KR20090073147A - Optical filter - Google Patents

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

Optical filter {OPTICAL FILTER}

The present invention relates to an optical filter comprising an organic dye compound. In particular, it relates to an optical filter provided on the surface of a display such as a plasma display television in order to improve image characteristics and to prevent malfunction by an electronic device using a near infrared remote control.

As high quality television broadcasting is started, the demand for television receivers of the plasma display system is rapidly increasing. Plasma display is an image display device using gaseous plasma discharge light, has a color purity comparable to that of a CRT, easy to full color, and a large viewing angle, and thus is a large image display device corresponding to high quality television broadcasting. Development and mass production are in progress. However, Uchiike Heiju, Journal of Image and Information Media, Vol. 51, No. 4, pages 459-463 (1997), and Shohei Nozaki, Monthly Display, Vol. 6, No. 4, 72 As reported on page 77 (2000) or the like, the plasma display, in principle, emits light of so-called "neon orange" in the vicinity of the wavelength of 600 nm emitted when the excited neon atoms return to the ground state. However, unnecessary near-infrared radiation cannot be avoided, and when these are mixed with red luminescence, there is a problem that a vivid red display with good color purity cannot be obtained or a malfunction of the infrared remote controller is caused. Moreover, the pigment | dye for improving the image characteristic of a display, such as preventing projection of a fluorescent lamp, and the film and optical filter using the pigment | dye are examined.

In order to solve these problems, as a countermeasure against light rays in the near infrared region, a method of conventionally providing a front member using a near infrared absorber on a display portion of a plasma display has been proposed. For example, Japanese Patent Laid-Open No. 9-241520 Japanese Unexamined Patent Application Publication No. 10-128898 discloses a heterocyclic, anthraquinone and dithienes in the Japanese Unexamined Patent Publication No. 10-128898. A front member using an organic pigment compound of an all nickel complex system has been proposed. Moreover, as a countermeasure for improving the image characteristic of a display, the scallium type pigment | dye is proposed by Unexamined-Japanese-Patent No. 2001-188121, for example.

However, since most of these organic dye compounds have insufficient light resistance to environmental light such as natural light and artificial light, there is a problem that the performance of the optical filter tends to be lowered when used for a long time.

In view of such a situation, the present invention provides an optical filter having excellent light resistance, which blocks infrared rays and / or neon lights, which are obstacles such as image characteristics, improves image characteristics of a display and maintains its performance for a long time. The task is to provide.

As a result of diligent research and search by the present inventors, the optical filter containing an ionic conjugate of cyclic disulfonylimide anion and a dye cation has an absorption maximum in the visible to infrared region, and an image such as a plasma display. It has been found that when used in an optical filter installed in a display device, unnecessary light radiated from the image display device is effectively blocked. In addition, it has been found that such an optical filter is excellent in light resistance and maintains its performance even after long-term use.

That is, this invention solves the said subject by providing the optical filter characterized by containing the ionic bond which the cyclic disulfonylimide anion represented by General formula (1) and the dye cation represented by General formula (2) ionically couple | bonded. .

Formula 1

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

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 heterocycles, and those aromatic rings. And the heterocycle may have a substituent.)

In addition to the ionic complex of the cyclic disulfonylimide anion and the dye cation, the present invention is 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. It is to solve the above problems by providing an optical filter comprising a.

Formula 3

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

Formula 4

(In formula (4), R <_17> -R <_20> respectively independently represents a hydrogen atom or a suitable substituent, and R <_17> , R <_18> , R <_19> and R <_20> may mutually connect and may 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 and can be used for various optical filters without deteriorating light absorption ability over a long period of time. In particular, when used in an optical filter installed in an image display device such as a plasma display, In the visible light region, since unnecessary light radiated from the video display device is effectively blocked without degrading the color purity of the three primary colors of the image, a high quality image having excellent contrast image characteristics can be obtained. In addition, even in the near infrared region, the infrared remote controller does not malfunction by the near infrared rays. Moreover, since the optical filter used by this invention is excellent in light resistance, even if it uses for a long time, it will become an optical filter which is hard to reduce performance.

1 is a light transmission spectrum of a near-infrared thin film filter containing Compound 34 prepared in Example 1. FIG.

The present invention will be described in detail below. As above-mentioned, this invention is an optical filter containing the ion bond of the cyclic disulfonylimide anion represented by General formula (1), and the dye cation represented by General formula (2).

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 both R ₁ and R ₂ are fluorine atoms is particularly preferable. n represents the carbon atom number of an alkylene group, it is an integer of 2-6, Preferably it is 2-5, More preferably, it is 3.

Formula 2

In the general formula (2), Y represents a methine chain, and specifically, a monomethine chain or a methine chain having 1 to 12 carbon atoms formed by combining a plurality of methine groups, and particularly, a methine having 1 to 7 carbon atoms. Chains are preferred.

Such a methine chain may have a cyclic structure, As an individual cyclic structure, it has a double bond and / or 1 or more hetero atoms, for example, a cyclobutene ring, a cyclopentene ring, a cyclohexene ring, a benzene ring, Monocyclic or condensed polycyclic compounds such as dehydrodecalin ring, pyridine ring, dihydropyridine ring, tetrahydropyridine ring, furan ring, dihydrofuran ring, thiophene ring, dihydrothiophene ring and hexahydroquinoline ring I can lift it.

