JPS62186205A - Optical filter composition - Google Patents

Abstract

PURPOSE:To obtain a compsn. which absorbs light of 400-800nm wavelength and has high fastness to light by incorporating at least one kind selected from specific methine dyes therein. CONSTITUTION:This compsn. contains at least one kind selected from the methine dyes expressed by the formula. R1 is preferably an alkyl group of <=18C substd. by an unsubstd. alkyl group (for example, methyl group) of <=18C. R1 which forms further a 5- or 6-membered ring by condensing with the benzene ring condensed to the 5- or 6-membered ring expressed by Z is equally preferable. A substd. or unsubstd. benzene ring group (for example, phenyl group, etc.) and substd. or unsubstd. naphthalene ring group are preferable as the aryl group of R2. R3, R4, R5, R6 may be the same of different from each other and denote an alkyl, etc. The optical filter which efficiently absorbs light near 400-800nm is thus obtd.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a composition having an optical filter function.
More specifically, the present invention relates to an optical filter composition with improved stability such as light fastness.

(Prior Art) The first requirement for an optical filter is that it does not transmit light of a desired specific wavelength.

The second requirement for an optical filter is high light fastness.

For these purposes, various efforts are being made to develop new dyes with different chemical structures.

(Problems to be Solved by the Invention) However, the development of dyes that have absorption in a specific and desired wavelength range and have high light fastness has not necessarily been sufficiently carried out. Therefore, the purpose of the present invention is, firstly, to provide an optical filter composition that absorbs light with wavelengths from ≠oonm to 10+17 nm, and secondly, to provide an optical filter composition with high light fastness. .

(Means for Solving the Problems) The present inventors have achieved the above object (as a result of various studies, it has been found that at least one methine dye represented by the following general formula (I) is contained). We have discovered that the above objectives can be achieved by using a characteristic optical filter.

(In the formula, n represents O or /, m represents 0, /, or λ. R1 represents a substituted or unsubstituted alkyl group,
R2 represents a substituted or unsubstituted aryl group or a heterocyclic group, and R3, R4, Rs, and R6 may be the same or different from each other, and represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted Represents an alkoxy group, a hydroxy group, a substituted or unsubstituted amino group, a rogen atom, or a substituted or unsubstituted heterocyclic group.

Further, R3 and R4, R3 and R5, or R4 and R5 may be fused to form a membered ring.

R represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a cyano group, or a substituted or unsubstituted acyl group. Further, R may be linked with R to form a condensed ring.

2 represents a j-membered ring or an atomic group necessary to form a j-membered ring, and these rings may have a substituent (or may be fused with another ring).

Here, the other ring may be combined with R to further form a condensed ring. Xe represents an anion. p is 1 or 2
and p is l when the dye forms an inner salt. ) Each substituent of the compound represented by the general formula [[ ] is preferably the substituent shown below.

That is, R1 is an unsubstituted alkyl group having 1r or less carbon atoms (for example, methyl group, ethyl group, propyl group, butyl group, methyl group, octyl group, decyl group, dodecyl group, octadecyl group, vinylmethyl group, cyclohexyl group, etc.) ), or a substituted alkyl group (substituents include, for example, a carboxyne group, a sulfo group, a cyano group, a rogene atom (for example, a fluorine atom, a chlorine atom, a bromine atom), a hydroxy group,
Aldoxycarbonyl groups with carbon numbers below (e.g., methoxycarbonyl group, ethoxycarbonyl group, phenoxycarbonyl group, benzyloxycarbonyl group, etc.), alkoxy groups with carbon numbers of r or less (e.g., methoxy group, ethoxy group, benzyloxy group, 7 phenethyloxy groups), monocyclic arylox groups with 10 or less carbon atoms (e.g., phenoxy group, p-tolyloxy group, etc.), acyloxy groups with the number of carbon atoms below (e.g., acyloxy group, propionyloxy group, etc.), carbon The number can be changed to the following acyl groups (e.g. acetyl group, propionyl group, benzoyl group, metal group, etc.), carbamoyl group (e.g. carbamoyl i, N, N-
dimethylcarbamoyl group, morpholinocarbonyl group, piperidinocarbonyl group, etc.), sulfamoyl group (e.g. sulfamoyl group, N,N-dimethylsulfamoyl group, morpholinosulfonyl group, piperidinosulfonyl group, etc.), carbon atoms of 10 or less Aryl group (e.g. phenyl group, ≠-chlorophenyl group, μm methylphenyl group, α
-naphthyl group, etc.) is preferable.

