KR930009258B1 - Liquid crystal element with near infrared absorbent - Google Patents

Abstract

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Description

Liquid crystal element containing a near infrared light absorber

The present invention relates to an ultra-infrared light absorber which plays an important role in the optoelectronic field such as information recording device, display sensor and protective glasses, and also includes an optical recording medium (including optical card), transmission and near-infrared filter (including glasses) and The present invention relates to a liquid crystal display device using near infrared rays.

Phthalocyanine as a near-infrared absorber as specified in Japanese Patent Laid-Open Publication No. 209, 583/1985, 152, 769/1986, 154, 888/1986, 197, 280/1986, 246, 091/1986 and 39, 286/1987. It is well known to use phthalocyanines, but these phthalocyanines are poorly absorbed because they are easy to combine. For this reason, in the case of an optical recording medium produced using such phthalocyanine, the reflectance at 780 to 830 mm is low, and the photosensitivity is also insufficient; In the case of a filter, the absorption spectrum is wide, so the selective transmission is bad; And in the case of liquid crystal display elements, the contrast is poor.

It is an object of the present invention to provide a novel near infrared light absorber which does not have the drawbacks mentioned above.

Another object of the present invention is to provide a method for producing a near infrared light absorber.

Another object of the present invention is to provide an optoelectronic material prepared using the above-mentioned near-infrared light absorber.

The inventors of the present application have made extensive studies to solve the above-mentioned problems and found that the novel phthalocyanine derivatives can be used as near-infrared light absorbers which achieve the above-mentioned object. That is, this invention relates to the near-infrared light absorber which has a molecular extinction coefficient of 200, 000 or more represented by general formula (I).

[Wherein Y ¹ , Y ² , Y ³ , Y ⁴ , Y ⁵ , Y ⁶ , Y ⁷ and Y ⁸ are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 15 carbon atoms, 4 to 15 Linear, branched or cyclic alkoxyl groups having 4 carbon atoms, linear, branched or cyclic alkylthio groups having 4 to 15 carbon atoms; Each combination of Y ¹ and Y ² , Y ³ and Y ⁴ , Y ⁵ and Y ⁶ , Y ⁷ and Y ⁸ is not a combination of a hydrogen atom, an alkyl group or an alkylthio group at the same time or a combination of an alkyl group and a hydrogen atom; A ¹ , A ² , A ³ , A ⁴ , A ⁵ , A ⁶ , A ⁷ and A ⁸ each represent a hydrogen atom, a halogen atom, a nitro atom, a straight or cyclic alkyl group having 1 to 10 carbon atoms, 7 to 20 Aralkyl group having 1 carbon atom, alkenyl group having 1 to 10 carbon atoms, alkynyl group having 1 to 10 carbon atoms, straight or branched alkoxyl group having 1 to 4 carbon atoms, or 6 to 10 carbon atoms Cyclic alkoxyl groups having atoms, aryloxy groups having 6 to 20 carbon atoms, straight chain, branched or cyclic alkylthio groups having 1 to 10 carbon atoms, or arylthio groups having 6 to 20 carbon atoms; Each pair of A ¹ and A ² , A ³ and A ⁴ , A ⁵ and A ⁶ , A ⁷ and A ⁸ combines with each other to form a ring. ; When A ¹ , A ² , A ³ , A ⁴ , A ⁵ , A ⁶ , A ⁷ and A ⁸ are all hydrogen and Y ¹ and Y ² , Y ³ and Y ⁴ , Y ⁵ and Y ⁶ and Y ⁷ and Y ⁸ each combination of a hydrogen atom and an alkoxyl group, the alkoxyl group has 4 to 9 carbon atoms and is branched or cyclic; And Met represents two hydrogen atoms, divalent metal atoms, trivalent and tetravalent substituted metal atoms or metal oxide groups.]

Moreover, the present invention relates to an optical card manufactured using the optical recording medium, the near infrared absorbing filters, the liquid crystal display element and the above-mentioned near infrared absorbing agent.

The near-infrared light absorber represented by the general formula (I) has a sharp absorption at 700 to 900 nm and a high molecular absorption coefficient, so that a semiconductor laser (optical disks and optical cards) and a near-infrared light absorption filter (laser reaction Elements, external light blocking filters and protective glasses), laser light recording or pass-through liquid crystal materials and blockers.

Now, a preferred embodiment of the present invention will be described.

In general formula (I), Y ¹ , Y ² , Y ³ , Y ⁴ , Y ⁵ , Y ⁶ , Y ⁷ and Y ⁸ are groups for preventing association between phthalocyanine molecules, and A ¹ , A ² , A ³ , A ⁴ , A ⁵ , A ⁶ , A ⁷ and A ⁸ consist of Y ¹ , Y ² , Y ³ , Y ⁴ , Y ⁵ , Y ⁶ , Y ⁷ and Y ⁸ extending vertically in the phthalocyanine ring It is for. Therefore, under the condition that the number of carbon atoms in Y ¹ , Y ² , Y ³ , Y ⁴ , Y ⁵ , Y ⁶ , Y ⁷ and Y ⁸ is the same, the side chain or the cyclic tries to have a higher reflectance and refractive index than the straight chain. .

Typical examples of the alkoxyl group represented by Y ¹ , Y ² , Y ³ , Y ⁴ , Y ⁵ , Y ⁶ , Y ⁷ and Y ⁸ are n-butyloxy group, iso-butyl oxy group, tert-butyl jade Period, secondary-butyloxy group, n-pentyloxy group, iso-pentyloxy group, neo-pentyloxy group, 1-methylbutyloxy group, 2-methylbutyloxy group, n-hexyloxy group, 2-ethyl Butyloxy group, 3-methylpentyloxy group, 4-tert-butylhexyloxy group, 1, 2-dimethylpropyloxy group, n-octyloxy group, n-nonyloxy group, n-dodecyloxy group and the like do. However, as a group having a large steric hindrance and extending vertically in the phthalocyanine ring to increase the absorbance per unit weight of the near-infrared light absorber, as a group to increase the photosensitivity in manufacturing an optical recording medium, and in the spin coating solvent As an effective group for increasing solubility, examples of particularly preferred alkoxyl substituents are iso-butyloxy group, iso-pentyloxy group, 1, 2-dimethylpropyloxy group, 2-ethylbutyloxy group, 1-ethylbutyloxy group , 1-ethyl-2-methylpropyloxy group, 1-iso-propyl-2-methylpropyloxy group, 2-ethylhexyloxy group, 1-iso-propyl-3-methylbutyloxy group, 3, 3, 5 -Trimethylhexyloxy group, 1-iso-butyl-3-methylbutyloxy group, cyclohexyloxy group, 2-methylcyclohexyloxy group, 2, 4-dimethylcyclohexyloxy group, etc. are mentioned.

Typical examples of the alkyl group represented by Y ¹ , Y ² , Y ³ , Y ⁴ , Y ⁵ , Y ⁶ , Y ⁷ and Y ⁸ include methyl group, ethyl group, propyl group, n-butyl group, iso-butyl group, 3 Tert-butyl group, secondary-butyl group, n-pentyl group, isopentyl group, neo-pentyl group, 1-methylbutyl group, 2-methylbutyl group, n-hexyl group, 2-ethylbutyl group, 3- Methylpentyl group, 2, 3-dimethylbutyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group, n-nonyl group, 2, 5, 5-trimethylhexyl group, n-decyl group, 4- Ethyloctyl group, 4-ethyl-4, 5-dimethylhexyl group, n-undecyl group, n-dodecyl group, 1, 3, 5, 7-tetramethyloctyl group, 4-butyloctyl group, 6, 6-di Ethyl octyl group, n-tridecyl group 6-methyl-4-butyloctyl group, n-tetradecyl group and n-pentadecyl group.

