JPS6043605A - Near infrared absorption filter - Google Patents

Abstract

PURPOSE:To stabilize near IR absorption characteristics and to enhance sensitivity and reliability of a photodetector by incorporating a specified dye derived from an anthraquinone compd. or naphthalocyanine compd. CONSTITUTION:An intended near IR absorption film or plate contains a dye derived from an anthraquinone compd. represented by formula I (X, Y is H, nitro, or the like; R1 is C1-C16 alkyl or the like; and R2 is H or C1-C4 alkyl) synthesized from a compd. of formula IV, or a naphthalocyanine compd. represented by formula II or III (R3-R6 are each H, sulfonic acid, or the like; (o), (p), (q), (r) are each 1-6; and Me is a metal atom) obtained by reacting urea and a metal salt, such as zinc salt with naphthalene-2,3-dicarboxylic acid deriv.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a near-infrared absorption film or absorption plate. More specifically, formula (1) [In formula (1), one of X and Y is 21
・Represents an atom or amino group, and the other represents a hydrogen atom. R1 is a linear or branched C1-6 alkyl group which may be interrupted by 1 to 5 oxygen atoms; a cycloalkyl group; an alkenyl group; an aralkyl group; a naryloxyalkyl group; a C1-12 R2 represents a hydrogen atom or a C1-4 alkyl group. ] An anthraquinone compound or an anthraquinone compound represented by formula (2) or (2) atom, sulfonic acid group, optionally substituted sulfonamide group, or optionally substituted aminomethyl group, O + p + q + r is the same - or one different number and an integer from 1 to 6. , Me each represents a metal atom.] The present invention relates to a near-infrared absorbing film or absorption plate characterized by containing at least one of the naphthalocyanine compounds represented by the following.

In recent years, as the amount of information has increased, technology in the information processing field has continued to make remarkable progress. Various improvements and developments have been made in the information reading methods used here, and optical reading devices are becoming increasingly important as input devices for computers, facsimile machines, and the like.

For example, in a POS system often used in mass retail stores, a barcode reader that uses near-infrared rays of a specific wavelength as reading light plays an important role in this system. In addition, robots are rapidly being introduced into factories and the like, and near-infrared rays are being applied to some parts of robot drive.

In all of these examples, a photodetector consisting of a semiconductor photodetector and a filter for canting specific wavelengths is used, but in order to prevent malfunctions and achieve high reliability, the filter used must be able to detect light other than the detected light. The device needs to be able to sufficiently cut out light and detect only light in a narrow wavelength range.

In this case, a black thread dye is used as a visible light cut filter, and it satisfactorily serves its purpose, but there is no good near-infrared cut filter that efficiently cuts near-infrared light.

The present inventors have been conducting extensive research to develop a near-infrared cut filter that exhibits stable absorption characteristics for near-infrared rays in the 700 to 900 nm wavelength range, greatly improving sensitivity and reliability as a photodetector. (1) or (2) or (
2) Excellent sensitivity and high (
・We discovered that reliability should be provided, and this led to the present invention. The compound (dye) represented by formula (1), (2), or (2) is used alone or in a mixture of two or more, and is usually applied to the surface or inside of a transparent plastic film or plate to form a near-infrared cut filter. It is applied to photodetection devices as a photodetector. The following method is used to apply the above-mentioned dye to a plastic film or plate.

(1) The above dye is mixed with a thermoplastic resin, heated and melted, and molded into a film or plate.

(11) A solution containing the above dye dissolved together with a binder is applied onto a transparent resin film or plate, and the binder solvent is evaporated to form a thin film containing the dye on the film or plate.

(iii') Dispersed particles obtained by micronizing the above dye with a dispersant etc. are dispersed in water, and a resin film or plate is immersed in the dispersed particles at a high temperature to transfer the dye into the interior of the film or plate.

Resins suitable for producing near-infrared absorbing films or plates include those that transmit infrared rays well and have excellent strength, such as polyethylene terephthalate, polymethacrylate, polyacrylate, polycarbonate, polystyrene, polyamide, epoxy, cellulose acetate, etc. Synthetic or semi-synthetic resins are suitable. In the method (11), the binder may include polyvinyl acetate, polyacrylic ester, polymethacrylic ester, polystyrene,
Resins or resin emulsions such as polyester, polychlorinated vinylopenitrocellulose, or water-soluble resins such as gelatin, polyvinyl alcohol, methylcellulose, carboxymethylcellulose, gum arabic, casein, and polyvinylpyrrolidone are used.