Also, R1 is represented by Z! Condensed with a benzene ring fused to a membered ring or a 6-membered ring, and more! Those forming a t@ ring are also preferred.

The aryl group for R2 includes substituted or unsubstituted benzene ring groups (e.g. phenyl group, μm nitrophenyl group,
μm chlorophenyl group, etc.), and substituted or unsubstituted naphthalene ring groups are preferred.

As the substituted benzene ring group for R2, a group represented by the following general formula (IIJ) is more preferable.

In the formula, R11, R12% R13 and R14 may be the same or different. R11 to R14 are unsubstituted alkyl groups having 1 to 7 carbon atoms (e.g. methyl group, ethyl group,
propyl group, butyl group, hexyl group, octyl group, decyl group, dodecyl group, vinylmethyl group, etc.), or substituted alkyl group (substituents include carboxyl group, cyano group, hydroxy group, sulfo group, halogen atom (e.g. fluorine atom, chlorine atom, etc.), alkoxycarbonyl groups with carbon numbers of r or less (e.g., methoxycarbonyl group, ethoxycarbonyl group, phenoxycarbonyl group, benzyloxycarbonyl group, etc.), alkoxy groups with carbon numbers of r or less (e.g., methoxy group, ' ethoxy group, benzyloxy group, phenethyloxy group, etc.), monocyclic aryloxy group having up to 10 carbon atoms (e.g., phenoloxy group, p-tolyloxy group, etc.), acyloxy group having up to 3 carbon atoms (e.g., acyloxy group). , propionyloxy group, etc.), acyl group having carbon number r or less (e.g., acetyl group, propionyl group, benzoyl group, mesyl group, etc.), carbamoyl group (e.g., carbamoyl group, N,N-dimethylcarbamoyl group, morpholinocarbonyl group, (e.g. lysinocarbonyl group), sulfamoyl group (e.g. sulfamoyl group, etc.).

hedimethylsulfamoyl group, morpholinosulfonyl group, lysinosulfonyl group, etc.), aryl groups having 10 or less carbon atoms (e.g. phenyl group, μ-chlorophenyl group, ≠-methylphenyl group, α-naphthyl group, etc.) An alkyl group having the following carbon number/substituted with etc. is preferable.

R13 and R14 are substituted or unsubstituted amine groups, carboxyl groups, cyano groups, hydroxy groups, sulfo groups, halogen atoms (e.g. 7 atoms, chlorine atoms, etc.), and alkoxycarbonyls having the following carbon atoms: groups (e.g. methoxycarbonyl group, ethoxycarbonyl group, phenoxycarbonyl group, benzyloxycarbonyl group, etc.)
, an alkoxy group having a carbon number of r or less (e.g., a methoxy group,
ethoxy group, benzyloxy group, phenethyloxy group), monocyclic acyloxy group with carbon number IQ or less (e.g. phenoxy group, p-tolyloxy group, etc.), acyloxy group with carbon number less than or equal to IQ (e.g. acyloxy group, propionyloxy group, etc.), acyl groups having carbon atoms of r or less (e.g., acetyl group, propionyl group, benzoyl group, mesyl group, etc.), carbamoyl groups (e.g., carbamoyl group, N
.

It may be different from the unsubstituted or substituted amino group of R13, R14 (, hydrogen atom, lower alkyl group having 1 to 1 carbon atoms (e.g. methyl group, ethyl group, propyl group, butyl group, etc.), carbon number - -r acyl groups (eg, acetyl group, propionyl group, benzoyl group, etc.) are preferred.

Furthermore, R17 and R18 may form a ring.

In addition, l'tia and R14 may form a benzo-fused ring (Also, it is preferable that R11 or R12 and R13 or R14 are connected to form a j-membered ring or a 6-membered ring.* Rtl and R12 It is also preferable to connect them to form a !-membered ring or a t-membered ring.

Further, the heterocyclic group for R2 is a pyrazole nucleus.

i,2-dihydro-/-azaazulene-λ-one nucleus, pyrrolo[yo,/-bJ quinazoline-terone nucleus, indole nucleus, pyrrole nucleus, pyrrolo (J, j-b) pyridine nucleus, etc. are preferred.