Typical examples of the alkylthio group include methylthio group, ethylthio group, n-propylthio group, iso-propylthio group, n-butylthio group, iso-butylthio group, tert-butylthio group and secondary-butyl Thiogi, n-pentylthio group, iso-pentylthio group, neo-pentylthio group, 1, 2-dimethylpropylthio group, n-hexylthio group, 1-ethyl-2-methylpropyl thio group, 2-ethyl Butylthio group, cyclohexylthio group, 2-methyl-1-iso-propylthio group, n-heptylthio group, 2-methylhexylthio group, 1-ethylpentylthio group, n-octylthio group, 2-ethyl Hexylthio group, 3-methyl-1-isopropylbutylthio group, n-nonylthio group, 3-methyl-1-isobutylbutylthio group, 3, 5, 5-trimethylhexylthio group, and 4-tertiary -Butylcyclohexylthio group, and the like.

Examples of the alkyl group represented by A ¹ , A ² , A ³ , A ⁴ , A ⁵ , A ⁶ , A ⁷ and A ⁸ include a methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, Iso-butyl group, tert-butyl group, n-pentyl group, iso-pentyl group, neo-pentyl group, n-hexyl group, cyclohexyl group, n-heptyl group, 1, 1-diethylpropyl group, n -Octyl group, n-nonyl group, n-decyl group, chloromethyl group, hydromethyl group, methoxymethyl group and methylthiomethyl group, but particularly preferred examples are methyl group, ethyl group, iso-propyl group, n-butyl group, iso- Butyl group and tert-butyl group.

Examples of the arylcal group include benzyl group, tert-butylbenzyl group, phenethyl group, 4-cyclohexylbenzyl group, naphthylmethyl group and the like.

Examples of alkenyl groups include allyl, crotyl and metallyl groups, and examples of alkynyl groups include ethynyl, propynyl and phenylethynyl.

Examples of the alkoxyl group are methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, n-butoxy group, iso-butoxy group, tert-butoxy group, n-butoxy group, iso-pentoxy group, neo -Pentoxy group, n-hexyloxy group, iso-hexyloxy group, neo-hexyloxy group, cyclohexyloxy group, heptyloxy group, n-octyloxy group, n-nonyloxy group, n-decyloxy group, etc. have.

Examples of the aryloxy group include a phenoxy group, a 4-tert-butylphenyloxy group and a naphthyloxy group.

Examples of the alkylthio group include methylthio group, ethylthio group, n-propylthio group, iso-propylthio group, n-butylthio group, iso-butylthio group, n-pentylthio group, iso-pentylthio group and Neo-pentylthio group and the like.

Examples of the arylthio group include a phenylthio group, a 4-tert-butylphenylthio group, a naphthylthio group, and the like.

When each pair of A ¹ and A ² , A ³ and A ⁴ , A ⁵ and A ⁶ and A ⁷ and A ⁸ may be combined with one another, the following groups are formed:

-N = CH-CH = CH-, -O-CH ₂ CH ₂ -O-, -S-CH ₂ CH ₂ -S-, -NH-CH ₂ CH ₂ -S-,

-CH ₂ CH ₂ CH ₂ CH ₂ -and -CH ₂ CH [C (CH ₃ ) ₃ ] CH ₂ CH _2- .

Examples of halogens include fluorine chlorine, bromine, iodine and the like.

Furthermore, examples of the divalent metal represented by Met in General Formula (I) include Cu (II), Zn (II), Fe (II), Co (II), Ni (II), Ru (II), and Rh. (II), Pd (II), Pt (II), Mn (II), Mg (II), Ti (II), Be (II), Ca (II), Ba (II), Cd (II), Hg (II), Pb (II), Sn (II), etc .; Monovalent trivalent metals include Al-Cl, Al-Br, Al-F, Al-I, Ga-Cl, Ga-F, Ga-I, Ga-Br, In-Cl, In-Br, In -I, In-F, Tl-Cl, Tl-Br, Tl-I, Tl-F, Al-C ₆ H ₅ , Al-C ₆ H ₄ (CH ₃ ), In-C ₆ H ₅ , In- C ₆ H ₄ (CH ₃ ), In—C ₁₀ H _7, Mn (OH), Mn (OC ₆ H ₅ ), Mn [Osi (CH ₃ ) ₃ ], FeCl, RuCl, and the like.

2 to divalent metal for example, substituted 4 _{CrCl 2, SiCl 2, SiBr 2} , SiF 2, SiI 2, ZrCl 2, GeCl 2, GeBr 2, GeI 2, GeF 2, SnCl 2, SnBr 2, SnI 2, SnF _{2, TiCl 2, TiBr 2,} TiF 2, Si (OH) 2, Ge (OH) 2, Zr (OH) 2, Mn (OH) 2, Sn (OH) 2, TiR 2, CrR 2, SiR 2, SnR ₂ , GeR ₂ (wherein R is an alkyl group, phenyl group, naphthyl group or derivatives thereof), Si (OR ′) ₂ , Sn (OR ′) ₂ , Ge (OR ′) ₂ , Ti (OR ′) ₂ , Cr (OR ′) ₂ (wherein R ′ is an alkyl group, phenyl group, naphthyl group, trialkylsilyl group, dialkylalkoxysilyl group or derivatives thereof), Sn (SR ″) ₂ and Ge (SR ″) ₂ ( Is an alkyl group, a phenyl group, a naphthyl group or a derivative thereof.

Examples of oxymetal groups include VO, MnO and TiO.

The above mentioned groups are preferable as the groups represented by Y ¹ , Y ² , Y ³ , Y ⁴ , Y ⁵ , Y ⁶ , Y ⁷ and Y ⁸ because they make the surface of each protalocyanine ring perpendicular and It is indicative of the function of steric hindrance. Therefore, in the case of alkyl groups, the latter has at least one carbon atom, preferably at least four carbon atoms; In the case of alkoxyl groups, the latter has four or more carbon atoms and is preferably branched or cyclic; And in the case of alkylthio groups the latter has one or more carbon atoms. On the other hand, the upper limit of the size of the group must be determined in consideration of the fact that the light absorption capacity per unit volume decreases if the ratio of chromophores in a certain volume is low. So with regard to alkyl groups, the upper limit of the number of carbon atoms is 15, preferably 10; The upper limit of the number of carbon atoms with respect to the alkoxyl group is 15, preferably 9.

Furthermore, A ¹ , A ² , A ³ , A ⁴ , A ⁵ , A ⁶ , A ⁷ and A ⁸ are Y ¹ , Y ² , Y ³ , Y ⁴ , Y extending vertically in the protalcyanine ring ^And groups assisting ⁵ , Y ⁶ , Y ⁷ and Y ⁸ . Likewise, the sizes of A ¹ , A ² , A ³ , A ⁴ , A ⁵ , A ⁶ , A ⁷ and A ⁸ must be determined in order not to reduce the absorbance capacity per unit volume. Preferably, the alkyl group, aralkyl group, alkenyl group, alkynyl group, alkoxyl group or alkalthio group has 1 to 4 carbon atoms when straight and 4 to 6 carbon atoms when branched or cyclic. Aryloxy groups such as phenyloxy groups, naphthyloxy groups or 4-tert-butylphenoxy groups preferably have 6 to 10 carbon atoms. Furthermore, arylthio groups such as phenylthio groups, 4-tert-butylphenylthio groups, naphthylthio groups or 2-methylphenylthio groups preferably have 6 to 10 carbon atoms.

The near-infrared light absorber of the present invention is an alkoxyl group having 4 to 15 carbon atoms, preferably 4 to 9 carbon atoms. -Position substituents Y ¹ , Y ² , Y ³ , Y ⁴ , Y ⁵ , Y ⁶ , Y ⁷ and Y ⁸ , in that they are introduced to successfully inhibit the phthalocyanine compounding by steric hindrance of the introduced groups Are characterized.

The compound represented by general formula (I) mixes 1-4 types of a compound which has general formula (II) or (III) first,

[The benzel ring in the formula may have a substituent as mentioned with respect to general formula (I).]

The mixture is then thermally reacted with the metallic derivative in the presence of, for example, 1, 8-diazo bicyclo [5, 4, 0] -7-undecyl (DBU) in alcohol, or alternatively chloronaphthalene, bromonaphthalene Or by reacting a mixture with a metallic derivative in a ring-point solvent such as trichlorobenzene.