Such methine chain and cyclic structure may have one or more substituents within the range which does not deviate from the objective of this invention. Examples of the substituent in the methine chain and the cyclic structure include methyl group, ethyl group, vinyl group, propyl group, isopropyl group, isopropenyl group, 1-propenyl group, 2-propenyl group, 2-propynyl group, and 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 Aliphatic hydrocarbon groups such as pentene-4-ynyl group, trifluoromethyl group, pentafluoroethyl group, heptafluoropropyl group, trichloromethyl group, pentachloroethyl group, heptachloropropyl group, tribromomethyl group, pentabromo Halogenated alkyl groups such as ethyl group and heptabromopropyl group, methoxy group, trifluoromethoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, sec-butoxy group, tert-butoxy group, pentyloxy group, Ether groups such as phenoxy group, alinino group, o-triidino group, m-triidino amino groups such as p-tridino group, quinolidino group, diphenylamino group, p-methoxydiphenylamino group, sulfonyl groups such as methylsulfonyl group and phenylsulfonyl group, and arylthio groups such as phenylthio group and naphthylthio group Heterocyclic groups such as halogen groups such as fluoro, chloro, bromo and iodine groups, barbituric acid groups, imidazolyl groups and pyridyl groups, cyclopropyl groups, cyclobutyl groups, cyclopentyl groups and cyclo Alicyclic hydrocarbon groups, such as a hexyl group and a cyclohexenyl group, a nitro group, a cyano group, and a hydroxyl group, etc. are mentioned.

Z ₁ and Z ₂ represent the same or different aromatic rings or heterocycles, and these aromatic rings and heterocycles may have one or more substituents. As an aromatic ring in Z <_1> and Z <_2> , a benzene ring, a naphthalene ring, an azulene ring, an anthracene ring, a phenanthrene ring, a biphenyl ring etc. are mentioned, for example, As a heterocyclic ring, for example, For example, an imide comprising one or a plurality of group 15 or group 16 heteroatoms in the periodic table such as a nitrogen atom, a person atom, an oxygen atom, a sulfur atom, a selenium atom, a tellurium atom, etc. Sleepy ring, imidazole ring, benzoimidazole ring, α-naphthoimidazole ring, β-naphthoimidazole ring, indole ring, isoindole ring, indolenin ring, isoindolenin ring, benzoindoleninization, pyridinoindole Lenin ring, oxazoline ring, oxazole ring, isoxazole ring, benzoxazole ring, pyridinooxazole ring, α-naphthooxazole ring, β-naphthooxazole ring, selenazolin ring, selenazole ring, benzo selenazole ring, α- Naphthoselenazole ring, β-naphthoselenazole ring, thiazolin ring, thiazole ring, isoty Sol ring, benzothiazole ring, (alpha)-naphthothiazole ring, (beta)-naphthoazole ring, tellurazoline ring, tellurazole ring, benzo tellurazole ring, (alpha)-naphtho tellurazole ring, (beta)-naphtho tellurazole ring, Acridine ring, anthracene ring, isoquinoline ring, isopyrrole ring, imidaoxaline ring, indandione ring, indazole ring, indarin ring, oxadiazole ring, carbazole ring, xanthene ring, quinazoline ring, quinoxaline ring, quinoline Ring, chromman ring, cyclohexanedione ring, cyclopentanedione ring, cinnoline ring, thiodiazol ring, thiooxazolidone ring, thiophene ring, thionaphthene ring, thiobarbiturate ring, thiohydrantoin ring, tetrazole ring, tria Round ring, naphthyridine ring, piperazine ring, pyrazine ring, pyrazole ring, pyrazoline ring, pyrazolidine ring, pyrazolone ring, pyran ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrilium ring, pyrrolidine ring, pyrrole Lin ring, pyrrole ring, phenazine ring, phenanthridine ring, phenanthroline ring, phthalazine ring, pte Lidine ring, furazane ring, furan ring, furin ring, benzoxazine ring, benzopyran ring, morpholine ring, rhodanine ring, etc. are mentioned.

As a substituent in Z <_1> and Z <_2> , a methyl group, an ethyl group, a vinyl group, a propyl group, isopropyl group, isopropenyl group, 1-propenyl group, 2-propenyl group, 2-propynyl group, butyl group, for example. , 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, Aliphatic groups such as 2-methylpentyl group, 2-pentenyl group, 2-penten-4-ynyl group, hexyl group, isohexyl group, 5-methylhexyl group, heptyl group, octyl group, nonyl group, decyl group, and dodecyl group Alicyclic hydrocarbon groups such as hydrocarbon group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cyclohexenyl group, phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, xylyl group Aromatic hydrocarbon groups such as mesityl group, o-cumenyl group, m-cumenyl group, p-cumenyl group and biphenylyl group, methoxy group, trifluoromethoxy group, ethoxy group, propoxy group, isopropoxy group, Ether groups such as butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group, pentyloxy group, and phenoxy group, methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, butoxycarbonyl group, acetyl group, benzoyl jade Ester group, methylamino group, dimethylamino group, ethylamino group, diethylamino 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, alinino group, o-triidino group, m-toludino group, p-toluidino group, xyldino group, diphenylamino group Heterocyclic groups, such as amino group, quinolyl group, piperidino group, pyridyl group, and morpholino group, such as alkyl sulfonyl group, methylsulfonyl group, ethylsulfonyl group, and trifluoromethylsulfonyl group, etc. And substituents formed by halogen groups such as a phenyl group, a fluoro group, a chloro group, a bromo group and an iodine group, a hydroxyl group, a carboxyl group, a cyano group, a nitro group, and a combination thereof.

