JPH01108265A - Near-infrared absorber and optical recording medium made by using it - Google Patents

Abstract

PURPOSE:To obtain a near-infrared absorber which is excellent as near-infrared absorbing coloring matter and has a proper degree of solubility, compatibility with resin, and excellent durability, by using a specified diphthalocyanine. CONSTITUTION:This near-infrared absorber comprises a diphthalocyanine of formula I [wherein the benzene rings A, B, C, D, E, F, G and H each may be substituted by (substituted) alkyl, alkoxy, aryl, alkylamino, arylamino, etc.; [Met]<4+> is Si, Sn, Ge or Ti] or its tautomer. This absorber has excellent durability and processability. It can be incorporated into resin or it can dye resin. An optical recording medium containing it has good durability and sensitivity. A compound of formula I can be obtained by reacting 1-4 compounds of formula II or III (wherein the benzene ring may be substituted as in formula I) with an alkali metal alkoxide through heating in an alcohol to give an alkali metal salt of phthalocyanine, which is then reacted with, e. g., tetrachlorotin or tetrachlorogermanium.

Description

[Detailed Description of the Invention] [Field of Industrial Application] In recent years, energy systems using light in the near-infrared range,
Many information recording systems and equipment control systems have been developed. The compounds of the present invention relate to near-infrared absorbers that can be used in these systems.

More specifically, it is used in fields such as optical recording media, organic photoreceptors, optical cards, light absorption for control mechanisms of televisions and audio equipment, shielding of external near-infrared light, safety glasses for laser processing, and growth control by shielding heat rays. Regarding the compounds that can be made.

[Conventional technology]

Until now, as an optical information recording medium using a phthalocyanine compound, there is a recording layer composed of a compound of metal, metal oxide, or metal halide and phthalocyanine on a substrate, as disclosed in Japanese Patent Application Laid-Open No. 55-97033. It is known from US Pat. No. 4,241,355 to use dyes selected from lead phthalocyanine, chloroaluminum phthalocyanine, vanadyl phthalocyanine, tin phthalocyanine or chloroaluminum chlorophthalocyanine as the recording layer.

However, recording layers using these phthalocyanine compounds alone have the drawback of weak absorption in the long wavelength region and poor recording sensitivity.

In addition, as an improved method, Japanese Patent Application Laid-open No. 154888 and 61-198
No. 1-148595 attempted to increase the wavelength by introducing heteroatoms such as sulfur, nitrogen, and selenium into the phthalocyanine ring. However, these compounds had insufficient film-forming properties and could not be processed into stable optical recording media.

[Problem that the invention seeks to solve]

The present invention was made to solve the above-mentioned problems, and an object of the present invention is to provide a long-wavelength absorbing phthalocyanine compound that has excellent durability, is easy to process, and can produce an optical recording medium with few defects. do.

[Means for solving problems]

The present inventors have accomplished the present invention by discovering that Shiftalodianine is excellent as a near-infrared light absorbing dye, has appropriate solubility, compatibility with resins, and is excellent in durability.

That is, the present invention provides the following formula (I) characterized in that two phthalocyanine rings are bonded to a tetravalent central element.
) and its tautomer.

(I) [In formula (I), benzene rings A, B, C, D, E, F, G
, H may each be independently substituted with a substituted or unsubstituted alkyl group, alkoxy group, alkylthio group, alkylamino group, aryl group, aryloxy group, arylthio group, or arylamino group; tin,
represents silicon, germanium, titanium] Another invention is an optical recording medium containing the same in two layers.

Examples of substituted or unsubstituted alkyl groups that may be substituted on each benzene ring of the compound represented by formula (I) include linear or branched alkyl groups having 1 to 20 carbon atoms, preferably 1 to 20 carbon atoms;
12 linear or branched alkyl groups; methoxymethyl group,
Alkoxyalkyl groups such as methoxyethyl group, methoxybutyl group, ethoxymethyl group, butoxymethyl group, phenodiethyl group, allyloxyethyl group, ethoxyethoxymethyl group, ethoxyethoxyethoxyethyl group;
Aralkyl groups such as benzyl group and phenethyl group; halogenated alkyl groups such as β-chloroethyl group, pentylfluoropropyl group, trifluoromethyl group, butyl iodide group, and propyl bromide group; N,N-diethylaminopropyl group; Examples include alkylaminoalkyl groups such as N,N-dimethylaminoethyl group; alkylthioalkyl groups such as ethylthiomethyl group, ethylthioethyl group, and phenylthiomethyl group.

Examples of alkoxy groups include methoxy group, ethoxy group,
Branched or straight-chain hydrocarbon oxy groups having 1 to 20 carbon atoms such as propoxy, butoxy, pentoxy, hexyloxy, heptyloxy, and octyloxy groups; methoxyethoxy, ethoxyethoxy, and propoxyethoxy groups , butoxyethoxy group, phenoxyethoxy group, methoxyethoxyethoxy group, ethoxyethoxyethoxy group, methoxyethoxyethoxyethoxy group, hydroxyethyloxy group, hydroxyethoxyethoxy group, etc. One formula R-(QC:HYI GHY2)-0-C formula where R is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, I/1
and Y2 are each independently a hydrogen atom, a methyl group, a chloromethyl group, an alkoxymethyl group, and n represents 1 to 5]; N,N-dimethylaminoethoxy group, N,N-diethylaminoethoxy basis,
Examples include fulkylaminoalkoxy groups such as N,N-dimethylpropyl groups: alkylthioalkoxy groups such as ethylthioethoxy groups, methylthioethoxy groups, phenylthioethoxy groups, methylthiopropoxy groups, and ethylthiopropoxy groups.

