the ionic conjugate of the present invention and dimonium salt in combination is more stable to light as the light irradiation time becomes longer (the amount of light irradiation increases) compared to the comparative example. Was prominently shown. The optical filter containing the ion conjugate of the present invention and a dimonium salt is more stable to light for a longer period of time than the optical filter containing the conventional dye of the comparative example. It was confirmed that there was.

[0135] Example 1: Optical filter

100 parts by mass of a 20% by mass toluene solution of a saturated copolymerized polyester resin (trade name “Byron 200” manufactured by Toyobo Co., Ltd.) and 0.5 mass% cyclohexanone of an ionic conjugate represented by the chemical formula 37 After mixing with the solution, toluene was added to adjust the concentration of the polyester resin to 9% by 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 Hequist Co., Ltd., thickness 100 m) and dried to dry the film thickness. An optical filter with a 4,1 m coating film was fabricated.

[0136] All of the optical filters of this example that effectively block unwanted light radiated from an image display device that does not impair the color purity of the three primary colors of the image are advantageous for image display devices such as plasma displays. Applicable.

[0137] Example 2: Optical filter

100 parts by mass of a 20% by mass toluene solution of a saturated copolymerized polyester resin (trade name “Byron 200” manufactured by Toyobo Co., Ltd.) and 0.5 mass% cyclohexanone of an ionic conjugate represented by the chemical formula 37 After mixing with the solution, 0.66% by mass of dimonium represented by Chemical Formula 52 was added, and toluene was added to adjust the concentration of the polyester resin to 9% by 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 Hequist Co., Ltd., thickness 100 m), and dried to form a film. An optical filter with a 4 m thick coating was fabricated.

[0138] All of the optical filters in this example that effectively block unwanted light radiated from video display equipment that does not impair the color purity of the three primary colors of the video are advantageous for video display equipment such as plasma displays. It was possible to create an optical filter that was applicable and improved in light resistance.

[0139] Example 3: Optical filter

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

[0140] All of the optical filters in this example that effectively block unwanted light radiated from video display equipment that does not impair the color purity of the three primary colors of the video are advantageous for video display equipment such as plasma displays. It was possible to create an optical filter that was applicable and improved in light resistance.

Industrial applicability

[0141] As described above, the optical filter of the present invention has excellent light resistance and does not deteriorate its light absorption ability over a long period of time, and can be used for various optical filter applications. When used in an optical filter attached to a video display device, in the visible light range, it effectively blocks unwanted light emitted from the video display device without impairing the color purity of the three primary colors of the image, thus improving contrast and color reproducibility. Excellent high-quality images can be obtained, and even in the near-infrared region, the infrared remote control does not malfunction due to near-infrared.

[0142] It can be said that this invention having such remarkable effects is a very significant invention that contributes to the world.

Claims

The scope of the claims

An optical system comprising an ionic conjugate of a cyclic disulfonylimide anion represented by the general formula 1 and a dye cationic represented by the general formula 2:

General formula 1:

[Chemical 75]

1 2

Represents the number of carbon atoms of the alkylene group, and is an integer of 2 to 6. )

General formula 2:

[Chemical 76]

+

(In General Formula 2, Y represents a methine chain, and the methine chain may have a substituent and / or a cyclic structure. Z and Z represent the same or different aromatic rings or heterocycles;

1 2

Those aromatic rings and heterocyclic rings may have a substituent. )

[2] 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. The optical filter according to 1.

General formula 5: [Chemical 77]

",-O

(9 ⁿ one

,,,

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

[Chemical 78]

(In General Formula 6, Z and Z represent the same or different aromatic or heterocyclic rings,

3 4

These aromatic rings or heterocyclic rings may have a substituent. A and A are

1 2

Stands for a carbon atom or a heteroatom. R and R are aliphatic hydrocarbon groups or aromatic

3 4

Represents a hydrocarbon group, and the aliphatic hydrocarbon group or the aromatic hydrocarbon group may have a substituent. R to R each independently represent a hydrogen atom or an appropriate substituent.

5 8

When A and A are heteroatoms, some or all of R to R are not present.

1 2 5 8

R to R are bonded to a substituent in Z or Z or Z or Z to form a condensed ring.

5 8 3 4 3 4

The power to do is S. In addition, R and R, R and R may combine to form a 3- to 8-membered ring.

5 6 7 8

come. L represents a methine chain, and the methine chain may have a substituent and / or a cyclic group.

[3] The cyclic disulfonylimide anion is an anion represented by the chemical formula 65, The optical filter according to claim 1 or 2.

Chemical formula 65:

[Chemical 79]

4. The optical device according to claim 1, comprising either a dimonium salt represented by the general formula 3 or an organometallic complex having a skeleton represented by the general formula 4 or both. 5. filter.

General formula 3:

[Chemical 80]

9 16

Represents ΧΊ ま versus anion. )

General formula 4: [Chemical 81]

17 20

R and R, or R and R may be connected to each other to form an aromatic ring. Y and Y are each

17 18 19 20 1 2

. )