Among the cyclic disulfonylimide anions represented by the general formula (1), particularly preferred compounds include compounds represented by the general formula (5) wherein R ₁ and R ₂ in the general formula (1) are fluorine atoms.

Formula 5

In the general formula (5), n represents the number of carbon atoms of the alkylene group, and represents the same value as n of the 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 relatively easily change the conjugated carbon number of the methine chain in synthesis, and its absorption wavelength is largely determined by the number of conjugated carbon atoms. Because of the change, the desired absorption wavelength can be obtained by changing the conjugated carbon number of the methine chain, and it is particularly preferable to select the desired absorption wavelength in the optical filter in that it has a high molecular absorption coefficient.

Formula 6

In said General Formula 6, Z <_3> and Z <_4> represent aromatic rings, such as a benzene ring, a naphthalene ring, a pyridine ring, a quinoline ring, and a quinoxaline ring, These aromatic rings may have one or more substituents. As an example of a substituent, the thing similar to the substituent couple | bonded with Z <_1> and Z <_2> in General formula 2 is mentioned. In addition, in General formula 6, Z <_3> and Z <_4> may mutually be same or different.

A <_1> -A <_2> in General formula 6 represents a carbon atom or a hetero atom, As an example of a hetero atom, it is a thing in a periodic table, such as a nitrogen atom, an oxygen atom, a sulfur atom, a selenium atom, a tellurium atom, etc., for example. And atoms of group 15 and group 16. The carbon atom in A ₁ to A ₂ may be, for example, an atomic group mainly composed of two carbon atoms such as an ethylene group and a vinylene group. In addition, A <_1> and A <_2> in General formula 6 may mutually be same or different.

R <_3> and R <_4> in General formula 6 represents an aliphatic hydrocarbon group or an aromatic hydrocarbon group. Examples of the aliphatic hydrocarbon group include, for example, methyl group, ethyl group, propyl group, isopropyl group, isopropenyl group, 1-propenyl group, 2-propenyl group, butyl group, isobutyl group, sec-butyl group and 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 , Isohexyl group, 5-methylhexyl group, heptyl group, octyl group and the like, and examples of the aromatic hydrocarbon group include phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, xylyl group and mesityl group , o-cumenyl group, m-cumenyl group, p-cumenyl group, biphenylyl group, and the like, and such an aliphatic hydrocarbon group or aromatic hydrocarbon group may also be a substituent in Z ₁ and Z ₂ of the general formula (2). You may have the same substituent as 1 or more. In addition, R <_3> and R <_4> in General formula 6 may mutually be same or different, respectively.

R <_5> -R <_8> in General formula 6 represents a hydrogen atom or a suitable substituent each independently. 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-pentene Aliphatic hydrocarbon groups, such as a methyl group, 1-methyl pentyl group, 2-methyl pentyl group, hexyl group, isohexyl group, 5-methylhexyl group, heptyl group, and octyl group, a phenyl group, o-tolyl group, m-tolyl group, aromatic hydrocarbon groups such as p-tolyl group, xylyl group, mesityl group, o-cumenyl group, m-cumenyl group, p-cumenyl group and biphenylyl group, trifluoromethyl group, pentafluoroethyl group and heptafluoropropyl Halogenated alkyl groups such as groups, trichloromethyl group, pentachloroethyl group, heptachloropropyl group, tribromomethyl group, pentabromoethyl group, heptabromopropyl group, methoxy group, trifluoromethoxy group, ethoxy group, propoxy group Ether groups such as butoxy group, tert-butoxy group, pentyloxy group, phenoxy group and benzoyloxy group The number, and this aliphatic hydrocarbon group, an aromatic hydrocarbon group, an ether group, and, 1, or may be with a plurality of the same substituents as the substituents in the general formula 2 Z ₁ and Z _2. In General Formula 6, when A ₁ to A ₂ are heteroatoms, some or all of R ₅ to R ₈ may not be present.

Moreover, R <_5> -R <_8> can combine with the substituent in Z <_3> or Z <_4> or Z <_3> or Z <_4> , and can form a condensed ring, and R <_5> and R <_6> , R <_7> and R <_8> are By combining, it is possible to form a 3 to 8 membered ring containing a carbon atom, an oxygen atom, a sulfur atom, a nitrogen atom and the like. L represents a methine chain, and the same thing as the methine chain Y in General formula 2 is mentioned, for example.

As an example of the ionic bond of the cyclic disulfonylimide anion and dye cation used by this invention, what is represented by General formula (1)-general formula (51) is mentioned, for example. These ion conjugates are, for example, neon light absorbing dyes having an absorption maximum in a wavelength region of 550 to 620 nm in an optical filter such as a plasma display, or near infrared rays having a maximum absorption in a near infrared region having a wavelength of 800 to 1200 nm. It is extremely useful as an absorbing dye. In addition, the compound used by this invention is not limited to these.