The alkyl group of R3, R4, R5, and R6 has a carbon number of 1
Lower alkyl groups from to (e.g.

thyl group, ethyl group, inopropyl group, butyl group, etc.), and as for the alkoxy group, alkoxy groups having carbon atoms from 1 to 1 (for example, butoxy group, ethoxy group, propoxy group, butoxy group, etc.) are preferable. stomach. Furthermore, as the substituents on the lower alkyl group and the lower alkoxy group, those listed for R1 are preferable.

may be the same or different, hydrogen atom, carbon number l
-Lower alkyl group with μ (e.g. methyl group, ethyl group, propyl group, butyl group, etc.), acyl group with carbon number λ to ♂ (e.g. acetyl group, propionyl group, benzoyl group, etc.)
is preferred.

Also, R15 and R16 are connected to each other, ! member ring or 6
It is also preferable to form a membered ring.

Furthermore, R15 and/or R16 may combine with the benzene ring of the benzopyrylium nucleus to form a condensed ring.

The heterocyclic group of R3, R4, R5s R6 is a copenzotriazolyl group, a λ-benzimidazolyl group, a copenzothiazolyl group, a copenzozolyl group, /, 2
．． 3-triazol-7-yl group, /, 2. ! -triazole-λ-yl group, l, 2. A μ-triazole-coyl group is preferred, and these may further have a substituent. Examples of the substituents on the heterocyclic group include the substituents represented by R.

R is a hydrogen atom, a cyano group, a substituted or unsubstituted alkyl group having up to 12 carbon atoms as preferably mentioned in the substituent R, a substituted or unsubstituted aryl group having up to 12 carbon atoms (e.g., phenyl group, ≠-methylphenyl group) , μm chlorophenyl group, l-naphthyl group, etc. Substituted or unsubstituted acyl groups having 72 or less carbon atoms (eg, acetyl group, propionyl group, benzoyl group, mesyl group, etc.) are preferred.

It is also preferable that R be linked with R to form a condensed ring.

2 is! represents the atomic group necessary to form a six-membered ring,
The ring is, for example, a thiazole nucleus (e.g. thiazole, μm
Methylthiazole, μm phenylthiazole,! -Methylthiazole, j-7 22ruthiazole, μ,! -dimethylthiazole, μ.

! -Schiff King nilthiazole, 4&, (J-?enylthiazole etc.), (nzothiazole nucleus (e.g. benzothiazole, μm chlorobenzothiazole, j-chlorobenzothiazole, t-chlorobenzothiazole, 7-chlorobenzothiazole, Hiroshi- Methylbenzothiazole, j-
Methylbenzothiazole, t-methylbenzothiazole,! -,l,-dimethylbenzothiazole,! -bromobenzthiazole, t-prosobenzothiazole, j-
Trifluoromethylbenzothiazole! -722benzothiazole, μmm metofudibenzothiazole! −
Meto-cow dipenzothiazole, t-methoxybenzothiazole,! -carboxybenzothiazole, j-cyanobenzothiazole,! -Fluoro(nzothiazole,!-
Ethoxybenzothiazole, tetrahydrozothiazole%j.

t-dimethodibenzothiazole, j-hydroxybenzothiazole, 6-hydroxybenzothiazole, etc.),
naphthothiazole nucleus (e.g. naphtho-(/, J-dJ thiazole, natto (J, /-dJ thiazole, natto [
Co, j-dJ thiazole, j-methoxynaphtho (,2,
/-d) Thiazole,! -ethoxynaphtho (J, /-d
J thiazole, t-methoxynaphtho(/,λ-d]thiazole, 7-methoxynaphtho[1,λ-d]thiazole, etc.), oxazole nucleus (e.g. Hiro-methyloxazole, !=methyloxazole, μm phenyloxazole) ---
Le, ≠,! -diphenyloxazole, μ-ethyloxazole, 1L, t-dimethyloxazole, j-phenyloxazole, etc.), benzoxazole nuclei (e.g. benzoxazole, !-chlorobenzooxazole, !-methylbenzoxazole, j- Phenylbenzoxazole, 6-methylbenzoxazole, !, t
- safusazole in dimethylbenzoate, t-dimethylbenzoxapur, j-methylbenzoxazole,! −
Ethoxybenzoxazole! -fluorobenzoxazole, 6-medoxybenzooxazole, j-hydroxybenzoxazole, 6-hydroxybenzoxazole, etc.), naphthoxazole nuclei (e.g.
/, J-d]oxazole, naphtho(J,/-d)oxazole, naphtho[co, j-d3oxazole, etc.), selenazole nucleus (e.g. heptanozoles, μm methylselenazole, phenylselenazole, μ).