Examples of substituted or unsubstituted furkylthio groups include straight chain or branched hydrocarbon groups having 1 to 30 carbon atoms such as methylthio group and ethylthio group; methoxymethylthio group, methoxyethylthio group, ethoxyethylthio group; Oligoalkoxyalkylthio groups such as butoxyethylthio group and methoxyethoxyethylthio group; methylthiomethylthio group,
Oligoalkylthioalkylthio groups such as ethylthioethylthio groups; N,N-dimethylamineethylthio groups,
Alkylaminoalkylthio groups such as N,N-diethylaminoethylthio group and N-methylaminopropylthio group; Halogens such as chloroethylthio group, bromoethylthio group, iodized ethylthio group, fluorinated ethylthio group, and dichloroethylthio group Examples include alkylthio groups.

Examples of substituted or unsubstituted alkylamine groups or dialkylamino groups include methylamine group, ethylamino group,
N, N-dimethylamino group, N, N-diethylamino group, etc. linear or branched alkyl group-substituted amine group having a total of 1 to 30 carbon atoms; N-(hydroxyethyl)amino group, N,
N-di(hydroxyethyl)amino group, N,N-di(methoxyethyl)amino group, N,N-di(ethoxyethyl)amine group, N,N-di(methoxyethoxyethyl)amino group, N,N Examples include hydroxylalkylamino groups such as -di(acetoxyethyl)amino groups, alkoxyalkylamino groups, and acyloxyalkylamino groups.

Examples of the aryl group include substituted or unsubstituted phenyl derivatives such as phenyl group, naphthyl group, and tolyl group, naphthyl group derivatives, thiophene, oxazole, thiazole,
Thiadiazole, furan.

Examples include substituted or unsubstituted heterocycles such as virol, quinoline, and pyridine.

Examples of the aryloxy group include phenyloxy group, naphthyloxy group, alkylphenyloxy group, alkylaminophenyloxy group, halogen-substituted phenyloxy group, nitrophenyloxy group, alkoxyphenyloxy group, alkylthiophenyloxy group, etc. It will be done.

Examples of the arylthio group include a phenylthio group, a naphthylthio group, an alkylphenylthio group, an aminophenylthio group, an alkylaminophenylthio group, an alkoxyphenylthio group, and the like.

An example of an arylamino group is anilino group.

N-alkylanilino group, 7 alkylphenylami groups,
Examples include an alkoxyphenylamino group and an alkylaminophenylamino group.

When the substituent is only an alkyl group or an aryl group,
It is preferable that 8 or more alkyl or aryl groups are substituted, and in the case of only alkyloxy or aryloxy groups, it is preferable that 4 or more are substituted, and each substituent is connected. Good too.

The compound represented by formula (I) of the present invention is produced as follows. That is, the following formula (II) or (III) Ni? H [The benzene ring of formula (II) and formula (III) may be substituted with the same substituent as the benzene ring A-H of formula (I)] in an alkali alcohol. It is obtained by reacting a phthalocyanine alkali metal salt obtained by heating with an earth alkoxide and tetrachlortin, tetrachlorogermanium, tetrachlorosilicon or tetrachlorotitanium, or by reacting the compound (II) or (m) with tetrachlortin. Dichlorotin phthalocyanine, dichlorogermanium phthalocyanine, dichlortin phthalocyanine or dichlorotitanium phthalocyanine synthesized by reacting chlortin, tetrachlorogermanium, tetrachlorosilicon or tetrachlorotitanium in the presence of a base in quinoline as described above. Obtained by reacting with alkaline thalocyanine.

The method for producing an optical recording medium using the dye of the present invention includes:
There is a method of coating or vapor depositing a dye on a transparent substrate, and the coating method includes a binder resin of 20% by weight or less, preferably 0%, and a dye of 0.05% to 20% by weight, preferably 0.5% by weight. There is a method of dissolving it in a solvent to a concentration of ~20% by weight and applying it with a spin coater. Also, as a vapor deposition method, 106 to 10'torr, 100 to 30
There is a method of injecting a dye onto a substrate at 0°C.

The substrate may be any optically transparent resin. For example, acrylic resin, polyethylene resin, vinyl chloride resin, vinylidene chloride resin, polycarbonate 4N resin, ethylene resin, polyolefin copolymer resin, vinyl chloride copolymer resin, vinylidene chloride. Examples include copolymer resins and styrene copolymer resins.

Further, the substrate may be surface-treated with a thermosetting resin or an ultraviolet curable resin.