Formula 1

Formula 2

Formula 3

Formula 4

Formula 5

Formula 6

Formula 7

Formula 8

Formula 9

Formula 10

Formula 11

Formula 12

Formula 13

Formula 14

Formula 15

Formula 16

Formula 17

Formula 18

Formula 19

Formula 20

Formula 21

Formula 22

Formula 23

Formula 24

Formula 25

Formula 26

Formula 27

Formula 28

Formula 29

Formula 30

Formula 31

Formula 32

Formula 33

Formula 34

Formula 35

Formula 36

Formula 37

Formula 38

Formula 39

Formula 40

Formula 41

Formula 42

Formula 43

Formula 44

Formula 45

Formula 46

Formula 47

Formula 48

Formula 49

Formula 50

Formula 51

The compounds represented by the general formulas (1) to (51) of the present invention can all obtain desired amounts according to known methods or according to known methods for preparing lead compounds. For example, FM Harmer, Heterocyclic Compounds Cyanine Dyes and Related Compounds, John Wiley & Sons, New York, London, 1964, and DM Sturmer, Heterocyclic Compounds-Special topics in heterocyclic chemistry, 18. Chapter 14, pp. 482–515, John Wiley & Sons, New York, London, 1977, Rodds Chemistry of Carbon Compounds, 2nd, Ed. vol. IV, part B, issued in 1977, Chapter 15, pages 369-422, by Elsevier Science Publishing Company Inc., New York, Japanese Patent Application Laid-Open No. 6-313939, and Japanese Patent Application Laid-open No. 5-88293. Can be synthesized.

Moreover, the optical filter of this invention makes a near-infrared absorber or light resistance improving agent any one or both of the dimonium salt represented by General formula (3), or the organometallic complex which has a skeleton represented by General formula (4) besides the said organic pigment | dye compound. It can be contained as.

Formula 3

Formula 4

In General formula 3, R <_9> -R <_16> respectively independently represents a hydrogen atom or a suitable 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 and tert-pentyl group Aliphatic hydrocarbon groups such as 1-methylpentyl group, 2-methylpentyl group, hexyl group, isohexyl group, 5-methylhexyl group, heptyl group, octyl group, nonyl group and decyl group, trifluoromethyl group, pentafluoro Halogenated alkyl groups such as low ethyl group, heptafluoropropyl group, trichloromethyl group, pentachloroethyl group, heptachloropropyl group, tribromomethyl group, pentabromoethyl group, heptabromo prote, cyanomethyl group, 2-cyano Cyanoalkyl groups such as ethyl group and 3-cyanopropyl group, phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, xylyl group, mesityl group, o-cumenyl group, m-cumenyl group, p- Aromatic hydrocarbon groups such as cumenyl group and biphenylyl group, hydroxyl group, benzyl group, phenethyl group, phenylpropyl group, finyl-α- And arylalkyl groups such as butylpropyl group, pinyl-β-methylpropyl group, phenylbutyl group, phenylpentyl group, phenyloctyl group, naphthylmethyl group and naphthylmethyl group, and substituents formed by a combination of these substituents. , R ₉ to R ₁₆ may be the same or different.

Although it does not specifically limit as R <_9> -R <_16> if it is the said substituent, Aliphatic hydrocarbon group, a halogenated alkyl group, a cyanoalkyl group, etc. which have a straight or branched chain of C1-C8 are preferable, and a C2-C6 linear aliphatic hydrocarbon group is especially desirable. As a specific example of especially preferable thing, an ethyl group, a propyl group, a butyl group, a pentyl group, isopropyl group, isobutyl group, isopentyl group etc. are mentioned, for example.

Moreover, as an arylalkyl group in R <_9> -R <_16> , a phenylalkyl group is preferable, and the phenyl group in a phenylalkyl group is also an aliphatic hydrocarbon group, a hydroxyl group, a sulfonic acid group, an alkyl sulfonic acid group, a nitro group, an amino group, and an alkoxy group. Or a substituent such as a halogenated alkyl group and a halogen may be used. Among these, as a more preferable arylalkyl group, the phenylalkyl group which does not have a substituent is mentioned.

As such a phenylalkyl group, a benzyl group and a phenethyl group are particularly preferable.

In general formula (3), X is an anion for forming a salt, and is an anion which keeps general formula (3) neutral. Such anions include, for example, organic acids, inorganic acids, and the like, and are not particularly limited.

In Formula 4, R ₁₇ to R ₂₀ each independently represent a hydrogen atom, an aliphatic hydrocarbon group, an aromatic hydrocarbon group, and a cyano group, and R ₁₇ and R ₁₈ , R ₁₉ and R ₂₀ are connected to each other to form an aromatic ring You can do it. The Examples of the aromatic ring are benzene ring or a naphthalene ring, a benzene ring or a naphthalene ring, as well may have a substituent, the substituent, for example, the same as the substituents in the general formula 2 Z ₁ and Z ₂ I can hear that.

As an aliphatic hydrocarbon group and aromatic hydrocarbon group in R <_17> -R <_20> , the same thing as the aliphatic hydrocarbon group and aromatic hydrocarbon group in R <_9> -R <_16> of General formula 3 is mentioned, for example.