! -diphenylselenazole, etc.], benzoselenazole core (e.g., benzoselenazole, j-chlorobenzoselenazole, !-methylbenzoselenazole, !-methokifinzoselenazole, j-phenylbenzoselenazole, etc.), naphthoselena Sol nuclei (e.g. naphtho(/, J
-dJ selenazole, nando [ko, /-d) selenazole, natu [2,j-d) selenazole, etc. J1 telllazole nucleus (e.g. penzotelllazole, !-methylbenzotelllazole, !, 6-dimethylbenzotelllazole) ,
Naphtho (/, 2-d) Tellurazole, Naphtho (J e
/a J Tellurazol, Naphtho [λ.

J-d) Tellurazole, t-methoxynaphtho (/.

λ-d] tellurazole, etc.), thiazoline nuclei (e.g. thiazoline, Hiro-methylthiazoline, μm phenylthiazoline, etc.), oxazoline nuclei (e.g.

j-dimethyloxazoline, etc.), inoxazole core (
(e.g., methyl isoxazole, etc.), benzoinoxazole core (e.g., penzoinoxazole%), J
, J-dialkylindolenine a (e.g. 3,3-dimethylindolenine, 3゜31-trimethylindolenine, !-Roreau J, J-dimethylindolenine, !-
ethoxycarbonyl-J, J-dimethylindolenine, etc.), λ-pyridine nucleus (e.g. pyridine, j-methylpyridine, etc.), Hiro-pyridine nucleus (e.g. pyridine, etc.), yoquinoline nucleus (e.g. t-ethoxyquinoline, -ethyl Chunoline, +-p-roloquinoline, r-fluoroquinoline, etc.), Hiro-quinoline nucleus (eg!-methylquinoline,
t-fluoroquinoline, 6-chloroquinoline l), /-
Isoquinoline nuclei (eg, inquinoline, etc.) are preferred.

The term represents an anion, and examples include chloride, bromide, yoshito, thiocyanate, perchlorate, /(
Radruenesulfonate and tetrafluoroborate are preferred.

The compound of general formula (I) can be synthesized by various synthetic methods, but for example, as shown in the reaction formula below, a heterocyclic quaternary salt derivative having an active methyl (or active methylene) group and a Hiro-methyl Intermediates obtained by reaction with -2-thiocoumarin derivatives (can be obtained by condensation reaction of AJ and aldehydes).

3 R4 intermediate (AJ intermediate (A J + OHC + CH-C river, 71Rz
-m-→3 R4 (Xe)p-1 In the above reaction formula, R1, R2-*R3, R4, R5゜R6
, R, z, Xe, m, n, and P have the same meanings as explained in general formula CI). Further, X1° and X2e represent anion groups, %P1 and P2 represent/or -2, and when the compound forms an inner salt, it is 1.

Examples of media for the compound represented by the general formula (IJ) are shown below, but the scope of the present invention is not limited thereto.

Compound-/ compound - co Compound-3 c7!04e Compound −≠ Compound-! Compound-6 Compound-7 compound-r Compound-2 c71!04e Compound-ll t04e Compound-ll Compound-13 α04e Compound-17 Ie compound-it αe Compound-7 C6O4θ Compound-20 Ie Compound-,! / Ie Compound-22 Ie Compound-23 Ie Compound-214 compound-ko 1O4e Compound-26 re Compound-27 Compound-21r Compound - Kota e Compound-30 Compound-31 Compound-32 α04e Compound-33 Compound-74C 104e Compound-3j αO4e Compound-36 fart c, o4e)15c2'j2)15 Compound-37 Compound-3F α04e Compound-Hiro O 0!04e Compound-Hiroshi 1o4e Compound-μ2 cl, 04e Compound-II-3 α04e Compound - Hirohiro α04e Compound-Hiroshi! 104e Compound-μt α04e Compound-Hiroshi 7 CIO4” Compound - Hiroshi 104e Compound-jQ 1O4e Compound-j/ 104e Compound - Yoko Compound-Yo3 α04e Compound - Yohiro Compound-! ! Engineering e Compound-! 6 E0 Compound-j? 104e compound-jri cJo 4.

