JPS62246963A - Anthraquinone compound - Google Patents

Abstract

PURPOSE:To provide anthraquinone compds, having a specified structure, which are useful as materials for a near-ultraviolet filter, an optical disc memory and a thermal writing liquid crystal element. CONSTITUTION:An thraquinone compds. of formula I or II wherein R, and R3 are independently hydrogen, fluorine, chlorine, bromine, cyano, methyl, ethyl, methyoxy, ethoxy or trifluoromethyl; R2 and R4 are independently a member selected from the group consisting of hydrogen, fluorine, chlorine, bromine, cyano nitro, trifluoromethyl, nonafluorobutyl, R2, -OR5,-(CH2)m, etc.; R5 is a 1-12C alkyl which may be substituted by cyclohexyl, cyclohexyloxy, phenyl or phenoxy; and m is 0.1 or 2. the anthraquinone compds, of formula I or II can be obtd. by reacting an anthraquinone compd. of formula III (wherein R1 and R2 areas defined above; and X is chlorine or bromine) with an o- aminothiophenol derivative of formula IV (wherein R2 and R4 are as defined above) in the presence of absence of a solvent with heating.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a novel anthraquinone compound that exhibits strong absorption in the near-infrared region, and more specifically to near-infrared filters, optical disk memories, and thermal writing liquid crystal devices. This invention relates to a novel anthraquinone compound that is useful as a material for.

BACKGROUND OF THE INVENTION There are many uses for organic materials that absorb in the near-infrared region, and three examples will be described below.

■ Near-infrared filters Near-infrared filters are used in electrical products such as televisions, radios, and stereos, wireless remote control devices for industrial robots, automatic focal length measurement devices for cameras, and barcode readers. For example, in a wireless remote control device for electrical appliances, the transmitting section has an infrared light emitting diode (emitting wavelength of 800 to 11,000 nm for general-purpose products), which is a near-infrared light emitting element, and the receiving section has a near-infrared sensitive photodiode, which is a light receiving element. A diode (general-purpose product with a sensitivity wavelength of 650 to 101,000 nm) is installed, but in the environment in which this device is used, malfunctions may occur due to visible light and near-infrared light from the sun, incandescent bulbs, fluorescent lights, etc. There is a possibility that

In order to cant visible light and near-infrared light in the environment in which these devices are used, if a near-infrared filter that absorbs visible light and near-infrared light below a specific wavelength is used in the light receiving section, near-infrared emission information can be obtained. can be selectively and efficiently received, reducing malfunctions.

Traditionally, this type of filter has been made by adding manganese or chromium oxides to lead glass, or by adding cadmium sulfide or selenium to potassium zinc glass, or by adding coloring ingredients to gelatin or acetate. Solvent Green 20, an anthraquinone oil-soluble dye listed in the color index. Solvent Green 28, or phthalocyanine pigments Pigment Green 7, Pigment Green 36,
Pigment Green 37, ・Pigment Green 3
8 and a transparent resin, such as ABS resin or methacrylic resin, are heated and melted to form a plate or film.

■ Optical disk memory Optical disk memory narrows down a laser beam to raise the temperature of its focal point, forms bits on a recording thin film on a rotating disk, records (writes) information, and reproduces (reads) information. ) is performed by irradiating a laser beam weaker than that during recording, making use of the difference in optical changes between recorded and unrecorded areas.

Solid solution alloys such as Te oxide, inorganic metal compounds such as Te oxide, and organic compounds such as polymethine dyes, cyanine dyes, merocyanine dyes, squalium dyes, and phthalocyanine dyes are used.

α Thermal writing liquid crystal element Thermal writing liquid crystal element using a laser beam is produced by irradiating a laser beam onto a liquid crystal sandwiched between a pair of aligned transparent electrodes or a suitable substrate to transform the liquid crystal into an isotropic phase (isotropic phase). liquid) by rapid cooling after K.
It provides an optically transparent part and an opaque part to write a desired image and display a desired signal.

As for the liquid crystal used in this liquid crystal element.