Coating solvents include halogenated hydrocarbons (eg, dichloromethane, chloroform, carbon chloride).

tetrachlorethylene, dichlorodifluoroethane, etc.)
, ethers (e.g., tetrahydrofuran, diethyl ether, etc.), ketones (e.g., acetone, methyl ethyl ketone, etc.), alcohols (e.g., methanol, ethanol, propatool, etc.), cellosolves (e.g.,
methyl cellosolve, ethyl cellosolve, etc.), hydrocarbons (hexane, cyclohexane, octane, benzene,
toluene, xylene, etc.) are preferably used.

〔Example〕

Example 1 260 parts by weight of 3-(p-tert-butylphenylthio)-phthalonitrile and 65 parts by weight of stannic chloride were reacted at 200°C for 3 hours in 1000 parts by weight of quinoline and 1000 parts by weight of tributylamine. After cooling to , it was discharged into 5000 parts by weight of methanol. Separate the precipitated crystals by filtration,
Methanol wash, dichlorotin phthalocyanine 10
0 parts by weight were obtained. On the other hand, 3-(p-tart-butylphenylthio)phthalonitrile 2 [10 parts by weight, N, N-
1000 parts by weight of dimethylaminoethanol, DBU20
0 parts by weight and 12 parts by weight of sodium were heated to reflux to produce sodium phthalocyanine in the system.

Subsequently, 200 parts by weight of the above-mentioned dichlorotin phthalocyanine was added, and the mixture was refluxed for 3 hours. The precipitated crystals were filtered off to obtain tin-shifthalodianine. Input maX near 40nm (
in CuCl2).

1 part by weight of the above tin sifthalodianine was added to chloroform.
It was dissolved in 00 parts by weight and spin-coded on a glass substrate. The obtained optical recording medium had high sensitivity. Further, the reflectance was 35% at 830 nm.

Example 2 Tin sifthalodianine was synthesized in the same manner as in Example 1 using 3.4,5.8-tetramethylphthalonitrile.* It was deposited on a polycarbonate substrate at 10-'' torr and 200°C. The recording medium had a reflectance of 35% and had good recording characteristics.

Example 3 Dichlorotin phthalocyanine was obtained in the same manner as in Example 1 using 3-ethoxyethoxyethoxyphthalonitrile. On the other hand, sodium phthalocyanine was synthesized in the system by heating and refluxing 3-ethoxyethoxyethoxyphthalonitrile in the presence of sodium in ethanol. Subsequently, the above-mentioned dichlorotin phthalocyanine was added, heated under reflux, and then the solvent was distilled off to obtain tin sifthalocyanine. Entering WaX (in ethyl cellosolve)
= 72Or+Otori.

This compound was dissolved in ethyl cellosolve and coated on a polycarbonate substrate to obtain an optical recording medium with a reflectance of 25%.
Met.

Example 4 3-(N,N-dioctylamino)phthalonitrile 30
0 parts by weight was reacted with 15 parts by weight of metallic sodium in ethanol to produce sodium phthalocyanine in the system. Subsequently, 30 parts by weight of stannic chloride was added, and the mixture was heated to reflux. After the solvent was distilled off, the residue was purified to obtain tin sifthalodianine. λ+max (in chloroform) = 8tOn layer.

Table 1 shows the results of the λWaX of the compounds obtained in Examples 1 to 4 and the durability and processability of optical recording media using them. was also shown.

O is good × represents defective.

Table-1 λwax Durability Processable wood V Invention example i 740 0 0 Comparative example 1 B2O0X 2 730 X Δ 3 7E10 0 Collection p 1519
(I987) Examples 5 to 40 Tin, silicon, and germanium were prepared in the same manner as in Example 4 using 1 to 8 intermediates of the following formula (ff) (intermediates represented by 1 to 32 in Table 2). Shiftalodianine was synthesized.

1 The λ layer ■ of the above compound obtained from different intermediates is shown in Table 3.
Optical recording media using these dyes shown in Figure 1 showed high reflectance and good sensitivity.

Table 3 Table 3 (Continued) [Effects of the Invention] The near-infrared absorber of the present invention is a compound with excellent durability and processability, and can be kneaded into resin or dyed. Optical recording media containing the agent have good durability and sensitivity.

Patent applicant: Mitsui Toatsu Chemical Co., Ltd. Yamaki Kasei Co., Ltd.

Claims (1)

[Claims] 1. The following formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) [In the formula (I), benzene rings A, B, C, D, E, F,
G and H may each be independently substituted with a substituted or unsubstituted alkyl group, alkoxy group, alkylthio group, alkylamino group, aryl group, aryloxy group, arylthio group, or arylamino group, [Met] ^4^+ represents tin, silicon, germanium, titanium] Diphthalocyanine near-infrared absorber and its tautomer. 2. The following formula (I) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (I) [In formula (I), benzene rings A, B, C, D, E, F,
G and H may each be independently substituted with a substituted or unsubstituted alkyl group, alkoxy group, alkylthio group, alkylamino group, aryl group, aryloxy group, arylthio group, or arylamino group, [Met] ^4^+ represents tin, silicon, germanium, and titanium] An optical recording medium containing a diphthalocyanine near-infrared absorber and a tautomer thereof in a recording layer.