Compound-4゜■ecl Compound-4/ Compound-62 Compound-t3 Compound-6≠ Compound-Otsu! α Compound-46 re Compound-z7 α04e α04e Compound-4ri αe Compound-70 C! , 04e Compound-71 ■e Compound-72 04e Compound-73 Compound-7μ α /N\ H5C2CzHs α04e Next, synthesis examples of the compounds according to the present invention will be described in detail below.

Synthesis example -/(intermediate (synthesis of AJ) / -(11j-ethyl-2-((≠-methyl-2H-
Chromene-λ-ylidene)methyl)benzothiazolium perchlorate 3-ethylruyomethylbenzothiazolium p-toluenesulfonate 17. After heating and reacting 1 methyl-2H-chromene-2-thione r, rg at ljOoC for /j hours, methanol, 2otn1 and acetone 1AOrtrl were added to the reaction mixture to form a homogeneous solution. After cooling to room temperature, add 40% perchloric acid/j.

7Ii was added and stirred at room temperature to precipitate crystals.

The crystals were collected by filtration, washed with a small amount of acetone, and then mixed with 20 ml of methanol and 4 cO1 of acetone at room temperature. The crystals were added to a mixed solvent of Ll, stirred for 30 minutes, collected by filtration, and washed with acetone to obtain the target products r and zp. (Yield≠Q%) Brown crystal mp
-2rooc or more (decomposition)/-(2) j-trifluoromethyl-3-ethylrouyo ((4A-methyl-λH-chromene-λ-ylidene°)methyl) Benzothiazolium p-toluenesulfonate j-trifluoromethyl -3-Ethyl-λ-methylbenzothiazolium p-toluenesulfonate, 37g
After reacting Tobiichimethyl-2H-chromene-2-thione/09 by heating at 110° C. for 2Q hours, 1 orrtt of methanol, then 10 ml of acetone, and 0 ml of ethyl acetate were added to the reaction mixture to form a homogeneous solution. When cooled to room temperature, crystals precipitated.

After collecting the crystals by filtration and washing with a small amount of acetone, add the crystals to a mixed solvent of 10 rd methanol, 0; 7 g of the target product/Hiroshi was obtained. (Yield 4A, <H) Brown crystal m9272-277°C (decomposition)/-(3)
j-Chloro-3-ethylrouyo((≠-methyl-coH-chromene-irigun)methyl) Benzothiazolium p-toluenesulfonate! -Chloro-3-ethyl-2-methylbenzthiazolium p-toluenesulfonate //, /l and Hiro-methyl-2H-chromene-λ-thione! .

5g! After heating the reaction at 0°C for 123 hours, 21 ml of methanol was added to the reaction mixture. Next is acetone! Od1 ethyl acetate/! Ord was added and the mixture was cooled to room temperature to precipitate crystals. The crystals were collected by filtration, washed with a small amount of acetone, and then washed with methanol at room temperature. Fu, Aceto 710wt1. Ethyl acetate/! The crystals were added to 0rnl of a mixed solvent, stirred for 20 minutes, collected by filtration, and washed with acetone to obtain the desired product 7.2y.

(Yield! 2%) Brown crystals mpJfJ~koIJ°C or above (decomposition) as shown below/-(4) to/-(9) are also mentioned/
-(11~/-) could be synthesized in the same manner as (3).

/-(4)j-Methyl-3-ethylruyo((4'-methyl-xH-chromene-yoylidene)methyl)benzothiazolium chino-chlorate brown crystals (np270~core j0C or higher (decomposition) yield!! / -(5) j-methox 3-ethyl-2-((
Hiro-methyl-2H-chromen-2-ylidene)methyl)
Benzothiazolium Yoshit brown crystal mp 273-4744 'C (decomposition) yield Jrq6/-(6)! -Ethylleuco((-methyl-λ)
H-chromene-koylidene)methyl)-naphtho(J,
/-dJ thiazolium iosito.