There are mixed liquid crystals of nematic and cholesteric liquid crystals with negative dielectric anisotropy, and smectic liquid crystals with positive dielectric anisotropy.

Since a portion that has been rapidly cooled after being heated by a laser beam exhibits a light scattering state, an appropriate projection optical system can display an image corresponding to the scanning pattern of the laser beam as "Black on -W".
It is possible to display it on a large screen in the form of "white".

Furthermore, in this type of liquid crystal element, it is also possible to erase images thermally written using the method described above. That is, the initial state can be achieved by heating the entire element with a heat source other than the laser beam, such as a heater, to heat the liquid crystal to an isotropic phase, and then cooling it while applying a voltage between the electrodes.

Semiconductor lasers have come to be used as beam sources for optical signal generators in this system because they are small and lightweight.
Despite having an oscillation wavelength of 50 nm or more, the above-mentioned liquid crystal elements have low heat exchange efficiency for near-infrared beams, making writing impossible or slowing down the writing speed. Attempts have been made to increase heat exchange efficiency by adding absorbing dyes to the region.

Polymethine dyes, cyanine dyes, phthalocyanine dyes, and the like are known as dyes added to increase the heat exchange efficiency of the liquid crystal element for semiconductor laser light.

Problems to be Solved by the Invention The materials used in the above applications (1) to (3) have the following drawbacks.

First, the inorganic glass filter used in application (2) has problems with processability, and gelatin filters have problems in handling and are expensive. In addition, resin filters have no problems in processability and handling, but the near-infrared cut wavelength limit is as short as 750 to 800 nm, for example, 800 to 9
It cannot satisfy the current market demand for something that cuts near-infrared rays down to 00 nm and has a steep rise in the transmission curve.

Next, Te alone and Te alloys used in application (2) are chemically unstable and easily deteriorate in the air, and the toxicity of the material itself is a problem. In addition, Te oxide is Te
Alloys and other materials are stable, but their chemical properties, such as absorption and reflectance, are sensitive to oxidation state. Therefore,
The disadvantage is that the oxidation state must be tightly controlled. In addition, polymethine dyes, cyanine dyes, merocyanine dyes, etc. are subject to so-called reproduction deterioration, in which the dyes are bleached by repeated irradiation with readout light during readout after writing, and the readout S/R ratio deteriorates. The drawback is that it cannot be put to practical use. Squalium dyes have low sensitivity and the formed film is in poor condition. Phthalocyanine dyes are known as high-fastness blue pigments, but those that absorb in the near-infrared region have thermally unstable crystal forms, and self-transform into more stable short-wavelength absorption. It has properties.

Furthermore, the polymethine dyes, cyanine dyes, etc. used in application (■) have problems with the light fastness of the plastic as explained in the above application (■), and phthalocyanine dyes cannot be used in application (■) due to their dissolution in liquid crystals. I have a sexual problem.

Means for Solving the Problems The present inventors have discovered that a synthetic material that exhibits strong absorption in the near-infrared region, is optically, thermally and chemically stable, and can be used for various applications including the above-mentioned applications After extensive research into organic materials that have good compatibility with resins, organic solvents, or liquid crystals, we found that the formula (1) or (II) [In formula (1) or (II), R1 and R3 are each independently hydrogen, Represents fluorine, chlorine, bromine, cyanide, methyl, ethyl, methquine, ethoxy or trifluoromethyl. In addition, horses and turtles each independently contain hydrogen, fluorine, chlorine, bromine,
Represents cyano, nitro, and −〇 bird. and horse represents C1-1□ alkyl optionally substituted with cyclohexyl, cyclohexyloxy, phenyl, phenoxy (in which the carbon chain may be interrupted by 1-3 oxygen atoms), Birds have at least three hydrogen atoms substituted with fluorine. represents alkyl, m is O
Represents ll or 2. ] The present invention was completed by discovering that a novel anthraquinone compound represented by the following possesses these properties.

The anthraquinone compound represented by formula (I) or (II) of the present invention can be synthesized, for example, by the following method.