The preparation of the optical record carrier using the near infrared absorber of the present invention can be accomplished by a method comprising the step of applying or depositing the near infrared absorber into a transparent organ. In the application method, the binder resin and the near infrared absorber are dissolved in a solvent so that the concentration of the binder resin and the near infrared absorber is 20% by weight or less, preferably 0%, i.e., absence and 0.05 to 20% by weight, preferably 0.5 to 20% by weight. The application may then be done in% using a spin coater. Moreover, in the above-mentioned precipitation method, the near infrared absorber is precipitated on the substrate under 10 ^-5 to 10 ^-7 Torr of 100 to 300 ° C.

However, the application method using the spin coater and the immersion method is preferable for the purpose of applying to the near-infrared light absorber according to the present invention which is superior to that of the conventional light absorber, and in particular, the method of applying only the near-infrared light absorber of the present invention is best. to be. The optical recording medium may be a worm (WORM) type or a CD-worm type (CD-WORM) type. The worm-type recording medium can be produced only by depositing the recording layer containing the near-infrared light absorber of the present invention on a substrate, and the CD-worm recording medium first deposits the recording layer on the substrate, and then a reflective layer containing gold or aluminum therein. It can be produced by superimposing and finally, protective layer with resin.

The substrate can be made from a visually clear resin. Examples of such resins are acrylic resins, polyethylene resins, vinyl chloride resins, vinylidene chloride resins, polycarbonate resins, ethylene resins, polyolefin copolymer resins, vinyl chloride copolymer resins, vinylidene chloride copolymer resins and styrene copolymers. There is a resin.

Moreover, the substrate may be a surface treated with a heat set resin or an ultraviolet set resin.

In the manufacture of optical recording media (optical disks and optical cards), it is preferable to use a spin coating technique, using a polyacrylate or polycarbonate substrate, in view of price and user's operation. .

In consideration of solvent resistance to the substrate, it is preferable to use a solvent having a lower polarity than carbon tetrachloride in the spin coating step. Examples of such solvents which are preferably used include hydrocarbon halides (e.g. dichloromethane, chloroform, carbon chloride, tetrachloroethylene, dichlorodifluoroethane), ethers (e.g. tetrahydrofuran and diethyl ether), ketones (e.g. acetone And methylethyl ketone), alcohols (eg methanol, ethanol and propanol), cellosolves (methylcellosolve and ethylcellosolve), and hydrocarbons (hexane, cyclohexane, octane, benzene, toloene and xylene) have.

In the manufacture of filters, the near-infrared light absorbent compound represented by formula (I) must have heat resistance so that the compound can be kneaded with the resin and the resin substrate can be dyed in a solvent in terms of cost and workability. It also requires that. Moreover, the molded article, for example the manufactured filter, must possess sharp absorbance and high absorbance.

A technique for producing a near-infrared light absorbing filter using a compound having formula (I) or a derivative thereof, the method comprising mixing a near-infrared light absorber of formula (I) with a resin and then molding a mixture; Mixing the near-infrared light absorber of general formula (I) with the resin unit and then molding-polymerizing the mixture; Dyeing the molded resin with a near-infrared light absorber of the general formula (I); And applying or precipitating a near infrared light absorber of general formula (I) to the surface of the substrate material.

The resin which can be used as the filter base material is preferably transparent. Examples of such preferred resins include thermoplastic resins such as polystyrene, polymethylmethacrylate, polycarbonate, polyethylene and polypropylene; And CR-39 (trade name; manufactured by PPG Co., Ltd.), MR-3 (trade name; manufactured by Mitsui Toatsu Chemical Co., Ltd.), MR-6 (trade name; manufactured by Mitsui Toatsu Chemical Co., Ltd.) Such as heat-setting resins.

Moreover, when the near-infrared light absorber of the present invention is used as a display material with a liquid crystal, the light absorber should be very melt in the liquid crystal, and the light absorber does not interfere with this change in the liquid crystal when the liquid crystal state is changed by applying an electric field or heat there. It is essential to avoid.

In the case of manufacturing the display material, examples of useful liquid crystals include nematic liquid crystals, smectic liquid crystals, and cholesteric liquid crystals. As the display technology, there are a customer / master display system and a liquid crystal panel system (near infrared light absorber is applied to the liquid crystal, and then an image is recorded using a laser beam).

The present invention will now be described in detail with reference to examples.

Example 1

906 parts of phthalonitrile derivative represented by the following structural formula (II-1), 79 parts of cuprous chloride, 1,8-diazabicyclo- [5, 4, 0] -7-undecene 608 parts, and n- The mixture of 7500 parts of amyl alcohol was heated to reflux for 5 hours:

The methyl alcohol was then added to the reaction solution obtained to precipitate the crystals, the latter was collected by absorption filtration and then purified through a column (silica gel / toluene) to form a phthalocyanine compound 600 represented by the following structural formula (I-1). Part (yield 60%) was obtained ( max 738 nm / hexane; max 227, 000):

Atomic analysis (as CuC ₉₆ H ₁₃₆ N ₈ O ₈ Cl ₈ ):

Calculated (%): C; 61.42, H; 7.30, N; 5.97, Cl; 15.11

Measured value (%): C; 61.20, H; 7.27, N; 5.93, Cl; 15.09

One part of Compound (I-1) obtained in 100 parts of n-octane was dissolved and the solution was then added to the polycarbonate optical disc substrate. The optical disk thus obtained had a reflectance of 29% and a photosensitivity of 50 dB at 8 mW, 700 nm and a direct speed of 5.5 m / sec.

Furthermore, 7 parts of the compound (I-1) was mixed with 1000 parts of the cyano-biphenyl liquid crystal mixture to prepare a liquid crystal panel. When the image was drawn over this panel using a laser beam, it was clearly visible there.

Example 2

A mixture of 320 parts of phthalonitrile derivative represented by Structural Formula (II-1), 75 parts of acetylacetone vanadium, 214 parts of DBU, and 2,700 parts of n-amyl alcohol was heated to reflux for 10 hours. After distilling off the solvent, the residue was purified through a column (toluene) to obtain 37 parts (yield 11%) of the phthalocyanine compound represented by the following structural formula (I-2) ( max 762 nm / hexane; max 220, 000):

Elemental analysis (as VC ₉₆ H ₁₃₆ N ₈ O ₉ Cl ₈ ):

Calculated (%): C; 61.31, H: 7.29, N: 5.96, Cl: 15.08

Measured value (%): C; 61.27, H: 7.25, N; 5.90, Cl: 15.06

The solution obtained after dissolving 15 parts of phthalocyanine represented by the general formula (I-2) in 1,000 parts of n-octane was applied to a polycarbonate optical disk substrate. The optical disk thus obtained had a reflectance of 27% and 50 dB photosensitivity (C / N ratio) at 8 mW, 780 nm and 5.5 m / sec linear speeds.

Further, 1 part of the compound (I-2) was dissolved in 100 parts of a liquid crystal mixture having the following formula to prepare liquid crystal phenyl.

When the image was drawn on this panel using a laser beam, it was clearly visible there.

Example 3

The mixture of 368 parts of phthalonitrile derivative represented by the following structural formula (II-2), 44 parts of 90% cuprous chloride, DBU 304 parts, n-aryl alcohol 3, 100 parts was heated to reflux for 5.5 hours.

Next, the obtained reaction solution was added to 3200 parts of methyl alcohol, followed by absorption filtration. The crystals thus obtained were purified by passing through a column (silica gel / hexane: toluene = 1: 1) to obtain 220 parts (yield 57%) of the phthalocyanine compound represented by the following structural formula (I-3) ( max 778 nm / hexanes: max 234, 000):

Elemental analysis (as CuC ₇₂ H ₈₈ N ₈ O ₈ Cl ₈ ):

Calculated (%): C; 56.13, H: 5.76, N: 7.27, Cl: 18.41

Measured value (%): C; 56.02, H: 5.80, N: 7.24, Cl: 18.34

1 part of the above-mentioned compound (I-3) was dissolved in 100 parts of dibutyl ether and the solution obtained was then applied to a polycarbonate optical disk substrate. The optical disk thus obtained had a reflectance of 39% and 51 dB photosensitivity at 8 mW, 780 nm and 5.5 m / sec linear speeds.

Further, 7 parts of the compound (I-3) was dissolved in 1,000 parts of a cyano biphenyl liquid crystal mixture to prepare liquid crystal phenyl. When the image was drawn on this panel using a laser beam, it was apparent there.

One part of the above-mentioned compound (I-3) was dissolved in 100 parts of n-octane, and the resulting solution was applied onto a polycarbonate optical card substrate. Thereafter, the applied substrate was protected with a resin to prepare an optical card. The optical card thus obtained had a reflectance of 39% and 50 dB photosensitivity at a linear speed of 8 mW, 780 nm, 2.8 m / sec. The durability of this card was good.

Four parts of the above-mentioned compound (I-3) were mixed with 1000 parts of polystyrene resin under heating and then molded into a plate. The filter thus prepared sufficiently absorbed light at 750-850 nm.

[Comparative Examples 1 to 3]

In each comparative example, the following known compounds were used. In Table 1, the results of the above examples are compared with the comparative examples in terms of the maximum absorption wavelength (λ max) in the solution state of each compound, the molecular extinction coefficient (ε), solubility, maximum reflectance and photosensitivity at that wavelength.

In Comparative Example 1:

Typical compound 4 in Japanese Patent Laid-Open No. 152, 769/1986:

Insoluble in n-octane, these compounds were dissolved in chloroform and then the resulting solution was applied to 2P substrates. The media so obtained were then evaluated.

In Comparative Example 2:

Compounds of Example 1 of Japanese Patent Application Laid-Open No. 209, 583/1985:

Insoluble in n-octane, this compound was dissolved in chloroform and then the resulting solution was applied onto a 2P substrate. The media so obtained were then evaluated.

In Comparative Example 3, typical compound 10 of Japanese Patent Laid-Open Publication No. 197, 280.1986: Deca (-OC ₅ H ₁₁ ) -H ₂ PC The carbon tetrachloride solution of this compound was added to a 2P substrate with a carbon solution, Evaluated.

With regard to the items to be measured, the measurement process and expression of the measured results are as follows:

1. the maximum absorption wavelength at its wavelength ( max) and molecular extinction coefficient

Each of these items was measured at a concentration of 5 mg / l of n-hexane or chloroform.

2. Solubility:

Solubility is as follows.

○: When dissolved in less than 5g / ℓ in n-hexane

: less than 5g / l in n-hexane and more than 5g / l in carbon tetrachloride and

X: when dissolved in carbon tetrachloride or less than 5 g / l

3. Maximum reflectance:

The maximum reflectance was first applied with a 5 g / l n-hexane solution on each polycarbonate substrate using a spin coater followed by irradiation of the applied substrate at 780 nm.

4. Sensitivity:

The photosensitivity was obtained from the C / N ratio when recording was made by semiconductor light beams of 780 nm, 8 mW and 5.5 m / sec linear speed.

40dB or more,

40 to 30 dB and

×: 30dB or less

TABLE 1

Example 4

A mixture of 4, 11 parts of phthalonitrile derivative represented by the following formula (II-3), 0.44 parts of cuprous chloride, DB4 3.04 parts, and 37.5 parts of n-amyl alcohol was heated at reflux for 5 hours:

The obtained reaction solution was poured into 400 parts of methyl alcohol to precipitate crystals, the latter was collected by absorption filtration and purified through a column (silica gel / hexane: toluene = 5: 2) according to the following structural formula (I-4). 2.50 parts of the shown phthalocyanine compound and the isomer thereof were obtained (λmax 742 nm / hexane; εmax2.3 × 10 ⁵ ):

Elemental analysis results (as CuC ₈₄ H ₁₁₂ N ₈ Cl ₈ O ₈ ):

Calculated (%): C; 59.03, H; 6.61, N; 6.56, Cl; 16.60

Measured value (%): C; 58.98, H; 6.63, N; 6.54, Cl; 16.55

Next, 5 parts of the obtained phthalocyanine derivative (I-4) were mixed with 1,000 parts of polystyrene resin under heating and then molded into a plate. The filter thus obtained sufficiently absorbed light at 750-850 nm.

Furthermore, 1 part of phthalocyanine (I-4) was dissolved in 100 parts of the liquid crystal mixture having the following formula, and then a liquid crystal panel was prepared using a solution.

When the image was recorded on this panel using a laser beam, it was apparent there.

Example 5

A mixture of 4.26 parts of phthalonitrile derivative represented by the following formula (II-4), 0.53 parts of cuprous chloride, 3.65 parts of DBU and 45.0 parts of n-amyl alcohol was heated under lubrication for 6 hours:

The obtained reaction mixture was added to 500 parts of methyl alcohol to precipitate crystals, and the latter was collected by absorption filtration and purified through a column (silica gel / hexane: toluene = 5: 3) to be represented by the following structural formula (I-5). 2.50 parts (yield 56%) of gin phthalocyanine compound was obtained ( max 739 nm / hexane; max 2.5 × 10 ⁵ ):

Elemental analysis (as Cu C ₆₈ H ₈₀ N ₈ Cl ₈ O ₈ ):

Calculated (%): C; 55.01, H; 5.43, N; 7.55, Cl; 19.10

Measured value (%): C; 54.98, H; 5.44, N; 7.53, Cl; 19.07

Next, 4 parts of the obtained phthalocyanine derivative (I-5) was mixed with 1000 parts of polystyrene resins under heating, and then molded into a plate. The filter so obtained absorbed light sufficiently at 750-850 nm.

Furthermore, 7 parts of phthalocyanine (I-5) was dissolved in 1000 parts of cyanobiphenyl liquid crystal mixture, and then a liquid crystal panel was prepared using a solution. When the image was recorded on the panel using this laser beam, it appeared clearly there.

Example 6

A mixture of 4.43 parts of phthalonitrile derivative represented by the following structure (II-5), 0.53 part of cuprous chloride, 3.65 parts of DBU and 45.0 parts of n-amyl alcohol was heated under reflux for 6 hours:

The obtained reaction mixture was precipitated from 500 parts of methyl alcohol, the latter was collected by absorption filtration, and then purified through a column (silica gel / hexane: toluene = 5: 2) to obtain the reaction mixture represented by the following structural formula (I-6). 2.45 parts (yield 53%) of phthalocyanine compounds and the isomers thereof were obtained ( max 739nm / hexane: max 2.42 × 10 ⁵ ):

Elemental analysis results (as Cu C ₈₀ H ₁₀₄ N ₈ Cl ₈ O ₈ ):

Calculated (%): C; 58.13, H; 6.34, N; 6.78, Cl; 17.16

Measured value (%): C; 58.90, H; 6.26, N; 6.83, Cl; 17.30

Next, 5 parts of the obtained phthalocyanine derivative (I-6) was mixed with 1000 parts of polystyrene resin under heating and then molded into a plate. The filter thus obtained sufficiently absorbed light at 750-850 nm.

Furthermore, 8 parts of phthalocyanine (I-6) was dissolved in 1000 parts of cyanobiphenyl liquid crystal mixture, and then a liquid crystal panel was prepared using a solution. When the image was recorded on this panel using a laser beam, it was apparent there.

Example 7

A mixture of 4.06 parts of phthalonitrile derivative, 0.53 parts of cuprous chloride, DB2 3.65 parts and 45.0 parts of n-amyl alcohol represented by the following formula (II-6) was heated under reflux for 7 hours:

The obtained reaction mixture was poured into 500 parts of methyl alcohol to precipitate crystals, the latter was filtered through absorption and then purified through a column (silica gel / hexane: toluene = 5: 2) to form a phthalocyanine compound represented by the following structural formula (I-7). 2.63 parts (yield 55%) and its isomers were obtained (λ max 739 nm / hexane; ε max 2.4 × 10 ⁵ ):

Elemental analysis results (as Cu C ₇₆ H ₉₆ N ₈ Cl ₈ O ₈ ):

Calculated (%): C; 57.17, H; 6.06, N; 7.06, Cl; 17.76

Measured value (%): C; 57.15, H; 6.09, N; 7.00, Cl; 17.73

Next, 5 parts of the obtained phthalocyanine derivative (I-7) was mixed with 1000 parts of polystyrene resin under heating and then molded into a plate. The filter so obtained absorbed light sufficiently at 750-850 nm.

Furthermore, 8 parts of phthalocyanine (I-7) was dissolved in 1000 parts of a cyano biphenyl liquid crystal mixture, and then a liquid crystal panel was prepared using a solution. When images were recorded on this panel using laser beams, they were clearly visible there:

Example 8

A mixture of 4.26 parts of phthalonitrile derivative, 0.53 parts of cuprous chloride, 3.65 parts of DBU and 45.0 parts of n-amyl alcohol shown in the following formula (II-7) was heated under reflux for 7 hours:

The obtained reaction mixture was poured into 500 parts of methyl alcohol to precipitate crystals, and the latter was filtered through absorption and then purified through a column (silica gel / hexane: toluene = 5: 2) to form a phthalocyanine compound represented by the following structural formula (I-8). 2.10 parts (yield 57%) were obtained (λmax 742 nm / hexane; εmax 2.23 × 10 ⁵ ):

Elemental analysis (as Cu C ₆₈ H ₈₀ N ₈ Cl ₈ O ₈ ):

Calculated (%): C; 55.01, H; 5.43, N; 7.55, Cl: 19.10

Measured value (%): C; 54.97, H; 5.45, N; 7.52, Cl: 19.08

Next, 4 parts of the obtained phthalocyanine derivative (I-8) was mixed with 1000 parts of polystyrene resin under heating and then molded into a plate shape. The filter so obtained absorbed light sufficiently at 750-850 nm.

Furthermore, 7 parts of phthalocyanine (I-8) was dissolved in 1000 parts of cyano biphenyl liquid crystal mixture, and then a liquid crystal panel was prepared using a solution. When images were recorded on this panel using laser beams, they were clearly visible there:

Furthermore, 1 part of phthalocyanine (I-8) was dissolved in 100 parts of dibutyl ether, and then the obtained solution was applied to a polycarbonate optical card substrate. The recording layer obtained after that was a protective film with resin to manufacture an optical card. The card so produced had a reflectance of 35% and a sensitivity of 50 dB (C / N ratio) at 780 nm, 8 mW and 2.8 m / sec linear speed. Moreover, the durability of the card was also good.

Example 9

A mixture of 43 parts of SiCl ₄ and 3000 parts of quinoline was heated to 200 ° C. To this mixture was added to 386 parts of diimino iso indoline derivative represented by the following structural formula (III-1) and the solution was heated at reflux for 5 hours:

The obtained reaction solution was poured into 500 parts of methyl alcohol to precipitate crystals. The latter was collected by absorption filtration, washed with methanol and dried to thereby give 157 parts of phthalocyanine compound represented by the following structural formula (I-9) (yield 40). %) Was obtained (λmax 740 nm / hexane; εmax 2.4 × 10 ⁵ )

Elemental analysis (as Si C ₇₂ H ₈₈ N ₈ O ₈ Cl ₁₀ ):

Calculated (%): C; 54.87, H; 5.63, N; 7.11, Cl; 22.49

Measured value (%): C; 54.69, H; 5.59, N; 7.09, Cl; 22.36

One part of the obtained compound (I-9) was then dissolved in 100 parts of diburyl ether and the obtained solution was applied to a polycarbonate optical disc substrate. The optical disk thus obtained had a reflectance of 36% and 51 dB photosensitivity (C / N ratio) at 780 nm, 8 mW and 5.5 m / sec linear speed.

Furthermore, 7 parts of phthalocyanine (I-9) was dissolved in 1000 parts of cyano biphenyl liquid crystal mixture, and then a liquid crystal panel was prepared using a solution. When the image was recorded on this panel using a laser beam it was clearly visible there.

Furthermore, 1 part of compound (I-9) was dissolved in 100 parts of dibutyl ether, and then the obtained solution was applied to a polycarbonate optical card substrate. The obtained recording layer was then protected with a resin to prepare an optical card. The card so produced had a reflectance of 36% and 51 dB photosensitivity (C / N ratio) at 780 nm, 8 mW and 2.8 m / sec linear speed.

Next, 4 parts of the obtained compound (I-9) were mixed with 1000 parts of polystyrene resin under heating and then molded into a plate. The filter thus obtained sufficiently absorbed light at 750 to 850 nm.

[Examples 10 to 44]

The phthalocyanine shown in Table 4 is a metal derivative of 1 to 4 types of phthalonitrile (Table 2) represented by the following general formula (II) or diiminoisoindolin (Table 3) represented by the following general formula (III): Reacted with and synthesized. Synthesized compounds have a large molecular extinction coefficient and when optical recording media were prepared from these compounds they were also excellent in reflectance, photosensitivity and durability:

Table 2 (Ⅰ) (Ⅱ)]

TABLE 3

Table 4 (Ⅰ) a]

Table 4 (I) b]

Example 45

A mixture of 240 parts of phthalonitrile derivative, 18 parts of cuprous chloride, 122 parts of DBU and 1500 parts of n-amyl alcohol represented by the following formula (II-33) was heated under reflux for 5.5 hours.

Subsequently, methyl alcohol was added to the obtained reaction solution to precipitate crystals, the latter was collected by absorption filtration, and then purified through a column (hexane: benzene = 1: 1) to form a phthalocyanine compound represented by the following structural formula (I-45). 140 parts (yield 60%) were obtained ((lambda) max 778 nm / hexane; (epsilon) max 2.8x10 <^5> ):

Elemental analysis results (as Cu C ₁₄₄ H ₁₇₆ N ₈ O ₈ S ₈ ):

Calculated (%): C; 70.11, H; 7.19, N; 4.54, Cl; 10.40

Measured value (%): C; 70.08, H; 7.13, N; 4.52, Cl; 10.36

Next, 1 part of the obtained phthalocyanine compound (I-45) was mixed with 100 parts of n-octane and the obtained solution was applied on a polycarbonate optical card substrate. Subsequently, the applied substrate was protected with a resin to prepare an optical card. The cards so produced had photosensitivity of 33% reflectivity, 830 nm, 8 mW and 2.8 m / sec linear speed. In addition, the durability of the card was also good.

Furthermore, 4 parts of compound (I-45) were mixed under heating with 1000 parts of polystyrene resin, and the mixture was molded into a plate shape. The filter thus obtained sufficiently absorbed light at 750-850 nm.

Example 46

A mixture of 120 parts of phthalonitrile derivative represented by structural formula (II-33), 22 parts of acetyl acetone vanadium, 61 parts of DBU, and 750 parts of n-amyl alcohol was heated under reflux for 12 hours. The residue obtained after the solvent was distilled off was then purified through column (toluene) to obtain 19 parts (yield 15%) of the phthalocyanine compound represented by the following structural formula (I-46) (λmax 809 nm / hexane; εmax 2.4 × 10 ⁵ ):

Elemental analysis results (as VC ₁₄₄ H ₁₇₆ N ₈ O ₉ S ₈ ):

Calculated (%): C; 70.01, H; 7.18, N; 4.54, S; 10.38

Measured value (%): C; 69.96, H; 7.14, N; 4.50, S; 10.36

Example 47

A mixture of 280 parts of phthalonitrile derivative, 18 parts of cuprous chloride, 122 parts of DBU and 1500 parts of n-amyl alcohol represented by the following structural formula (II-34) was heated under reflux for 5.5 hours:

Subsequently, methyl alcohol was added to the obtained reaction solution to precipitate crystals, the latter was collected by absorption filtration, and then purified through a column (toluene), 190 parts (yield 66%) of the phthalocyanine compound represented by the following structural formula (I-47). (Λmax 787 nm / chloroform; εmax 2.47 × 10 ⁵ ) was obtained:

Elemental analysis results (as Cu C ₁₇₆ H ₁₉₂ N ₈ O ₈ S ₈ ):

Calculated (%): C; 73.72, H; 6.75, N; 3.91, S; 8.95

Measured value (%): C; 73.66, H; 6.72, N; 3.88, S; 8.91

Example 48

A mixture of 140 parts of phthalonitrile derivative represented by Structural Formula (II-34), 22 parts of acetyl acetone vanadium, 61 parts of DBU and 750 parts of n-amyl alcohol was heated under reflux for 12 hours. After distilling off the solvent, the obtained residue was purified through a column (toluene) to obtain 35 parts (yield 25%) of a phthalocyanine compound represented by the following structural formula (I-48) (λmax 815 nm / hexane; εmax 2.4 × 10 ⁵ ):

Elemental analysis (as VC ₁₇₆ H ₁₉₂ N ₈ O ₉ S ₈ ):

Calculated (%): C; 73.63, H; 6.74, N; 3.90, S; 8.93

Measured value (%): C; 73.58, H; 6.71, N; 3.86, S; 8.87

Example 49

The mixture was heated under reflux for 5 hours under a mixture of 413 parts of phthalonitrile derivative represented by the following formula (II-35), 22 parts of 90% cuprous chloride, DBU 244 parts, and 2,500 parts of n-amyl alcohol.

The reaction solution obtained was then poured into 400 parts of methyl alcohol and crystals were precipitated. The latter was collected by absorption filtration, and then the column (silica gel / hexane: toluene = 1: 1) was dissolved and purified to obtain 260 parts (yield 61%) of a phthalocyanine compound represented by the following structural formula (I-49) (λmax 778 nm / Hexane; εmax 2.5 × 10 ⁵ ):

Elemental analysis results (as CuC ₁₂₀ H ₁₂₈ N ₈ O ₈ S ₈ ):

Calculated (%): C; 67.65, H; 6.06, N; 5.26, S; 12.04

Measured value (%): C; 67.59, H; 6,07 N; 5.22, S; 12.00

Next, 1 part of the obtained phthalocyanine compound (I-49) was dissolved in 100 parts of dibutyl ether and the obtained solution was applied on a polycarbonate optical disk substrate. The optical disk thus produced had a reflectance of 40% and a sensitivity of 50 dB at linear speeds of 830 nm, 8 mW and 5.5 m / sec.

Furthermore, 7 parts of compound (I-49) were dissolved in 1000 parts of cyanobiphenyl liquid crystal mixture, and then a liquid crystal panel was prepared using a solution. The image was clearly there when it was recorded on this panel using laser beams.

Furthermore, 1 part of phthalocyanine compound (I-49) was dissolved in 100 parts of dibutyl ether, and the solution obtained was then applied onto a polycarbonate optical card substrate. Thereafter, the upper layer was further protected with a resin to prepare an optical card. The optical card thus manufactured had a reflectance of 40%, a sensitivity of 50 dB (C / N ratio) at 830 nm, 8 mW and 2.8 m / sec linear speed. The durability of this card was also good.

Further, 4 parts of compound (I-49) were mixed with 1000 parts of polystyrene resin under heating to form a plate. The filter so prepared absorbed light sufficiently at 750-850 nm.

Example 50

A mixture of 464 parts of phthalonitrile derivative, 40 parts of 90% cuprous chloride, DBU 247 parts and n-amyl alcohol, 2,800 parts represented by the following formula (II-36) was heated under reflux for 6 hours.

Thereafter, the obtained reaction solution was poured into 160 parts of methyl alcohol to precipitate crystals, and the latter was absorbed and filtered, and then the column (silica gel / hexane: toluene = 1: 1) was dissolved and purified in the following structural formula (I-50). 350 parts (yield 73%) of phthalocyanine compounds represented by (λmax 778 nm / hexane; εmax 2.6 × 10 ⁵ ) were obtained:

Elemental analysis results (as CuC ₁₂₀ H ₁₂₈ N ₈ O ₈ S ₈ ):

Calculated (%): C; 67.65, H; 6.06, N; 5.26, S; 12.04

Measured value (%): C; 67.58, H; 6.08, N; 5.25, S; 12.02

Next, 1 part of the obtained phthalocyanine compound (I-50) was dissolved in 100 parts of dibutyl ether, and the obtained solution was applied to a polycarbonate optical disk substrate. The optical disk thus produced had 50 dB photosensitivity at 41% reflectivity, 830 nm, 8 mW and 5.5 m / sec linear speed.

Furthermore, 7 parts of compound (I-50) were dissolved in 1000 parts of cyanobiphenyl liquid crystal mixture, and then a liquid crystal panel was prepared using a solution. When the image was recorded on this panel using a laser beam, it was clearly there.

Furthermore, 1 part of phthalocyanine compound (I-50) was dissolved in 100 parts of dibutyl ether, and then the obtained solution was applied onto a polycarbonate optical card substrate. Thereafter, the upper layer was further protected with a resin to prepare an optical card. The optical card thus manufactured had a 41% reflectivity and a photosensitivity (C / N ratio) of 50 dB linear speed at 830 nm, 8 mW and 2.8 m / sec. The durability of this card was also good.

Furthermore, 4 parts of compound (I-50) were mixed under heating with 1000 parts of polystyrene resin and then molded into a plate. The filter so prepared absorbed light sufficiently at 750-850 nm.

Example 51

A mixture of 377 parts of phthalonitrile derivative, 27 parts of 90% cuprous chloride, 182 parts of DBU and 1, 900 parts of n-amyl alcohol represented by the following structural formula (II-37) was heated under reflux for 6 hours:

Thereafter, the obtained reaction solution was poured into 3,200 parts of methyl alcohol to precipitate crystals, and the latter was collected by absorption filtration, and then purified through a column (silica gel / hexane: toluene = 1: 1) to obtain the following structural formula (I-51). 270 parts (yield 70%) of phthalocyanine compounds represented by were obtained ( max 778 nm / hexane; max 2.82 × 10 ⁵ ):

Elemental analysis results (as CuC ₁₅₂ H ₁₉₂ N ₈ O ₈ S ₈ ):

Calculated (%): C; 70.78, H; 7.50, N; 4.34, S; 9.95

Measured value (%): C; 70.51, H; 7.47, N; 4.36, S; 9.90

Next, 1 part of the obtained phthalocyanine compound (I-51) was dissolved in 1000 parts of dibutyl ether, and the obtained solution was applied to a polycarbonate optical disk substrate. The optical disk thus produced had a reflectance of 34% and 50dB photosensitivity at 830nm, 8mW and 5.5m / sec linear speeds.

Furthermore, 7 parts of compound (I-51) were dissolved in 1000 parts of cyanobiphenyl liquid crystal mixture, and then a liquid crystal panel was prepared using a solution. When the image was recorded on this panel using a laser beam, it was apparent there.

Furthermore, 1 part of phthalocyanine compound (I-51) was dissolved in 100 parts of dibutyl ether, and then the obtained solution was applied on a polycarbonate optical card substrate. Thereafter, the layer was further protected with a resin to prepare an optical card. The optical card thus produced had a reflectance of 34% and 50 dB photosensitivity (C / N ratio) at 830 nm, 8 mW and 2.8 m / sec linear speeds. The durability of this card was also good.

Furthermore, 4 parts of compound (I-51) were mixed with 1000 parts of polystyrene resins under heating, and then molded into a plate. The filter so prepared absorbed light sufficiently at 750-850 nm.