Brown crystals mpλro'c or higher (decomposition) yield 2j% /-(7) J-(iomethoxyethyl)-4-((Hiro-
Methyl-2H-chromene-λ-ylidene)methyl)penzothiazolium-R-chlorate brown crystals mp2100c or higher (decomposition) yield μ3% /-(81j, A-dimethyl-3-ethyl-λ-((4
'-Methyl-2H-chromene-yoylidene)methyl)
Penzothiazolium p-toluenesulfonate brown crystal mp20/=2036C single 20/=) Yield≠
Section j/-(9) j-methyl-2-((μm methyl-2
H-chromen-2-ylidene)methyl)benzoxacilium perchlorate brown crystals mp,? 42~Core 10C (Decomposition) Yield l Kochi Synthesis Example (Synthesis of Compound-1) 3-Ethylleuco((4cm methyl-λH-chromen-2-ylidene)methyl)benzothiazolium perchlorate z, op and Hiro-dimethyl Aminobenzaldehyde /, /ji was added to acetic anhydride JOrd, and 1ro was added on an oil bath.
μ at 0c! Heat to reflux for minutes. After cooling to room temperature, the precipitated crystals were separated and washed with methanol. Recrystallization from methanol and chloroform was performed j times to obtain 4 cg of the desired product.

Green-black crystal m9202-21100M e O)I
M e OHλ j 4'nm
g = J, IJ x 10' m a x
m a x synthesis example 3 (compound-
Synthesis of 2) 3-Ethyl-co-((4'-methyl-2H-chromen-ylidene)methyl)benzothiazolium nomi-chlorate j, Og and dimethylaminocinnamaldehyde i, zg were added to 5 ornl of acetic anhydride. Eh, on the oil bath/j
The mixture was heated to reflux at 00C for vO minutes.

After cooling to room temperature, 10orrtl of ethyl acetate was added, and stirring was continued for 3Q minutes at room temperature. The precipitated crystals are mixed with methanol/
Using a mixed solvent of chloroform; lr (V/V),
Purified through a silica gel column, then methanol-
Recrystallize twice from chloroform to obtain target product o, IAg
I got it.

Dark green crystal mp/9! ~/l'A °C (decomposition) max Max Synthesis Example Hiro (Synthesis of compound-3) 3-ethyl-2-((Hiro-methyl-2H-chromene-koylidene)methyl)benzothiazolium nomi-chlorate 2. ! l and/, lr-trimethylene-/, 2.
J,≠-te)dihydroquinoline-6-aldehyde/,!
Add 77 to acetic anhydride and place on an oil bath! 4 at 0°C
The mixture was heated under reflux for Cj minutes. After cooling to room temperature, the precipitated crystals were collected, washed with methanol, and then recrystallized three times in methanol-chloroform to obtain 2.7 g of the desired product.

Dark green crystal mp; 24j-241'C (decomposition) max
max synthesis synthesis (compound 3
synthesis) J-: Lf-trifluoromethyl ((μm
Methyl-2H-chromen-2-ylidene) methyl) benzothiazolium p-toluenesulfonate 4, ni 9 and 2.6 g of Hiro-dimethylaminocinnamaldehyde were added to 1001 nl of acetic anhydride, and the mixture was heated on an oil bath/jO0C for 7 minutes. The mixture was heated to reflux. After cooling to room temperature, it was purified through a silica gel column using a mixed medium of methanol/chloroform = 271 (V/V). The obtained crystals were dissolved in methanol and cooled to 00C, and sodium perchlorate 2. An aqueous solution of tli (water j Otu!) was added.

The precipitated crystals were collected and recrystallized three times from methanol-chloroform to obtain the desired product 3. ! I got I.

Dark green crystal mpλJ10C, (decomposition) max
max Synthesis The methine dyes shown below were also synthesized in the same manner as shown in Synthesis Examples 2-j.

ax The key is shown below.

Table 1 Synthesis Example 7 (Synthesis of Compound -≠Hiro) 3-Ethylruco=. 7.3 g of dimethylaminobenzaldehyde was added to acetic anhydride JOrnl and heated to reflux on/on an oil bath at O0C for 30 minutes. After cooling to room temperature, the precipitated crystals were separated and washed with methanol. Recrystallize from methanol-chloroform five times to obtain the target object O0r! iI was obtained.

Green-black crystal mp2co0-22j'C max max synthesis synthesis (synthesis of compound-Hiro!) 3-ethyl-λ-((Hiro-methyl-2H-chromene-2
-ylidene) methyl) benzothiazolium perchlorate 3.011 and 2-hydroxy-Hiro-diethylaminobenzaldehyde i, sg to acetic anhydride! In addition to Qgo, oil bath top/! Heat to reflux at 00C for tAO minutes. After cooling to room temperature, 100 ml of ethyl acetate was added, and stirring was continued for 3Q minutes at room temperature. The precipitated crystals were mixed with methanol/chloroform;
The product was purified by passing through a silica gel column using a mixed solvent of (v/v), and then recrystallized twice from methanol-chloroform to obtain the desired product (0.79).

Dark green crystal m p 2 J / -2j JoC (decomposition) max max synthesis synthesis (synthesis of compound -jO) 3-ethyl-j-chloro-2-((≠-methyl-λH-
Chromene-koylidene) methyl) benzothiazolium perchlorate λ,! rll and j-methoxy-/1I
r=trimethylene-7. 3゜≠-tetrahydro-t-aldehyde.

Add zg to acetic anhydride and heat on an oil bath at iro°C.
De Hiro! The mixture was heated to reflux for a minute. After cooling to room temperature, the precipitated crystals were collected, washed with methanol, and then recrystallized three times from methanol-chloroform to obtain 2.7 g of the desired product.

Dark green crystal mp27j-271'C (decomposition) m a
x m a x Synthesis Example IO The methine dye shown below is also a synthesis example! It was synthesized in the same manner as shown in ~.

Table 1/Table 2 The optical filter composition of the present invention contains the dye described above in a binder. The binder is not particularly limited and can be used regardless of whether it is organic or inorganic.

Such binders include polymeric materials such as plastics, inorganic materials such as glass, and the like.

Preferably, the binder used is one that forms a film with excellent transparency and mechanical properties. Examples of such film-forming binders include polyesters such as polyethylene terephthalate;
Cellulose diacetate, cellulose triacetate,
Cellulose esters such as cellulose acetate butyrate, polyolefins such as polyethylene and polypropylene, polyvinyl chloride, polyvinylidene chloride, vinyl chloride-vinyl acetate copolymer, and polyethylene (7)
Known film-forming binders such as holivinyl compounds, acrylic addition polymers such as polymethyl methacrylate, polycarbonates made of polycarbonate esters, phenolic resins, urethane resins, and hydrophilic binders such as gelatin can be mentioned.

The first method for forming a film by retaining the dye on the tooth side of the plastic material is to incorporate it into the plastic at the time of film production. That is,
A film in which the above compound is uniformly dispersed can be obtained by mixing the dye with various additives into a polymer powder or pellet, melting it and extruding it by a T-die method or an inflation method, or forming it into a film by a calendar method. Further, when producing a film from a polymer solution by a casting method, the dye may be contained in the solution.

A second method is to form an infrared absorbing layer by applying a polymer solution or dispersion containing the dye to the surface of various plastic films or glass plates manufactured by an appropriate method.

As the binder polymer used in the coating solution, one is selected that dissolves the dye as well as possible and has excellent adhesion to the plastic film or glass plate serving as the support. Polymethyl methacrylate, cellulose acetate butyrate, polycarbonate, etc. are suitable for this purpose. The support film may be previously coated with a suitable primer to improve adhesion.

A third method is to mix a dye and a polymerizable monomer in the light incident window frame of the element whose desired wavelength of light is to be cut.
There is a method in which a suitable polymerization initiator is added, the polymer is polymerized by applying heat or light, and the resulting polymer is formed into a filter on the window frame. In this method, the entire device can also be embedded in a plastic made from an ethylenically unsaturated polymerizable monomer or a polyaddition composition such as Ebony resin.

In the optical filter composition of the present invention, one or more of the above dyes may be used in combination. In particular, when used in combination with absorbers of different absorption wavelengths, the absorption wavelength range can be expanded.

In the optical filter composition of the present invention, in order to further improve the light fastness, it is effective to add an ultraviolet absorber.
Resorcin monobenzoate, substituted or unsubstituted benzoic acid esters such as methyl salicylate, conaxy-3
- cinnamate esters such as gtyl methoxycinnamate;
λ, benzophenones such as lA-dioxybenzophenone, α, β-unsaturated ketones such as dibenzalacetone,! , % coumarins such as 7-cyoxycoumarin/1 carbostyrils such as Hiro-dimethyl-7-oxycarbostyryl, λ-phenylbenzimidazole, 2-(,
Azoles such as 2-hydroxyphenyl)hencytriazole are used.

In addition, in the case of a film made by a coating method using the optical filter composition of the present invention, a thin plastic film is pasted or coated on the surface of the coating layer for the purpose of protecting the coating layer and imparting droplet properties. You can do it.

For example, a laminated film can be obtained by stacking polyvinyl chloride films having a thickness of 0, oz mm and heat-pressing them to /λO to /AO0C.

The optical filter composition of the present invention contains o parts of the dye component or dye compound per ioo parts of binder expressed in parts by weight.
, oi-J″o part, preferably □.

/-10 parts.

The optical filter obtained by processing and treating the optical filter composition of the present invention only needs to have a transmittance in the wavelength range that should be blocked functionally as low as to achieve the intended purpose, and the transmittance is 10%. It is important to adjust the amount added per binder and the thickness of the filter so that the transmittance is preferably 2.0% or less, particularly preferably 0, ies or less.

The practical thickness is o, ooam or 7.5mm, but it is possible to design a filter with a thickness of 9 mm other than this am depending on the application.

(Effect of the invention) According to the optical filter composition of the invention, ≠00nm-r
It is possible to obtain an optical filter that efficiently absorbs light in the vicinity of 7 nm.In addition, by appropriately processing the optical filter composition of the present invention, it is possible to obtain a low-cost optical filter with excellent heat and light fastness. Obtainable.

This optical filter composition can be used not only as an independent optical filter, but also as one layer in a multi-layered photosensitive material, or mixed into a photosensitive layer.

(Example) Next, the present invention will be explained in more detail based on examples.

Example 1 An optical filter composition was prepared using Compound-7 synthesized in Synthesis Example 2, and an optical filter was produced.

That is, mix each component with the composition shown below in parts by weight (stir, filter, apply on a metal support by casting method, form a film, and peel off to form the desired optical filter. Several types of optical filters were obtained with dry film thicknesses varying between 0.02 and 0.3 mm.The optical densities of the optical filters thus obtained (thickness 25 microns) were It is shown in Figure 1.

Composition example TAC (cellulose triacetate) / 70 parts TPP
(triphenyl phosphate) io part methylene chloride 100 parts methanol
ito part compound -/
0. HirobeAlso, compound-/instead of compound-
FIG. 2 shows the optical density of an optical filter (thickness: 25 microns) prepared using No. 13 in the same manner as described above.

As is clear from FIGS. 1 and 2, it can be seen that by using the compound of the present invention, an optical filter that absorbs light in the vicinity of 4400-r00 nm can be obtained.

Example 2 The optical filter produced in Example 1 was used with a xenon lamp/
Light irradiation was performed using a fading tester at 7000 lux.

The number of days required for the concentration to decrease to the initial concentration of rocII was calculated using an optical filter made using compound-7.
It took 2 days for the optical filter prepared using 8 compounds -/-2. For comparison, a similar light emitting test was conducted on an optical filter prepared by the method shown in Example 1 using the following comparative compound having an extremely thick absorption near toonm. As a result, the number of days required for the concentration to decrease to the initial concentration of t0 was 0.7 days.

From this result, it is clear that the light fastness of the optical filter using the compound according to the present invention is greatly improved.

Comparative Compound Example 3 Optical filters were similarly prepared using the following compounds in place of Compound-7 used in Example 1.

Compound-2 #-3 1-! r -λ YOl -26 I -36 # -70 Each of the optical filters thus obtained had a dark blue color (with absorption near tAoo-1r00 nm) and had excellent light resistance. there were.

[Brief explanation of drawings]

FIG. 1 is an optical density curve of an optical filter (thickness: 2J microns) obtained from an optical filter composition using Compound-1 of the present invention, and FIG. 2 is Compound-/J of the present invention.

Claims (1)

[Claims] An optical filter composition characterized by containing at least one kind of methine dye represented by the following general formula (I) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [ I ] ( In the formula, n represents 0 or 1, m represents 0, 1, or 2. R_1 represents a substituted or unsubstituted alkyl group, R_2 represents a substituted or unsubstituted aryl group or heterocyclic group, R_3, R_4, R_5, and R_6 may be the same or different from each other, and include a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a hydroxy group, a substituted or unsubstituted amino group, a halogen atom, or a substituted or represents an unsubstituted heterocyclic group. Also, R_3 and R_4, R_3 and R_5, or R_4 and R
_5 may form a fused 6-membered ring. R represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a cyano group, or a substituted or unsubstituted acyl group. Further, R may be linked to R_1 to form a condensed ring. Z represents an atomic group necessary to form a 5-membered ring or a 6-membered ring, and these rings may have a substituent or be fused with another ring. Here, another ring may be combined with R_1 to further form a condensed ring. X^■ represents an anion. p represents 1 or 2, and when the dye forms an inner salt, p is 1
It is. )