That is, an anthraquinone compound represented by Formula 1 (III) [Formula (■D, R7, horse represents the same meaning as above, X represents chlorine or bromine] and Nirunhiki [Formula, R3, R4 represents the same meaning as above.] It can be synthesized by reacting the orunaminothiophenol derivative represented by the following without a solvent or in the presence of a solvent, and optionally in the presence of an acid binder under heating. .

Specific examples of solvents that are optionally used when reacting the compound of formula (U) with the compound of 2) include N-methylpyrrolidone, N,N-dimethylformamide, dimethylsulfoxide, dimethylimidazolidinone, etc. In addition, when reacting the compound of formula ([Il with the compound of formula (5), acid binders that may be allowed to coexist if necessary include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, Examples include sodium hydrogen carbonate, and the amount used is 1 mol or more, preferably 1 to 3 mol, per 1 mol of the anthraquinone compound of formula (@).

By controlling the reaction temperature when reacting the compound of the formula (rabbit) and the compound of the formula (1) or (
The compound II) can be synthesized.

That is, when the reaction temperature is around 100 to 160°C, the compound of formula (1) is formed, and when the reaction temperature is around 180 to 220°C, the compound of formula (I) is formed.
Compound t) is produced as the main product.

When the reaction temperature is around 160 to 180°C, formula (1)
It is synthesized as a mixture of (II). The obtained compound has the formula (1) by recrystallization or column chromatography.
Although it is possible to isolate and purify the compound 1 or (ff), the mixture may be used as it is when used in the above-mentioned industrial applications.

The novel anthraquinone compound represented by formula (1) or (II) thus obtained can be used in synthetic resins, organic solvents, or liquid crystals with a wavelength of 700 to 950 nm, depending on the substrate.
It exhibits strong absorption in the near-infrared region, is photothermally and chemically stable, and has good compatibility with synthetic resins, organic solvents, and liquid crystals.

The anthraquinone compound represented by (I) or (II) of the present invention can be used for various purposes, and the above three examples of uses will be specifically described.

First, when used as a near-infrared filter, the formula (I
) or (It), one or more anthraquinone compounds represented by polystyrene, As resin, ABS resin,
Methacrylic resin, polyvinyl chloride, polycarbonate,
After mixing with a synthetic resin such as a fluororesin or an epoxy resin and additives such as a plasticizer and a hardening agent that may be added as the case may be, and heating, the mixture is molded into a plate or film.

At this time, one or more anthraquinone compounds represented by formula (I) or (II) are added in a weight ratio of 0.0001 to 5%, preferably 0.01 to 1%, based on the synthetic resin. It is desirable to do so.

Next, when using it for optical disk memory, use 2 (1).
One or more anthraquinone compounds represented by (It) or (It) are dissolved in a solvent, applied onto a substrate, and dried.

Further, if necessary, a resin binder or the like may be added. Examples of solvents that can be used include dichloromethane, dichloroethane, acetone, methyl ethyl ketone, and the like. The coating method is 10 to 11,000 nm, preferably 50 to 20 nm using a spray or spinner.
Apply to a thickness of 0 parts m.

The material of the substrate forming the recording layer is not particularly limited and may be any of various resins, glasses, ceramics, metals, etc., but there are certain issues such as molding of the substrate, difficulty in handling, storage stability, prevention of dye migration to the substrate, etc. An acrylic resin board or a polycarbonate resin board is preferred.

It is convenient to use a near-infrared laser, such as a semiconductor laser with an oscillation wavelength of 750 to 850 parts m, as a light source for recording and reading.

Furthermore, when used for thermal writing liquid crystal devices, one or more anthraquinone compounds represented by formula (1) or (II) are added at a weight ratio of 0.01 to 1 to the liquid crystal.
A liquid crystal composition can be prepared and used by adding 0%, preferably 0.1 to 5%.

The liquid crystal compound for preparing this liquid crystal composition is as follows:
biphenyl type, terphenyl type, phenylcyclohexane type, cyclohexylcyclohexane type, ester type,
There are mixed systems of pyrimidine-based, dioxane-based, cyclohexyl methyl ether-based, Schiff-based, azo-based, and azoxy-based nematic liquid crystals with negative dielectric anisotropy, and mixed systems of smectic liquid crystals with positive dielectric anisotropy. . Cholesteric liquid crystals added to nematic liquid crystals having negative dielectric anisotropy include cholesteryl bromide, nyllesteryl acetate, cholesteryl propionate, cholesteryl hexyl ether, chic type, azo type, -
There are azoxy-based, ester-based, biphenyl-based, and terphenyl-based liquid crystals in which optically active 2-methylbutyl groups, 3-methylbutyl groups, etc. are introduced at the ends.

A writing light source for a thermal writing liquid crystal element using a liquid crystal composition containing one or more anthraquinone compounds represented by formula (1) or (II) has an oscillation wavelength of 750 to 850 parts m. It is convenient to use a semiconductor laser of .

The uses of the anthraquinone compound represented by formula (1) or (II) of the present invention are not limited to the above three examples, but can be used in near-infrared absorbing inks, electrophotographic photoreceptors, electrophotographic toners, etc. .

The anthraquinone compound of the present invention exhibits strong absorption in the near-infrared region, is stable against light, heat, and chemical effects, and has extremely high compatibility with organic solvents and resin liquid crystals, so it can be used for near-infrared filters, optical disk memories, etc. It is extremely useful as a dye for thermal writing liquid crystal devices.

EXAMPLES The present invention will be specifically explained with reference to Examples below. In the examples, "part" and "chi" mean parts by weight and % by weight, respectively.

Example 1 To 350 parts of N-methylpyrrolidone were added 125 parts of O-aminothiophenol and 69.2 parts of 1,8-bis(p-n-butylanilino)-45-dihydroxy-3,6-dipromuanthraquinone to 150 parts. Raise the temperature to 'C. After raising the temperature, the mixture was reacted at 155°C for 6 hours. 70℃ after completion of reaction
Cool to 500 parts of methanol. The precipitated crystals are filtered, washed with methanol and water, and then dried.

The obtained crude product was purified by column chromatography to obtain 55.8 parts of dye 1 of the following formula.

Dye 1° Melting point: 126-129° C. Maximum absorption wavelength (hereinafter expressed as λmax) and molecular extinction coefficient (hereinafter expressed as ε) in xylene were 784 parts m and 33,500, respectively.

λmax in MariBDH liquid crystal E-8 is 803 parts m
Yes, the solubility was 1 or more.

The structure was confirmed by mass spectrometry.

Example 2゜The same reaction as in Example 1 was carried out except that the reaction temperature was changed to 190 to 200°C in contrast to the reaction temperature of 150 to 155°C in Example 1, and the resulting next product was recrystallized with Xin/. Then, 43.5 parts of dye 2 of the following formula was obtained.

Dye 2° Melting point 275-279°C λmax 824 parts m, e 40300 (in xylene) λmax 847 parts m (E-8
(Middle) The structure was confirmed by mass spectrometry.

Example 3 2-Amino-5 was added to 35 parts of N,N-dimethylformamide.
-Ethoxythiophenol 16.9 parts, 1,8-bis(
p-n-butylanilino)-4,5-dihydroxy-3
, 6-dibromoanthraquinone was added, and 140
Raise the temperature to ℃. After raising the temperature, the reaction is carried out at 140 to 145°C for 3 hours. After the reaction was completed, it was cooled to 70'G and methanol 50
Add part. The precipitated crystals are filtered, washed with methanol and water, and then dried. The obtained crude product was purified by column chromatography to obtain 5.1 parts of dye 3 of the following formula.

Dye 3° Melting point 103-105°C λmax 803 nm, ε34,500 (
in xylene) λmax 825 parts m (E
-8) The structure was confirmed by mass spectrometry.

Example 4 1,8-bis(P-
methylanilino)'-4,5-dihydroxy-3,6-
Add 10 parts of dibromoanthraquinone and raise the temperature to 150°C. After raising the temperature, the reaction is carried out at 150 to 155°C for 5 hours. After the reaction is completed, the mixture is cooled to 70°C and 100 parts of methanol is added. The precipitated crystals are filtered, washed with methanol and water, and then dried. The obtained crude product was purified by column chromatography to obtain 7.8 parts of dye 4 of the following formula.

Dye 4° Melting point 172-175°C λmax 778 nm + ε 31,800
(in xylene) The structure was confirmed by mass spectrometry.

Example 5 300 parts of N-methylpyrrolidone, 125 parts of 0-7 minothiophenol, 1,8-bis(p-methylanilino)-
Add 59.4 parts of 4,5-dihydroxy-3,6-dipromoanthraquinone and raise the temperature to 190°C. After heating 1
React at 90-200°C for 6 hours. After the reaction is completed, the mixture is cooled to 70°C and 500 parts of methanol is added. The precipitated crystals are filtered, washed with methanol and water, and then dried. When the obtained crude product was recrystallized from xylene, 42 parts of dye 5 of the following formula was obtained.

Dye 5° Melting point 295-298°C λmax 816 parts m, g 33,000 (in xylene) The structure was confirmed by mass spectrometry.

Example 6゜30 parts of dimethylimidazolidinone, 12.5 parts of O-aminothiophenol, 1,8-bis(anilino)-4,5
-dihydrox/-3゜6-dipromanthraquinone5.
Add 8 parts and raise the temperature to 150'C. 150-1 after heating up
React at 55°C for 5 hours. After the reaction is completed, the mixture is cooled to 70°C and 50 parts of methanol is added.

The precipitated crystals are filtered, washed with methanol and water, and then dried. The obtained crude product was recrystallized from xylene to obtain 4.1 parts of dye 6 of the following formula.

Dye 6° Melting point 205-207°C λmax 778 parts m (in xylene) The structure was confirmed by mass spectrometry.

Example 7 To 30 parts of N-methylpyrrolidone, 12.5 parts of 0-aminothiophenol 1,8-bis(p-methoxyanilino)
Add 6.3 parts of -4,5-dihydroxy-3,6-dibromoanthraquinone and raise the temperature to 170°C. 170 after heating
React for 5 hours at ~175°C. After the reaction is completed, the mixture is cooled to 70°C and 50 parts of methanol is added. The precipitated crystals are filtered, washed with methanol and water, and then dried. The obtained crude product was purified by column chromatography to obtain 2.4 parts and 2.5 parts of dye 7 and dye 8 of the following formulas, respectively.

Dye 7° Melting point 155-159°C λmax 781 parts m (in xylene) Dye 8° Melting point 305-309°C λmax 824 parts m (in xylene) Example 8° 1,8-bis(P-methylanilino) in Example 4
-4,5-dihydroxy-1°8-bis(P-chloroanilino)- instead of 3°6-dibromoanthraquinone
When the same reaction as in Example 4 was carried out except that 4,5-dihydroxy-3,6-dibromanthraquinone was used, dye 9 of the following formula was obtained.

Dye 9° Melting point 173-175°C λmax 776 parts m (in xylene) The composition was confirmed by mass spectrometry.

Application Example 1 0.02 part of dye 1 synthesized in Example 1 was added to 100 parts of polystyrene (Styron 666, Asahi Kasei ■) and mixed thoroughly. Next, the mixture is heated to 200°C and melted, and molded into a mold to form a plate with a thickness of 1 mm.

A pale green colored polystyrene plate was obtained.

The light absorption curve of the obtained polystyrene plate is shown in FIG.

It was found that near-infrared rays with a wavelength of 700 to 810 nm were effectively absorbed, and it is clear that it is effective as an infrared absorbing filter.

Application example 2゜Epoxy resin (R-140) Mitsui Petrochemicals epoxy ■)
1'000 parts of hardening agent (MH-700, New Japan Chemical ■)
700 parts of tin octylate, 3.4 parts of tin octylate, and 8.5 parts of dye 4 synthesized in Example 4 were added and mixed thoroughly. Next, it is heated at 100°C for 4 hours and molded to make a plate with a thickness of 2 mm. An epoxy resin plate with a light green color was obtained.