Y ₁ and Y ₂ each independently represent an oxygen atom, a sulfur atom or a nitrogen atom, and a sulfur atom is particularly preferable. M represents a metal atom or metal ion, and typically, scandium, yttrium, titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, technetium, rhenium, iron, ruthenium, osmium, cobalt, rhodium The transition metals of Groups 3 to 12 in the periodic table of iridium, nickel, palladium, platinum, copper, silver, gold, zinc, cadmium, mercury, etc. are selected, among which manufacturing costs and handling are easy. In view of the above, 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 counterion in order to keep the organometallic complex neutral. Examples of cationic counterions include quaternary ammonium salts such as tetramethylammonium, tetraethylammonium, tetrabutylammonium, octyltriethylammonium, phenyltrimethylammonium, triphenylbutylammonium, triphenylbenzylammonium and tetraphenylammonium, tetramethyl Quaternary phosphonium salts such as phosphonium, tetraethylphosphonium, tetrabutylphosphonium, octyltriethylphosphonium, phenyltrimethylphosphonium, triphenylbutylphosphonium, triphenylbenzylphosphonium and tetraphenylphosphonium There is a number.

Examples of the dimonium salt include those represented by the chemical formulas 52 to 56. Examples of the dimonium salts include those represented by the chemical formulas 57 to 62 as the organometallic complex.

Formula 52

Formula 53

Formula 54

Formula 55

Formula 56

Formula 57

Formula 58

Formula 59

Formula 60

Formula 61

Formula 62

The dimonium salt and the organometallic complex can all obtain desired amounts according to a known method or according to a known method for preparing a flexible compound. A dimonium salt can be manufactured, for example with reference to Unexamined-Japanese-Patent No. 2005-325292, The organometallic complex is "Synthesis and utilization method of an organic metal compound", Akio Yamada supervision, Tokyo Chemical Co., Ltd. (1991 Can be manufactured with reference to).

Referring to the optical filter of the present invention containing such an ionic conjugate of a cyclic disulfonylimide anion and a dye cation, the use member of the optical filter of the present invention comprises at least a transparent base which is a main body of the use member, It is comprised by the ion bond of a cyclic disulfonylimide anion and a dye cation as a light absorber. As a light absorber, a dimonium salt, an organometallic complex, etc. can be used together in addition to the ionic complex of a cyclic disulfonylimide anion and a dye cation. In addition, the term "light absorbing agent" used in the present invention refers to a light absorbing organic compound that substantially blocks unnecessary light emitted from a video display device or natural light, especially light in the near infrared region, by being used in such a use member. Or it means the composition containing a light absorbing organic compound.

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 per unit area of the optical filter, and preferably 5 to 100 mg / m 2.

As the transparent substrate, the light transmittance in the entire visible region is 50% or more, preferably 70% or more, for example, ABS resin, polyacrylic acid resin, polyacrylic acid ester resin, polyallylate resin, polyester resin, Polyether sulfone resins, polyvinyl chloride resins, polyolefin resins, polycarbonate resins, polyvinyl acetate resins, polystyrene resins, polymethacrylic acid resins, polymethacrylic acid ester resins, glass, ceramics, and the like. As needed, these are used in combination suitably. Among them, in view of light transmittance and mechanical strength, polyacrylic acid resin, polyacrylic acid ester resin, polyallylate resin, polyester resin, polyether sulfone resin, polyolefin resin, polycarbonate resin, polymethacrylic acid resin, polymethacryl Acid ester resins are particularly preferred.

In the optical filter of the present invention, the light absorbing agent is mixed with such a transparent substrate and then molded into a film shape, a sheet shape, a panel shape or the like according to the shape of the use part, or according to the shape of the use part. The light absorbing agent can be brought into close contact with one or both surfaces of the transparent substrate molded into a film, sheet, panel, or the like to form a light shielding layer made of the light absorbing agent. The thickness of the transparent base material after molding varies depending on the material of the transparent base material and the area of use, but is preferably 0.1 µm to 10 mm, more preferably 0.5 µm to 100 µm. Depending on the situation of use, instead of directly attaching the transparent substrate to the use portion, the transparent substrate is once bonded to a glass plate or the like corresponding to the shape of the use portion, and the glass plate may be attached to the use portion. In such a case, the transparent substrate is formed in a relatively thin thickness, for example, in the form of a film or sheet, and an adhesive layer for bonding the transparent substrate to the glass plate is formed on one surface thereof.

In the former method of mixing a light absorbent with a transparent substrate, for example, a resin and a light absorbent, which are transparent substrates, are melt-kneaded and, if necessary, pelletized or the like, and then extruded, injection molded or pressed. By molding or the like, molding is performed in accordance with the shape of the display portion in the video display device, or the raw material monomer and the light absorbing agent of the transparent base material are mixed and cast in accordance with the shape of the display portion.

On the other hand, in the latter method of being in close contact with a transparent substrate to form a layer of a light absorber, for example, a binder is coexisted as necessary, and the light absorber is, for example, chloroform, cyclohexanone, ethyl methyl ketone. And dissolving or dispersing in a suitable organic solvent such as ketones, isopropyl methyl ketones, halogenated hydrocarbons, ethers, including ethylene glycol monopropyl ether, esters, and the like, depending on the shape of the use part, for example, in the form of a film, Apply directly to one side or both sides of the transparent substrate molded into sheet, panel, or the like, or apply the same solution or dispersion to the film or sheet of the same material as that of the transparent substrate, and then The film or sheet is bonded to one or both sides of the transparent base material molded according to the shape of the use portion.

As the binder, for example, ethylene-vinyl acetate copolymer resin, ethylene-vinyl alcohol copolymer resin, cellulose acetate-based resin, vinyl acetate resin, cellulose-based resin, nylon, phenolic resin, phenoxy resin, polyester resin, polyethyl Methacrylate resins, polycarbonate resins, polystyrene resins, polysulfone resins, polyvinyl butyral resins, polymethyl methacrylate resins, and the like, and the like, and these are suitably used in combination. Such a binder is usually used in a weight ratio of 10 to 1,000 times, preferably 50 to 500 times with respect to the light absorbing agent of the present invention. In the case of applying the light absorbing agent as a dispersion, the solid state light absorbing agent is dispersed as fine particles having a particle diameter of 0.1 to 10 m, preferably 0.5 to 5 m.

To apply a solution or dispersion containing a light absorbing agent to a transparent substrate or the like, it is widely used in the art, for example, a dipping method, a flow coat method, a spray method, a bar coat method, a gravure coat method, a roll coat method, a blade A coating method, an air knife coat method, etc. are applied, and these are applied in combination as needed.

In the optical filter of the present invention, an ionic bond of a cyclic disulfonylimide anion and a dye cation, or an ionic bond of a cyclic disulfonylimide anion and a dye cation within the range not departing from the object of the present invention, and In general, for example, ammonium salt compound, amino compound, amino thiol nickel complex system compound, anthraquinone compound, immonium compound, and cyanine in general in the relevant field, together with a light absorbing agent composed of an immonium salt or an organometallic complex Near-infrared absorbers, benzotriazole compounds, benzophenone compounds, containing compounds, triallyl methane compounds, naphthoquinone compounds, nitroso compounds and metal salts thereof, phthalocyanine compounds, carbon black, indium tin oxide, antimony tin oxide, and the like, Contains hydroxy benzoate compound, titanium oxide, zinc oxide, celium oxide, iron oxide, barium sulfur An ultraviolet absorber, and, an antioxidant, a flame retardant (難燃 化 劑), a stabilizer, a lubricant, an antistatic agent, a heat-resistant anti-aging agent, may contain one or a plurality of release agents to. An ionic complex of the cyclic disulfonylimide anion and the dye cation of the present invention, or an ionic complex of such a cyclic disulfonylimide anion with the dye cation, and a dimonium salt or an organic metal complex When used in combination with the above-mentioned near-infrared absorber and ultraviolet absorber, the light resistance of the organic pigment compound contained in the light absorber is remarkably improved, and it is effectively suppressed from fading, denaturing and decomposing by environmental light such as natural light and artificial light.

Moreover, the optical filter of this invention contains silver, silver-palladium alloy, indium oxide, indium oxide-tin oxide mixture (ITO), zinc oxide, etc. which are common in the said field as needed. It may be used in combination with one or a plurality of antireflection agents containing an electromagnetic wave shielding agent, a metal oxide, a metal fluoride, a metal silicide, a metal boride, a metal carbide, a metal nitride, a metal sulfide, or the like. These materials are usually formed as a layer independent of the light shielding layer containing a light absorbing agent on a transparent substrate by, for example, a vacuum deposition method, a sputtering method, an ion plating method, an ion beam assist method, or the like. On the film or sheet of the same material as that of the transparent substrate, one or more of an ultraviolet blocking layer, an electromagnetic wave blocking layer, an antireflection layer, etc. are formed, and the film or sheet is bonded to the transparent substrate.

In addition, the optical filter of the present invention, if necessary, to mount a non-glare layer for suppressing reflected light and widening the viewing angle, a hard coat layer for protecting the surface, and mounting the optical filter to an image display device or a glass plate. 1 or more, such as an adhesive layer for this, may be provided.

The optical filter of this invention obtained in this way is an ion bond of a cyclic disulfonylimide anion and a dye cation, or an ion bond of a cyclic disulfonylimide anion and a dye cation, and a dimonium salt or an organometallic complex. In the light absorbing agent containing, by selecting an ion binder having an appropriate absorption region corresponding to the wavelength of light to be blocked, unnecessary light in the near infrared region, in particular, in a plasma display, without lowering the color purity of the three primary colors of light Can selectively block infrared rays and / or neon light and reproduce three primary colors of light in the visible light region, so that a high-quality image with excellent contrast and color reproducibility can be obtained. There is no malfunction. As an image display apparatus to which the optical filter of the present invention can be applied, for example, a direct-type television using a cathode ray tube, a plasma display, an electroluminescent display using a light emitting panel type television using a non-luminescent display, or a liquid crystal display. A light emitting panel television, a rear projection television with a liquid crystal projector, and the like can be given. Among these, the optical filter of the present invention can, in principle, be extremely advantageously applied to light emitting panel televisions using plasma displays, electroluminescent displays, etc., which tend to radiate unnecessary light.

EMBODIMENT OF THE INVENTION Hereinafter, embodiment of this invention is described based on an experiment example and an Example.

Experimental Example 1: Photostability of near infrared absorbing pigment

The photostability of the cyclic disulfonylimide anion and the dye cation contained in the optical filter of the present invention was examined for light stability under thin film conditions alone. Using the formula (34), formula (37) and the comparative compound (63) and formula (64), which are the ionic binders of the present invention, 0.1% by mass of dye and polymethyl methacrylate (trade names "PMMA" and SIGMA-) 2.5 mass% of ALDRICH company make it melt | dissolve in methyl ethyl ketone (henceforth "MEK".). Thereafter, a thin film filter was prepared on the polycarbonate base by spin coating. The thin film absorption at that time was measured, and the absorbance (initial absorbance) of the pigment | dye in absorption maximum wavelength ((lambda) max) was measured. Subsequently, using the trade name, "Senon Weather Meter XL-75" (manufactured by Suga Test Instruments Co., Ltd.), measurement conditions: 180 W / m 2, temperature in tank (tank): 15 ° C, humidity: 60% After a predetermined time exposure (300 KJ / m 2), absorbance (absorbance after irradiation) at an absorption maximum wavelength (λ max) (λ max in Formula 34 is 947 nm and λ max in Formula 37 is 865 nm) is measured and absorbed. What represented the value of "post-absorption absorbance / initial absorbance" in 100 fraction in maximum wavelength as the pigment | dye persistence. The results are shown in Table 1. Moreover, the light transmission spectrum of the optical filter containing the ion bond represented by General formula (34) is shown in FIG.

Chemical Formula 63 (Comparative Compound 1)

Chemical Formula 64 (Comparative Compound 2)

From the results in Table 1, it was found that the ion binder contained in the optical filter of the present invention had about 10% improvement in stability compared with the comparative example conventionally used as the near infrared absorbing material. It is understood that the ion binder contained in the optical filter of the present invention outperforms the material used in the past, and is improved in light stability of about 10%, and is effective in light stability when used in the optical filter.

Experimental Example 2 Photo-stability of Near Infrared Absorption Pigment-Combination of Organometallic Complex

The light stability under the thin film conditions of the light absorber containing an ionic bond and an organometallic complex was investigated about the ionic bond of the cyclic disulfonylimide anion and dye cation contained in the optical filter of this invention. 0.1 mass% of a dye, 0.1 mass% of dithiol metal complexes represented by general formula 57 with respect to each pigment | dye with respect to each pigment | dye using Formula 34, Formula 37 which are the ion binder of this invention, and Formula 63 and Formula 64 which are comparative compounds, 2.5 mass% of polymethyl methacrylate (brand name "PMMA", the product made by SIGMA-ALDRICH) was dissolved in MEK. Thereafter, a thin film filter was prepared on the polycarbonate base by spin coating. The thin film absorption at that time was measured and the absorbance (initial absorbance) of the pigment | dye in absorption maximum wavelength (lambda max) ((lambda max in Formula 34 is 947 nm, (lambda max in Formula 37) is 865 nm) was measured. Subsequently, exposure was performed for a predetermined time (300 KJ /) at a measurement condition of 180 W / m 2, an in-house temperature of 15 ° C., and a humidity of 60% using `` Senon Weather Meter XL-75 '' (manufactured by Suga Test Instruments Co., Ltd.). M 2, 600 KJ / m 2, 1200 KJ / m 2), and then the absorbance at λ max (absorbance after irradiation) was measured, and the value of “post-irradiation absorbance / initial absorbance” at the absorption maximum wavelength was expressed in 100 fractions. This was calculated | required as a pigment | dye persistence. The results are shown in Table 2.

From the results in Table 2, when the organometallic complex chemical color 57 is used in combination, when light is 300 KJ / m 2, there is no significant difference in light stability compared with the comparative example, but when light is 600 KJ / m 2, about 6% In the case of 1200KJ / m2 light irradiation, about 10% of light stability was improved, and as the light irradiation time became longer (the amount of light irradiation was increased), the thin film filter using the ion binder and the organic metal complex of the present invention in combination It was confirmed that the light stability is superior to that of the comparative example, and the optical filter containing the dye of the present invention and the organometallic complex is more stable to light for a longer period of time than the optical filter containing the conventional dye of the comparative example. Has been confirmed.

Experimental Example 3 Photo-Stability of Near Infrared Absorption Pigment-Use of Dimonium Salt in Combination

The ion stability of the cyclic disulfonylimide anion and the dye cation contained in the optical filter of the present invention was examined for the light stability under the thin film condition of the light absorber containing the ion binder and the dimonium salt. With respect to each pigment | dye, 0.6 mass% of dimonium salts represented by general formula (53), the dimonium salt represented by general formula (53), and polymethyl with respect to each pigment | dye using Formula 34, Formula 37 which are the ion binder of this invention, and Formula 63, Formula 64 which are comparative compounds 2.5 mass% of methacrylate (brand name "PMMA", the product made by SIGMA-ALDRICH) was dissolved in MEK. Thereafter, a thin film filter was prepared on the polycarbonate base by spin coating. The thin film absorption at that time was measured and the absorbance (initial absorbance) of the pigment | dye in absorption maximum wavelength (lambda max) ((lambda max in Formula 34 is 947 nm, (lambda max in Formula 37) is 865 nm) was measured. Subsequently, using a "Senon Weather Meter XL-75" (manufactured by Suga Test Instruments Co., Ltd.), a predetermined time exposure (600KJ / M 2, 2400 KJ / m 2), and then the absorbance at λ max (absorbance after irradiation) was measured, and the pigment residual ratio was obtained by expressing the value of “post-irradiation absorbance / initial absorbance” at 100% of the absorption maximum wavelength. Obtained as The results are shown in Table 3.

From the results in Table 3, when the dimonium salt represented by the formula (53) is used in combination, when light was irradiated at 600 KJ / m 2, no significant difference was observed in light stability compared to the comparative example, but when light was irradiated at 2400 KJ / m 2, Photo stability of 9% was confirmed. It was shown that the thin film filter which used the ion binder of this invention and the dimonium salt together is more stable with respect to light as the time of light irradiation becomes long (the amount of light irradiation increases) compared with the comparative example. It was confirmed that the optical filter containing the ion binder and dimonium salt of this invention is stable with respect to light for a long time compared with the optical filter containing the conventional pigment | dye of a comparative example.

Example 1 Optical Filter

Toluene was mixed after mixing 100 parts by mass of a 20% by mass toluene solution of saturated copolyester-based resin (trade name "Byron 200", Tongyang Spinning Co., Ltd.) with a 0.5% by mass cyclohexanone solution of the ionic binder represented by the formula (37). It added and adjusted the density | concentration of polyester-type resin to 9 mass%. Subsequently, using a bar coater, this solution was uniformly applied to one side of a polyethylene terephthalate film (trade name "T100E", manufactured by Daiyahoruhekisuto Co., Ltd., 100 µm thick), By drying, the optical filter which has a coating film with a film thickness of 4 micrometers was produced.

All of the optical filters of the present embodiment which effectively block unnecessary light radiated from an image display device without degrading 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

After mixing 100 mass parts of 20 mass% toluene solution of saturated copolymerized polyester-type resin (brand name "Byron 200", Tongyang Spinning Co., Ltd.), and the 0.5 mass% cyclohexanone solution of the ionic binder represented by Formula 37, Formula 52 0.66 mass% was added to dimonium shown by the following, toluene was added, and the density | concentration of polyester-type resin was adjusted to 9 mass%. Subsequently, using a bar coater, this solution is uniformly applied to one side of a polyethylene terephthalate film (trade name "T100E", manufactured by Daiyahoruhekisuto Co., Ltd., 100 µm thick) and dried. An optical filter having a coating film having a film thickness of 4 μm was produced.

The optical filters of the present embodiment effectively block unnecessary light radiated from the image display device without degrading the color purity of the three primary colors of the image, which can be advantageously applied to an image display device such as a plasma display, and has improved optical resistance. You can now create filters.

Example 3 Optical Filter

After mixing 100 parts by mass of a 20% by mass toluene solution of saturated copolyester-based resin (trade name "Byron 200", Tongyang Spinning Co., Ltd.) and a 0.5% by mass cyclohexanone solution of the ionic binder represented by the formula (37), the formula (57) 0.2 mass% of the dithiol metal complex shown by this was added, toluene was added, and the density | concentration of polyester-type resin was adjusted to 9 mass%. Subsequently, using a bar coater, this solution is uniformly applied to one side of a polyethylene terephthalate film (trade name "T100E", manufactured by Daiyahoruhekisuto Co., Ltd., 100 µm thick) and dried. An optical filter having a coating film having a film thickness of 4 μm was produced.

All of the optical filters of the present embodiment effectively block unnecessary light radiated from the image display device without degrading the color purity of the three primary colors of the image. You can now create filters.

As described above, the optical filter of the present invention is excellent in light resistance, does not degrade light absorption ability over a long period of time, and can be used for various optical filters, for example, installed in an image display device such as a plasma display. When used in an optical filter, it is possible to effectively block unnecessary light radiated from an image display device in the visible light region without lowering the color purity of the three primary colors of the image, thereby obtaining a high quality image having excellent contrast and color reproducibility. In addition, even in the near infrared region, the infrared remote controller does not malfunction by the near infrared rays.

The present invention exhibiting such a remarkable effect can be said to be a meaningful invention that can contribute a great deal to this field.

Claims (4)

An optical filter containing the ionic bond of the cyclic disulfonylimide anion represented by General formula (1), and the dye cation represented by General formula (2). Formula 1:

(In General Formula 1, R ₁ and R ₂ each independently represent a hydrogen atom or a halogen atom. N represents the number of carbon atoms in the alkylene group and is an integer of 2 to 6). 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 heterocycles, and those aromatic rings. And the heterocycle may have a substituent.) The method of claim 1, 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). Formula 5:

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

(In General formula 6, Z <_3> and Z <_4> represent the same or different aromatic ring or heterocycle, and those aromatic rings or heterocycle may have a substituent. A <_1> and A <_2> respectively independently represent carbon It represents an atom or a hetero atom. R ₃ and R ₄ is an aliphatic monovalent hydrocarbon group or an aromatic hydrocarbon may have a substituent group is their aliphatic hydrocarbon group or a room hyangjok hydrocarbon group. R ₅ to R ₈ are, each independently, a hydrogen atom Or a suitable substituent, and when A ₁ and A ₂ are heteroatoms, some or all of R ₅ to R ₈ are absent, and R ₅ to R ₈ are Z ₃ or Z ₄ or Z ₃ or Z _A condensed ring can be formed by combining with the substituent in _{4. In} addition, R ₅ and R ₆ , R ₇ and R ₈ can be bonded to form a 3 to 8 membered ring, L represents a methine chain, The methine chain May have a substituent and / or a cyclic group. The method according to claim 1 or 2, An cyclic disulfonylimide anion is an anion represented by the formula (65). Formula 65:

The method according to claim 1, wherein An optical filter comprising any one or both of a dimonium salt represented by the general formula (3) or an organometallic complex having a skeleton represented by the general formula (4). Formula 3:

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

(In formula (4), R <_17> -R <_20> respectively independently represents a hydrogen atom or a suitable substituent, and R <_17> , R <_18> , R <_19> and R <_20> may mutually connect and may 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.)

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