The amount of the dye shown in (1) or (2) or (2) above to be used in preparing the near-infrared absorbing film or absorbing plate is 0.0'QO1 to 0.0'QO1 to the absorbing film or absorbing plate. 5%, which is more suitable for 0
．． 01-1%. The thickness of the absorption film or absorption plate is usually 01μ to 5mm, more preferably 05μ to 5mm.
It is ITRm.

The anthraquinone compound (dye) of formula (1) is synthesized as follows.

, ↓(b) [Formula CA], CB], CCI, CD] and x, y in (1).

R1 and YL2 have the same meanings as above. ] That is, CA
,] is alkylated at 50-10'0°C using potassium carbonate as an acid binder in methyl cellosolve as in the method of JP-A-51-41735 to obtain [B]. . For example, as an alternative method,
React at 50-100°C in the presence of a cyanide such as sodium cyanide in formamide as in the method of No. 624 ([D] is obtained by the method of cl, followed by ring closure by heating in a solvent ( (B: l % is obtained by the method of d). Next, [B] is dissolved in dioxybenzene as in the method of Japanese Patent Publication No. 47-4635, and hydrogen sulfide gas is passed at 80 to 90'C (b). ) to obtain a compound (dye) of formula (1).

Examples of the alkylating agent used to obtain [B] from [A] include halogen compounds such as methyl iodide, ethyl iodide, butyl bromide, hexyl bromide, benzyl bromide, and allyl bromide; n-octyl tosylate, dodecyl tosylate, hexyloxyethyl tosylate, octyloxyethyl tosylate, butoxyethyl) sylate,
Ethoxyethyl tosylate, ethoxyethoxyethoxyethyl tosylate, octyloxyglopyl I sylate, hexyloxyethyl tosylate, enoxyethyl tosylate, cyclo'\xyloxyethyl tosylate, phenylethyl tosylate, cyclohexyl tosylate rate,
Methyl cyclohexyl tosylate, allyloxytyl tosylate, 2-butenyl tosylate, cinnamon tosylate or I-■3C-5O20 (C21140) 3-5C
Examples include sulfonic acid esters such as No. 2-15, sulfuric acid esters such as dimethyl sulfate, diethyl sulfate, triethyl phosphoric acid, and tributyl phosphoric acid, and phosphoric esters.

In addition, examples of amines represented by formula 1 formula % (3) (in the formula, horse represents the same meaning as in formula (1)), which are raw materials for producing [C], include nonyloxypropylamine, octyloxy Globylamine, hexyloxyglobylamine, dodecyloxyglopylamine, ethoxyglobylamine, octylamine, hexylamine, butylamine, propylamine, ethylamine,
Methylamine, allylamine, benzylamine, cyclo-\xylamine, aniline, toluidine, ethylaniline, xylidine, mezidine, hexylaniline, anisidine, phenetidine, 2゜5-dimethoxyaniline,
Examples include amines such as cresidine, butoxyaniline, hexyloxyaniline, butylaniline, dodecylaniline, and octyloxyaniline.

Further, the naphthalocyanine compound (dye) of formula (2) can be synthesized, for example, as follows.

i.e. Inorganica chimica AcLa
, Volume 44 (1980) 20! According to page J-210,
A naphthalene-2,3-dicarboxylic acid derivative, urea, and a metal salt described below are reacted at 250-310°C, and then impurities are extracted with a solvent to obtain a purified product. Furthermore, the obtained naphthalocyanine compound is induced into a sulfonamide after sulfonation or chlorosulfonation, or induced into aminomethyl after chloromethylation to obtain a naphthalocyanine compound (dye) of formula (2).

Naphthalene-2,3-dicarboxylic acid derivatives as raw materials include naphthalene-2,3-dicarboxylic acid, 5,8-dichloronaphthalene-2,3-dicarboxylic acid, 5.6.7
．． Examples include 8-tetrachloronaphthalene-2,3-dicarboxylic acid. Further, as the metal salt, zinc salt, magnesium salt, copper salt, nickel salt, cobalt salt, tin salt, etc. may be used.

Next, the present invention will be specifically explained with reference to Examples.

Example 1 1003 parts of dye are thoroughly mixed with 100 parts of polystyrene. Heat it to 200℃, melt it, put it in a mold and mold it to a thickness of 1.
Make the body board. A pale green colored polystyrene plate was obtained.

The light absorption characteristics of the obtained near-infrared absorbing plate are shown in FIG.

It can be seen that near-infrared rays with wavelengths of 600 to 860 p are effectively absorbed.

Dye 1 used here was synthesized as follows.