The light transmission curve of the obtained epoxy resin plate is shown in FIG.

It has been observed that near-infrared rays of 920 parts m or less are completely cut out, and it is clear that it is effective as an infrared absorption filter.

Application example 3゜Pigment 2 synthesized in Example 2 3 parts Dichloroethane 100 parts The mixture consisting of the above composition was uniformly dissolved, applied to an acrylic substrate (Acrylic Light MR-200 manufactured by Mitsubishi Rayon) with a spinner, dried and thickened. An optical recording layer of 150 parts m was obtained. When this recording layer was irradiated with a semiconductor laser (s3onm) with a beam diameter of 1 μm, clear bits were formed in the irradiated area.

Application example 4゜Dye 5 synthesized in Example 5 3 parts polystyrene 1 part dichloroethane 100 parts A mixture having the above composition was uniformly dissolved, coated on a glass substrate with a spinner, and dried to a thickness of 200 parts m. An optical recording layer was obtained. When this recording layer was irradiated with a semiconductor laser (830 parts m) with a beam diameter of 1.5 μm, clear pits were formed in the irradiated area.

Application Example 5: A liquid crystal composition was obtained by adding 0.5 g of Dye 3 synthesized in Example 3 to smectic liquid crystal S2 manufactured by BDH. Next, this liquid crystal composition was sealed in a cell in which two vertically aligned transparent glass electrode substrates were placed facing each other at an interval of about 10 μm to obtain a liquid crystal element. A semiconductor laser (
When 830 parts m) were irradiated with a beam diameter of 10 μm, the irradiated part rose in temperature and became an isotropic liquid, which was then rapidly cooled and became in a scattering state.

When a halogen lamp was passed through this liquid crystal element and the image was enlarged on a screen, a clear 1ack-on-white image was obtained.

Examples 9 to 115 Anthraquinone compounds represented by formula (1) or (II) were synthesized according to Examples 1 to 8.

Tables 1 and 2 show the structural formula and λmax in xylene of the anthraquinone compound represented by formula (1) or (U).

In addition, for R8, the or-position and meta-position relative to one group are each expressed as 0-lm-, and for R3, -8
- The ortho, meta, and para positions of the group are each 0.
+ ” + p-.

Effects of the Invention An anthraquinone compound exhibiting strong absorption in the near-infrared region (700 to 950 nm) was obtained. This material is optically, thermally, and chemically stable, and has good compatibility with synthetic resins, organic solvents, and liquid crystals, and is extremely useful as a material for near-infrared filters, optical disk memories, and thermal writing liquid crystal elements. is high.

[Brief explanation of drawings]

FIG. 1 shows the light absorption curve of the polystyrene plate obtained in Application Example 1 described in the text, and FIG. 2 shows the light transmission curve of the epoxy resin plate obtained in Application Example 2.

Claims (1)

[Claims] (1) Formula (I) or (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) [In formula (I) or (II), R_1, R_3 each independently represents hydrogen, fluorine, chlorine, bromine, cyano, methyl, ethyl, methoxy, ethoxy or trifluoromethyl. In addition, R_2 and R_4 are each independently hydrogen, fluorine,
Chlorine, bromine, cyano, nitro, trifluoromethyl, nonafluorobutyl, -R_5, -OR_5, -SR_5, -
SO_2R_5, -COR_5, -(CH_2)mCO
_2R_5, -NHCOOR_5, -NHCOOR_5,
▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲Mathematical formulas, chemical formulas,
There are tables, etc. ▼, -OR_6. And R_5
is cyclohexyl, cyclohexyloxy, phenyl,
C_1_-_1_2 optionally substituted with phenoxy
(in which the carbon chain may be interrupted by 1 to 3 oxygen atoms), R_5 represents C_2_~ in which at least three or more hydrogens are replaced by fluorine
_9 alkyl, m represents 0, 1 or 2. ] Anthraquinone compound represented by