Example 52

A mixture of 377 parts of the phthalonitrile derivative represented by the following formula (II-38), 27 parts of 90% cuprous chloride, 182 parts of DBU and 1, 900 parts of n-amyl alcohol was heated under reflux for 6 hours:

Thereafter, the obtained reaction solution was poured into 3,200 parts of methyl alcohol to precipitate crystals, and the latter was collected by absorption filtration and purified through a column (silica gel / hexane: toluene = 1: 1) to obtain the following structural formula (I-52). 290 parts (yield 75%) of phthalocyanine compounds represented by (λ max 778 nm / hexane; ε max 2.66 × 10 ⁵ ) were obtained:

Elemental analysis results (as CuC ₁₅₂ H ₁₉₂ H ₈ O ₈ S ₈ ):

Calculated (%): C; 70.78, H; 7.50, N; 4.34, S; 9.95

Measured value (%): C; 70.59, H; 7.48, N; 4.33, S; 9.89

Next, 1 part of the obtained phthalocyanine compound (I-52) was dissolved in 100 parts of dibutyl ether, and the obtained solution was applied to a polycarbonate optical disk substrate. The optical disk thus produced had a reflectance of 34% and 50dB photosensitivity at 830nm, 8mW and 5.5m / sec linear speeds.

Furthermore, 7 parts of compound (I-52) were dissolved in 1000 parts of cyanobiphenyl liquid crystal mixture, and then a liquid crystal panel was prepared using a solution. When the image was recorded on this panel using a laser beam, it was apparent there.

Furthermore, 7 parts of phthalocyanine compound (I-52) was dissolved in 100 parts of dibutyl ether, and then the obtained solution was applied onto a polycarbonate optical card substrate. Thereafter, the layer was further protected with a resin to prepare an optical card. The optical card thus produced had a reflectance of 34% and 50 dB photosensitivity (C / N ratio) at 830 nm, 8 mW and 2.8 m / sec linear speeds. The durability of this card was also good.

Furthermore, 4 parts of compound (I-52) were mixed with 1000 parts of polystyrene resins under heating, and then shaped into a plate. The filter so prepared absorbed light sufficiently at 750-850 nm.

Example 53

A mixture of 43 parts of SiCl ₄ and 3,000 parts of quinoline was heated to 200 ° C. To the heated mixture, a solution to which 533 parts of diimino isoindolin derivatives represented by the following formula (III-7) was added was heated under reflux for 5 hours.

Thereafter, the obtained reaction solution was poured into 3,200 parts of methyl alcohol to precipitate the crystals, and the latter was collected by absorption filtration, washed with methanol, and dried, followed by 195 parts of phthalocyanine represented by the following structural formula (I-53) ( Yield 36%) was obtained ( max 780 nm / hexane; max 2.48 × 10 ⁵ ):

Elemental analysis results (as SiC ₁₂₀ H ₁₂₈ N ₈ O ₈ S ₈ Cl ₂ ):

Calculated (%): C; 66.57, H; 5.92, N; 5.18, Cl; 3.28, S; 11.84

Measured value (%): C; 66.46, H; 5.95, N; 5.14, Cl: 3.22, S; 11.79

Next, 1 part of the obtained phthalocyanine compound (I-53) was dissolved in 100 parts of dibutyl ether, and the obtained solution was applied to a polycarbonate optical disk substrate. The optical disk thus produced had a reflectance of 33% and 50dB photosensitivity at 780mm, 8mW and 5.5m / sec linear speeds.

Furthermore, 1 part of compound (I-53) was dissolved in 1000 parts of cyanobiphenyl liquid crystal mixture, and then a liquid crystal panel was prepared using a solution. When the image was recorded on this panel using a laser beam, it was clearly visible there.

Furthermore, 7 parts of compound (I-53) were dissolved in 100 parts of dibutyl ether, and then the obtained solution was applied onto a polycarbonate optical card substrate. The obtained recording layer was then further protected with a resin to prepare an optical card. The optical card thus produced had a reflectance of 33% and 50 dB photosensitivity (C / N ratio) at 780 nm, 8 mW and 2.8 m / sec linear speeds.

Furthermore, 4 parts of compound (I-53) were mixed under heating with 1000 parts of polystyrene resin and then molded into a plate. The filter so prepared absorbed light sufficiently at 750-850 nm.

[Examples 54 to 97]

1 to 4 kinds of phthalonitrile (Table 5) represented by the following formula (II) or diimino isoindolin (Table 6) represented by the following formula (III) were reacted with metal derivatives, Phthalocyanine was synthesized.

The synthesized compound had a maximum molecular extinction coefficient and the optical record medium made from this compound was also excellent in reflectance, photosensitivity and durability.

Table 5 (I)

Table 5 (II)

Table 5 (III)

TABLE 6

Table 7 (Ⅰ)]

Table 7 (II)

Table 7 (III)

Table 7 (IV)

Example 98

The mixture of 10 parts of phthalonitrile derivative represented by the following structural formula (II-69), 2 parts of PdCl ₃ , 4 parts of DBU and 200 parts of n-amyl alcohol was heated under reflux:

The obtained reaction solution was then poured into water, and the precipitated tar was purified by column chromatography to obtain 2 parts of phthalocyanine compounds represented by the following structural formula (I-98) ( max 692 nm / hexane; max 2.5 × 10 ⁵ ):

Elemental analysis results (as Pd C ₆₀ H ₇₂ N ₈ O ₄ ):

Calculated (%): C; 67.88, H; 6.43, N; 10.39

Measured value (%): C; 67.00, H; 6.75, N; 10.42

Next, 1 part of the obtained phthalocyanine compound (I-98) was dissolved in 100 parts of methylcyclohexane, and the obtained solution was applied onto a polycarbonate substrate. Afterwards, gold was splashed there, and the UV fixing resin was further applied thereto to cure there, thereby producing a CD-WORM type optical recording medium.

The CD-WORM type optical recording medium thus prepared had a reflectance of 72% and a sensitivity of 52 dB at 8 mW and 2.5 m / sec linear speed.

Furthermore, compound (I-98) was applied over polycarbonate to make a film there. The film had high refractive indices, namely 2.78 (at 720 nm), 2.05 (at 780 nm) and 1.95 (at 830 nm).

Example 99

A mixture of 10 parts of phthalonitrile derivative, ₂ parts of PdCl ₂ , 4 parts of DBU and 200 parts of n-amyl alcohol represented by the following formula (II-70) was heated under reflux:

Thereafter, the obtained reaction solution was poured into water and the precipitated tar was purified by column chromatography to obtain 2.5 parts of phthalocyanine compound represented by the following structural formula (I-99) (λmax 686 nm / hexane; εmax 2.5 × 10 ⁵ ) :

Elemental analysis results (as Pd C ₅₂ H ₅₆ N ₉ O ₄ ):

Calculated (%): C; 64.83, H; 5.86, N; 11.68

Measured value (%): C; 64.90, H; 5.80, N; 11.60

Next, 1 part of the obtained phthalocyanine compound (I-99) was dissolved in 100 parts of methylcyclohexane and the obtained solution was applied onto a polycarbonate substrate. Thereafter, the acrylic UV fixing resin was further applied and cured therein to prepare an optical card.

The optical card thus manufactured had a reflectance of 28% and a sensitivity of 50 dB at 8 mW and 1.8 m / sec linear speeds.

Furthermore, compound (I-99) was applied on polycarbonate to make a film. This film had high refractive indices, 2.37 (at 720 nm), 2.01 (at 780 nm), and 1.89 (at 830 nm).

Example 100

According to the same procedure as in Example 99, a compound having the following structural formula (II-71) was reacted to obtain a compound represented by the following formula (I-100) ( max 720 nm / hexane; max 2.01 × 10 ⁵ ):

This compound (I-100) was applied over polycarbonate to prepare a film there. This film had a high refractive index, 1.96 (at 780 nm) and 1.86 (at 830 nm).

Furthermore, 4 parts of compound (I-100) were heated to be molded together with 1000 parts of PMMA resin, and then the mixture was stretched to produce a film having a thickness of 200 mu m. The film so produced absorbed light sufficiently at 700 to 830 nm.

Example 101

A mixture of 10 parts of phthalonitrile derivative, 2 parts of NiCl ₃ , 4 parts of DBU and 200 parts of n-amyl alcohol represented by the following structural formula (II-72) was heated under reflux.