In 65 parts of ethylene glycol monomethyl ether, 214 parts of anhydrous potassium carbonate, 1,4-diamino-2,3-
Prepared with 14.4 parts of dicyanoanthraquinone 70-80
Incubate at ℃ for 6 hours. Next, 27.5 parts of γ-methoxybutyl tosylate was charged and reacted at 90-95°G for 4 hours. After cooling, 50 parts of methanol was added and the crystals were filtered, washed with water, and dried to obtain 159 parts of a compound represented by the following formula (Tl).
Dissolve 59 parts in 200 parts of 0-dichlorobenzene,
The reaction was carried out at −90° C. while blowing hydrogen sulfide gas, and 1136 parts of the dye (crude material) were obtained. m9 192-4℃ when recrystallized in xylene, λmax 75 in acetone
A purified product exhibiting a wavelength of 3 nm is obtained.

0.1 part of the mixture of dyes 2 and 3 is thoroughly mixed with 100 parts of polymethyl methacrylate. This was heated to 220° C. to melt it, and was molded into a mold to obtain a pale green colored absorption plate having a thickness of Q and 5 mm. The light absorption characteristics of the obtained near-infrared absorbing plate are shown in FIG.

It can be seen that it effectively absorbs near-infrared rays with a wavelength of 600 to 860 nm.

The mixture of dye 2 and dye 3 used here was synthesized as follows.

In 65 parts of ethylene glycol monomethyl ether, 21.4 parts of anhydrous potassium carbonate and 166 parts of 1,4-diamino-5-nitro-2,3-dicyanoanthraquinone are charged and reacted at 70-80°C for 6 hours. Next, 27.5 parts of γ-methoxybutyl tosylate was added and heated to 90-95°C.
Let it react for 4 hours. After cooling, 50 parts of methanol was added, and the crystals were filtered, washed with water, and dried to obtain 164 parts of a mixture of compounds represented by formulas (n) and (111). Next, 164 parts of this mixture was dissolved in 200 parts of 0-dichlorobenzene,
While blowing hydrogen sulfide gas at 80-90'C, the compounds of formulas (Company) and (11) were analyzed by thin layer chromatography.
The reaction is carried out at such a temperature that the intermediate products Dye 5 and Dye 6 are no longer observed.

After cooling, 300 parts of methanol was added, and the crystals were filtered, washed with methanol, then hot water, and dried to obtain 14.3 parts of a crude dye. The crude dye was recrystallized from xylene to obtain a mixture of Dye 2 and Dye 3. (λrnaX in acetone 7
551m) Example 3 Dye 4 45 parts of the dye was mixed with 5 parts of dinaphthylmethane disulfonic acid and 4 parts of water.
The mixture was sufficiently wet-pulverized with 0 parts in a sand mill to form a finely dispersed state, and then dried in a spray dryer to obtain a powder that can be finely dispersed in water. To 5 parts of this powder, 3000 parts of water adjusted to pi-14.5 with acetic acid and sodium acetate was added to prepare an aqueous dispersion of dye 4. , made by Toshi) 5
0 part was immersed and dyed in a high-temperature, high-pressure dyeing machine at 130°C for 30 minutes. A transparent, yellowish-green colored film was obtained. The obtained near-infrared absorption film has excellent near-infrared absorption properties. When the resulting near-infrared absorbing film was placed under sunlight for 10 minutes, the temperature of the film rose from 25°C to 35°C.In contrast, the temperature of the undyed film rose to 25°C.
There is only one way to increase the temperature from °C to 31 °C. The heat ray absorption effect of the near-infrared absorbing film of the present invention is clear.

Example 4 A mixture of dyes 5 and 6 was treated in the same manner as in Example 3 to obtain a dispersible powder. To 4 parts of this powder, 3,000 parts of water and 6 parts of Tetrosin (manufactured by Yamakawa Pharmaceutical Co., Ltd.) were added to prepare an aqueous dispersion.
50 copies (manufactured by Toshi) were immersed and dyed at 100°C for 30 minutes. A transparent, blue-green colored film was obtained. The obtained near-infrared absorption film had excellent near-infrared absorption properties. Furthermore, by treating a polycarbonate film in the same manner as in Example 3 and a cellulose acetate film in the same manner as in Example 4, a near-infrared absorbing film having the same effects as in Example 3.4 can be obtained. .

Example 5 7001 parts of dye and 100 parts of polycarbonate are thoroughly mixed. This was heated and melted at 300°C, molded into a mold, colored pale green to a thickness of 1m+n, and an absorbing plate was folded.

The light absorption characteristics of the obtained near-infrared absorbing plate are shown in FIG.

It can be seen that the near-infrared absorption characteristics are excellent. Dye 7 is synthesized as follows.

