JPH0615671B2 - Near infrared absorber and optical recording medium using the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial field of application] In recent years, an energy system utilizing light in the near infrared region,
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 photoconductors, optical cards, optical absorption of control mechanisms such as televisions and audio equipment, external near-infrared light blocking, protective glasses for laser processing, growth control by heat ray blocking, etc. Regarding compounds that can be made.

[Conventional technology]

Heretofore, as an optical information recording medium using a phthalocyanine compound, in JP-A-55-97033, a metal on a substrate,
The one having a recording layer composed of a metal oxide or a compound of a metal halide and a phthalocyanine is also disclosed in U.S. Pat. It is known to use dyes selected from phthalocyanines.

However, the recording layer using these phthalocyanine compounds alone has a defect that the absorption is weak in the long wavelength region and the recording sensitivity is poor.

Further, as an improved method thereof, JP-A-61-154888 and 61-146595
According to the publication, the introduction of heteroatoms such as sulfur, nitrogen, and selenium into the phthalocyanine ring made the wavelength longer. However, these compounds have insufficient film-forming properties and cannot be processed into stable optical recording media.

[Problems to be solved by the invention]

The present invention has been made to solve the above problems, and an object thereof is to provide a long-wavelength absorbing phthalocyanine compound which is excellent in durability, easy to process, and capable of obtaining an optical recording medium with few defects. To do.

[Means for solving problems]

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

That is, the present invention is a diphthalocyanine near-infrared absorber represented by the following formula (I) and a tautomer thereof, wherein two phthalocyanine rings are bonded to a tetravalent central element. .

[In the formula (I), benzene rings A, B, C, D, E, F,
G and H are each independently unsubstituted or unsubstituted or substituted with halogen, alkylthio, alkyl-substituted phenoxy, alkoxy, alkyl-substituted phenylthio, alkylamino group; unsubstituted or alkoxy, alkylamino, alkoxy Alkoxy group substituted with carbonyl; Alkylthio group unsubstituted or substituted with an alkoxy group; Alkylamino group unsubstituted or substituted with an alkoxy group; Phenyl group; Unsubstituted or alkyl substituted phenoxy group: Unsubstituted or alkyl substituted phenylthio Group; naphthylthio group: alkyl-substituted phenylamino group; may be substituted with a substituent selected from alkylene groups, and [Met] ⁴⁺ represents tin, silicon, or germanium. Another invention is an optical recording medium containing the same in a recording layer.

Examples of the substituted or unsubstituted alkyl group which may be substituted on each benzene ring of the compound represented by the formula (I) include a linear or branched alkyl group having 1 to 20 carbon atoms, preferably 1 to 12
A linear or branched alkyl group; methoxymethyl group, methoxyethyl group, methoxybutyl group, ethoxymethyl group,
Alkoxyalkyl groups such as butoxymethyl group, phenoxyethyl group, allyloxyethyl group, ethoxyethoxymethyl group, ethoxyethoxyethoxyethyl group; β
-Halogenated alkyl groups such as chloroethyl group, pentylfluoropropyl group, trifluoromethyl group, butyl iodide group and propyl bromide group; alkylamino such as N, N-diethylaminopropyl group and N, N-dimethylaminoethyl group Alkyl group; examples thereof include an alkylthioalkyl group such as an ethylthiomethyl group, an ethylthioethyl group, and a phenylthiomethyl group.

Examples of the alkoxy group include methoxy group, ethoxy group,
A branched or linear hydrocarbon oxy group having 1 to 20 carbon atoms such as a propoxy group, a butoxy group, a pentoxy group, a hexyloxy group, a heptyloxy group, an octyloxy group; a methoxyethoxy group, an ethoxyethoxy group, a propoxyethoxy group. An alkoxyalkoxy group such as a butoxyethoxy group, a methoxyethoxyethoxy group, an ethoxyethoxyethoxy group, a methoxyethoxyethoxyethoxy group;
Alkylaminoalkoxy groups such as N, N-dimethylaminoethoxy group, N, N-diethylaminoethoxy group and N, N-dimethylpropyl group; and the like.

Examples of the substituted or unsubstituted alkylthio group include a linear or branched hydrocarbon thio group having 1 to 30 carbon atoms such as methylthio group and ethylthio group; methoxymethylthio group, methoxyethylthio group, ethoxyethylthio group, butoxy. Oligothioalkyloxythio groups such as ethylthio group and methoxyethoxyethylthio group; and the like.

Examples of the substituted or unsubstituted alkylamino group or dialkylamino group include a methylamino group, an ethylamino group,
N, N-Dimethylamino group, N, N-diethylamino group and other linear or branched alkyl group-substituted amino groups having 1 to 30 carbon atoms; N, N-di (methoxyethyl) amino group, N, N- Examples thereof include alkoxyamino groups such as di (ethoxyethyl) amino group and N, N-di (methoxyethoxyethyl) amino group.

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

The compound of formula (I) of the present invention is produced as follows. That is, the following formula (II) or (III) [The benzene rings of the formulas (II) and (III) may be substituted with the same substituents as the benzene rings A to H of the above formula (I)]. It may be obtained by reacting an alkali metal salt of phthalocyanine obtained by heating with an alkoxide and tetrachlorotin, tetrachlorogermanium, tetrachlorosilicon or tetrachlorotitanium, or a compound of (II) or (III) and tetrachlorotin. , Dichlorotin phthalocyanine, dichlorogermanium phthalocyanine, dichlorosilicon phthalocyanine or dichlorotitanium phthalocyanine synthesized by reacting tetrachlorogermanium, tetrachlorosilicon or tetrachlorotitanium with quinoline in the presence of a base, and an alkali metal phthalocyanine described above. It is obtained by reacting with.

The method for producing an optical recording medium using the dye of the present invention,
There is a method of coating or vapor depositing a dye on a transparent substrate. As a coating method, the binder resin is 20% by weight or less, preferably 0%, and the dye is 0.05% by weight to 20% by weight, preferably 0.5%.
There is a method in which it is dissolved in a solvent so as to be from 20% by weight to 20% by weight and applied by a spin coater. As a vapor deposition method, there is a method of placing a dye on a substrate at 10 ^-5 to 10 ^-7 torr and 100 to 300 ° C.

The substrate may be any optically transparent resin. Examples thereof include acrylic resin, polyethylene resin, vinyl chloride resin, vinylidene chloride resin, polycarbonate resin, ethylene resin, polyolefin copolymer resin, vinyl chloride copolymer resin, vinylidene chloride copolymer resin, and styrene copolymer resin.

The substrate may be surface-treated with a thermosetting resin or an ultraviolet curable resin.

As the coating solvent, halogenated hydrocarbons (eg, dichloromethane, chloroform, carbon chloride, tetrachloroethylene, dichlorodifluoroethane, etc.), ethers (eg, tetrahydrofuran, diethyl ether, etc.), ketones (eg, acetone, methyl ethyl ketone, etc.) , Alcohols (eg, methanol, ethanol, propanol, etc.), cellosolves (methyl cellosolve, ethyl cellosolve, etc.), hydrocarbons (hexane, cyclohexane, octane, benzene, toluene, etc.)
Xylene) is 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 in 1000 parts by weight of quinoline and 1000 parts by weight of tributylamine at 200 ° C. for 3 hours to room temperature. After cooling to, the mixture was discharged into 5000 parts by weight of methanol.
The precipitated crystals were separated by filtration and washed with methanol to obtain 100 parts by weight of dichlorotin phthalocyanine. On the other hand, 3- (p-tert-
Butylphenylthio) phthalonitrile 260 parts by weight, N, N-
1000 parts by weight of dimethylaminoethanol, 200 parts by weight of DBU and 12 parts by weight of sodium were heated and refluxed to generate 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 out to obtain tin diphthalocyanine. λ max: 740 nm (in CHCl ₃ ).

1 part by weight of the above tin diphthalocyanine was added to 10 parts of chloroform.
It was dissolved in 00 parts by weight and spin-coated on a glass substrate.
The obtained optical recording medium had high sensitivity. The reflectance is 830
It was 35% in nm.

Example 2 Example 1 using 3,4,5,6-tetramethylphthalonitrile
Tin diphthalocyanine was synthesized in the same manner as in. 10 ^-10
A polycarbonate substrate was vapor-deposited at torr and 200 ° C. This optical 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-ethoxyethoxyethoxy-phthalonitrile. Meanwhile, sodium phthalocyanine was synthesized in the system by heating and refluxing 3-ethoxyethoxyethoxy-phthalonitrile in the presence of sodium in ethanol. Subsequently, the above-mentioned dichlorophthalocyanine was added and heated under reflux, and then the solvent was distilled off to obtain tin diphthalocyanine. λmax (in ethyl cellosolve) = 720 nm.

This compound was dissolved in ethyl cellosolve and applied on a polycarbonate substrate to obtain an optical recording medium. The reflectance was 25%.

Example 4 300 parts by weight of 3- (N, N-dioctylamino) phthalonitrile was reacted with 15 parts by weight of metallic sodium in ethanol,
Sodium phthalocyanine was formed in the system. Subsequently, 30 parts by weight of stannic chloride was added and the mixture was heated to reflux. After distilling off the solvent, purification was performed to obtain tin diphthalocyanine. λma
x (in chloroform) = 810 nm.

Table 1 shows the results of the λmax of the compounds obtained in Examples 1 to 4 and the durability and processability of optical recording media using these compounds. In the table, as a comparative example, known compound 3
The species is also shown.

○ means good, and × means bad.

1) JP-A-58-36490 2) Proceedings of the 54th Annual Meeting of the Chemical Society of Japan p1519 (1987) 3) JP-A-61-154888 Examples 5 to 40 Diphthalocyanines of tin, silicon and germanium were prepared in the same manner as in Example 4 using 1 to 8 intermediates of the following general formula (IV) (intermediates represented by 1 to 32 in Table 2). Was synthesized.

Table 3 shows the λ max of the above compounds obtained from different intermediates.
Shown in. Optical recording media using these dyes have high reflectance and good sensitivity.

[Effects of the Invention] The near-infrared absorber of the present invention is a compound having excellent durability and processability, and can be kneaded into a resin or dyed, and an optical recording medium containing this near-infrared absorber is durable. , The sensitivity is also good.

Front page continuation (72) Inventor Masakatsu Nakatsuka 2882 Iijima-cho, Sakae-ku, Yokohama-shi, Kanagawa Prefecture (72) Ken Enomoto 180 Tsukui, Yokosuka-shi, Kanagawa Prefecture

Claims (2)

[Claims] 1. The following formula (I) [In the formula (I), benzene rings A, B, C, D, E, F,
G and H are each independently unsubstituted or unsubstituted or substituted with halogen, alkylthio, alkyl-substituted phenoxy, alkoxy, alkyl-substituted phenylthio, alkylamino group; unsubstituted or alkoxy, alkylamino, alkoxy Carbonyl-substituted alkoxy group; unsubstituted or alkoxy-substituted alkylthio group; unsubstituted or alkoxy-substituted alkylamino group; phenyl group; unsubstituted or alkyl-substituted phenoxy group: unsubstituted or alkyl-substituted phenylthio group A naphthylthio group: an alkyl-substituted phenylamino group, which may be substituted with a substituent selected from an alkylene group, and [Met] ⁴⁺ represents tin, silicon or germanium. ] The diphthalocyanine near-infrared absorber shown by these, and its tautomer. 2. The following formula (I) [In the formula (I), benzene rings A, B, C, D, E, F,
G and H are each independently unsubstituted or unsubstituted or substituted with halogen, alkylthio, alkyl-substituted phenoxy, alkoxy, alkyl-substituted phenylthio, alkylamino group; unsubstituted or alkoxy, alkylamino, alkoxy Alkoxy group substituted with carbonyl; Alkylthio group unsubstituted or substituted with alkoxy group; Alkylamino group unsubstituted or substituted with alkoxy group; Phenyl group; Unsubstituted or alkyl substituted phenoxy group: Unsubstituted or alkyl substituted phenylthio Group; naphthylthio group: alkyl-substituted phenylamino group; may be substituted with a substituent selected from alkylene groups, and [Met] ⁴⁺ represents tin, silicon, or germanium. ] An optical recording medium containing a diphthalocyanine near-infrared absorber represented by and its tautomer in a recording layer.