Thereafter, the obtained reaction solution was poured into water, and the precipitated tar was purified by column chromatography to obtain 2 parts of phthalocyanine compounds represented by the following structural formula (I-101) ( max 690 nm / hexane; max 2.4 × 10 ⁵ ):

Elemental analysis results (as Ni C ₆₀ H ₆₈ N ₁₂ O ₁₂ ):

Calculated (%): C; 59.66, H; 5.63, N; 13.92

Measured value (%): C; 60.01, H; 5.75, N; 14.02

Next, 1 part of the obtained phthalocyanine compound (I-101) was dissolved in 100 parts of methylcyclohexane, and the obtained solution was then applied to a polycarbonate substrate. Afterwards, gold was splashed there, and the UV fixing resin was further applied there and cured therein to produce a CD-WORM type optical recording medium.

The CD-WORM type optical recording medium thus prepared had a reflectance of 71%, a 52 dB sensitivity at 7 mW, and a 1.5 m / sec linear speed.

Furthermore, compound (I-101) was applied over polycarbonate to make a film there. This film had high refractive indices, 2.65 (at 718 nm), 2.08 (at 780 nm) and 1.94 (at 830 nm).

Example 102

A mixture of 10 parts of phthalonitrile derivative, 2 parts of PdCl ₃ , 4 parts of DBU and 200 parts of n-amyl alcohol represented by the following structural formula (II-73) was heated under reflux:

The reaction solution thus obtained was poured into water, and the precipitated tar was purified by column chromatography to obtain 2.5 parts of phthalocyanine compound represented by the following structural formula (I-102) ( max 688 nm / hexane; max 2.4 × 10 ⁵ ):

Elemental analysis results (as Pd C ₅₂ H ₅₂ N ₈ O ₄ Br ₄ ):

Calculated (%): C; 64.90, H; 5.50, N; 11.60

Measured value (%): C; 65.10, H; 5.46, N; 11.68

Next, 1 part of the obtained phthalocyanine compound (I-102) was dissolved in 100 parts of methylcyclohexane, and the obtained solution was applied onto a polycarbonate substrate. Thereafter, the arc was further applied by UV fixing resin to cure there to manufacture an optical card.

The optical card had a reflectance of 32% and 50dB sensitivity at 780nm, 8mW and 1.8m / sec linear speeds.

Furthermore, compound (I-102) was applied over polycarbonate to make a film there. This film had high refractive indices, namely 2.40 (at 720 nm), 2.02 (at 780 nm) and 1.88 (at 830 nm).

Example 103

Ten parts of the above-mentioned formula (I-99) phthalocyanine was poured into 200 parts of acetic acid, and three parts of fuming nitric acid were further added thereto. The solution was reacted at room temperature for 1 hour and at 50 ° C for 2 hours to obtain 8 parts of phthalocyanine having the following structural formula ( max 682 nm / hexane; max 2.03 × 10 ⁵ ):

Next, a solution obtained by dissolving 1 part of the obtained phthalocyanine compound (I-103) in 100 parts of methylcyclohexane was applied onto a polycarbonate substrate. Thereafter, the acrylic UV fixing resin was further applied to thereby cure the optical card.

The optical card thus produced had a reflectance of 28% and a sensitivity of 50 dB at 780 nm, 8 W and 1.8 m / sec linear speed.

Furthermore, compound (I-103) was applied over polycarbonate to make a film there. This film had high refractive indices, 2.47 (at 720 nm), 2.22 (at 780 nm) and 1.89 (at 830 nm).

[Comparative Example 4]

(Example (iii) in Japanese Patent Laid-Open No. 39, 286/1987)

One part of the compound represented by the following structural formula (A) was dissolved in 100 parts of cellosolve, and the obtained solution was then applied onto a polycarbonate substrate:

Thereafter, gold was splashed onto the substrate, and a UV fixing resin was applied thereon and cured to prepare a CD-WORN optical medium.

The media so produced had a reflectance of 50% and a C / N ratio of 30 dB at 8 mW, 780 nm and 2.5 m / sec linear speeds.

Moreover, the film consisted of the compound (A) mentioned above and the reflectance of this film was 1.70 (at 780 nm).

[Comparative Example 5]

(Example 에서 in Japanese Patent Laid-Open No. 39, 286/1987)

4 parts of compound represented by structural formula (B)

Was heated and molded together with 100 parts of PMMA to elongate the mixture to prepare a film having a thickness of 200 μm. At this time, it was confirmed that the compound was thermally decomposed.

Claims (4)

Liquid crystal element containing the near-infrared light absorber of general formula (I) whose molecular extinction coefficient is 200, 000 or more in a recording layer [Wherein Y ¹ , Y ² , Y ³ , Y ⁴ , Y ⁵ , Y ⁶ , Y ⁷ and Y ⁸ are each a hydrogen atom, a straight or branched chain alkyl group having from 1 to 15 carbon atoms, having from 4 to 15 carbon atoms Linear, branched or cyclic alkoxyl groups, straight chain, branched or cyclic alkylthio groups having 4 to 15 carbon atoms, each of Y ¹ and Y ² , Y ³ and Y ⁴ , Y ⁵ and Y ⁶ , Y ⁷ and Y ⁸ Is not a combination of a hydrogen atom, an alkyl group or an alkylthio group at the same time or a combination of an alkyl group and a hydrogen atom; A ¹ , A ² , A ³ , A ⁴ , A ⁵ , A ⁶ , A ⁷ and A ⁸ each independently represent a hydrogen atom, a halogen atom, a nitro group, a straight-chain, branched or cyclic alkyl group having 1 to 10 carbon atoms Aralkyl group having 7 to 20 carbon atoms, Alkenyl group having 1 to 10 carbon atoms; Alkynyl groups having 1 to 10 carbon atoms, straight or branched alkoxyl groups having 1 to 4 carbon atoms, or cyclic alkoxyl groups having 6 to 10 carbon atoms, aryloxy groups having 6 to 20 carbon atoms, 1 to 10 carbon atoms A straight, branched or cyclic alkylthio group having 6 carbon atoms or an arylthio group having 6 to 20 carbon atoms, each of A ¹ and A ² , A ³ and A ⁴ , A ⁵ and A ⁶ and A ⁷ and A ⁸ The pair may combine with each other to form a ring; A ¹ , A ² , A ³ , A ⁴ , A ⁵ , A ⁶ , A ⁷ and A ⁸ are all hydrogen atoms and Y ¹ and Y ² , Y ³ and Y ⁴ , Y ⁵ and Y ⁶ and Y ⁷ And when each pair of Y ⁸ is a combination of a hydrogen atom and an alkoxyl group, the alkoxyl group described above has 4 to 9 carbon atoms and is branched or cyclic; And Met represents two hydrogen atoms, a divalent metal atom, a substituted trivalent and tetravalent metal atom or an oxymetal group.]. The method according to claim ¹ , wherein each group represented by Y ¹ , Y ² , Y ³ , Y ⁴ , Y ⁵ , Y ⁶ , Y ⁷ and Y ⁸ is hydrogen or branched or cyclic having 4 to 9 carbon atoms. An alkoxyl group or a linear or branched alkyl group having 1 to 8 carbon atoms; And each combination of Y ¹ and Y ² , Y ³ and Y ⁴ , Y ⁵ and Y ⁶ and Y ⁷ and Y ⁸ simultaneously contains a near infrared light absorber which is not a combination of a hydrogen atom or an alkyl group or a combination of an alkyl group and a hydrogen atom. Liquid crystal device. The compound according to claim ¹ , wherein, among the groups represented by Y ¹ , Y ² , Y ³ , Y ⁴ , Y ⁵ , Y ⁶ , Y ⁷ and Y ⁸ , Y ¹ and Y ² , Y ³ and Y ⁴ , Y ⁵ And a near-infrared light absorbing agent, wherein each combination of Y ⁶ , Y ⁷ and Y ⁸ is a combination of another alkoxyl group having 4 to 9 carbon atoms in a straight, branched or cyclic form. A compound according to claim ¹ , wherein each group represented by A ¹ , A ² , A ³ , A ⁴ , A ⁵ , A ⁶ , A ⁷ and A ⁸ is independently an alkyl group having 1 to 6 carbon atoms or 6 to 10 carbon atoms. A liquid crystal device containing a near infrared light absorber which is an arylthio group having two carbon atoms.