Naphthalene 2, 8 parts of 3-dicarboxylic anhydride, 12 parts of urea
1 part and 4 parts of zinc acetate were heated and reacted with stirring. 12
Reacts with vigorous foaming at 0 to 160°C. Furthermore, the temperature was gradually increased to 300℃ in 1 hour, and the temperature was increased to 300-310℃ for 3 hours.
Hold for 0 minutes and let cool.

Add hot water to loosen solids and filter. Further, the mixture is washed with a 5% sodium carbonate solution, washed with water, and dried to obtain a crude product. The crude pigment is then heat-extracted with pyridine, and the process is repeated until the extract loses its brown color. The remaining residue was washed with water and hot water to obtain 46 parts of Dye 7. The melting point is 300° C. or higher, and the color of this dye dissolved in dimethylformamide is pale green-blue.

λmax 759 nm (DM, P) Example 6: 81 parts of dye and 10 parts of polymethyl methacrylate were dissolved in a mixed solution consisting of 15 parts of acetone, 15 parts of toluene, and 15 parts of dimethylformamide, and the mixture was cast to a thickness of 0.5 cm by casting. A near-infrared absorbing film colored pale green with a color of 0.02m was obtained. Dye 8 used here was synthesized as follows.

In 65 parts of ethylene glycol monomethyl ether, 214 parts of anhydrous potassium carbonate, 1,4-diamino-2,3-
Add 144 parts of dicyanoanthraquinone to 70-80°
G for 9 hours.

Next, add 32 parts of n-hexyloxyethyl tosylate and react at 90-95°C for 4 hours.

After cooling, 50 parts of methanol was added, and the crystals were filtered, washed with water, and dried to obtain 17 parts of a compound represented by the formula (q).

Next, 17 parts of the compound of formula (EV) was dissolved in 230 parts of 0-dichlorobenzene, and at 80 to 90°C, while blowing hydrogen sulfide gas, the compound of formula (■
) until the compound is no longer observed.

After cooling, 300 parts of methanol was added, and the crystals were filtered, washed with methanol and then hot water, and dried to obtain 14 parts of a crude dye.

The crude dye was dissolved in xylene, the undissolved matter was filtered out, and then subjected to silica gel column chromatography, developed with xylene, purified and fractionated, and after concentrating the solvent, the precipitated crystals were dried in a separate F to obtain blue dye 8. Obtained.

Melting point: 126-127° The color of the dye dissolved in acetone is blue-green.

λmax 74.3 nm (Ace'tone) Near-infrared absorbing films and absorbing plates can be produced using the compounds (dyes) represented by the structural formulas in the following table in the same manner as in Examples 1 to 6.

Reference Example 1 Composition of X Reducer ■1□0 22 parts Emulgen 911 (manufactured by Kao Soap) 5 parts Mineral turpentine 73 parts The above composition was passed through a colloid mill and then treated with a sand grinder for 4 hours to obtain a coating liquid for fiber processing. I got it. The coating solution was applied to a cotton cloth by stiching so that the amount of coating after drying was the same as that of the fibers, and heat treatment was performed at 150°C for 5 minutes to obtain a treated cotton cloth whose surface was treated with a resin containing a pigment. . When this treated cotton cloth is placed under sunlight for 10 minutes,
The temperature of the treated cotton fabric increased from 25°C to 36°C. On the other hand, unprocessed cotton fabric only has a temperature increase of 25 to 32 degrees Celsius. It is recognized that Dye 1 of the present invention absorbs near-infrared rays well.

[Brief explanation of drawings]

FIG. 1 is a diagram showing the light absorption characteristics of the near-infrared absorption plate obtained in Example 1. FIG. 2 is a light absorption characteristic diagram of the near-infrared absorbing plate obtained in Example 2. FIG. 3 is a light absorption characteristic diagram of the near-infrared absorbing plate obtained in Example 5. Patent applicant Nippon Kayaku Co., Ltd.

Claims (1)

[Claims] (1) Formula (1) [In formula (1), one of X and Y represents a nitro group or an amino group, and the other represents a hydrogen atom. R1 is a linear or branched C7-16 alkyl group which may be interrupted by 1 to 5 oxygen atoms; a cycloalkyl group; an alkenyl group; an aralkyl group; an aryloxyalkyl group; C1-,2 represents a hydrogen atom or a C1-4 alkyl group. ] or formula (2) % formula % (2) [Formula (21, (2i, R3,1 4.R5 and
6 is the same or different atom or group, and is a hydrogen atom, a chlorine atom, a sulfonic acid group, an optionally substituted sulfonamide group, or an optionally substituted aminomethyl group,
0. p, q, and r are the same or different numbers and represent integers of 1 to 6, and Me represents a metal atom. ] A near-infrared absorbing film or absorbing plate characterized by containing at least one kind of naphthalocyanine compound represented by: