KR920005479B1 - Naphthalocyanine derivatives and their use in optical recording medium - Google Patents

Abstract

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Description

Optical recording medium and manufacturing method thereof

1 is a diagram relating to an IR spectrum of 3,4-bis (dibromo-methyl) bromobenzene.

2 is a diagram for an NMR spectrum of 6-bromo-2,3-dicyonanaphthalene.

3 shows the IR spectrum of 6-Brmo-2,3-dicyonanaphthalene.

4 is a diagram of an IR spectrum (KBr) of 6-bromo-1,3-diobenz [f] -isoindolin.

5 is a diagram relating to a spectrum of dichlorosilicon-tetrabromonaphthalocyanine.

6 is an electron spectrum (tetrahydrofuran solution) of dichlorosilicon-tetrabromonaphthalocyanine.

7 shows the IR spectrum (KBr) of dihydroxysilicone-tetrabromonaphthalocyanine.

8 is a diagram of an electron spectrum (tetrahydrofuran solution) of dihydroxysilicone-tetrabromonaphthalocyanine.

9 is a diagram for an NMR spectrum of bis (tri-n-propylsiloxy) silicone-tetrabromonaphthalocyanine.

10 is a diagram of an electron spectrum of bis (tri-n-propylsiloxy) silicone-tetrabromonaphthalocyanine.

FIG. 11 is a diagram showing an IR spectrum of bis (tri-n-propylsiloxy) silicone-tetrabromonaphthalocyanine.

12 is a diagram of an NMR spectrum of bis (tri-n-butylsiloxy) silicone-tetrabromonaphthalocyanine.

FIG. 13 is a diagram of an NMR spectrum of bis (tri-n-butylsiloxy) silicone-tetrabromonaphthalocyanine.

14 shows the IR spectrum of bis (tri-n-butylsiloxy) silicone-tetrabromonaphthalocyanine.

FIG. 15 is a diagram of an NMR spectrum of bis (tri-n-hexylyloxy) silicone-tetrabromonaphthalocyanine.

FIG. 16 is a diagram of an electron spectrum of bis (tri-n-hexyloxyoxy) silicon-tetrabromonaphthalocyanine.

FIG. 17 is a diagram of an IR spectrum of bis (tri-n-hexylyloxy) silicone-tetrabromonaphthalocyanine.

FIG. 18 is an electron spectrum of bis (triethylsiloxy) silicone-tetrabromonaphthalocyanine.

FIG. 19 shows an IR spectrum of bis (triethylsiloxy) silicone-tetrabromonaphthalocyanine.

FIG. 20 is a diagram showing an NMR spectrum of bis (tri-n-propylsiloxy) silicone-tetra (n-dodecylthio) naphthalocyanine.

FIG. 21 shows electron spectra of bis (tri-n-propylsiloxy) silicone-tetra (n-dodecylthio) naphthalocyanine.

FIG. 22 is a diagram of an IR spectrum of bis (tri-n-propylsiloxy) silicone-tetra (n-dodecylthio) naphthalocyanine.

FIG. 23 is a diagram of an NMR spectrum of bis (tri-n-propylsiloxy) silicone-tetra (n-tetradecylthio) naphthalocyanine.

FIG. 24 is a diagram showing an electron spectrum of bis (tri-n-propylsiloxy) silicone-tetra (n-tetradecylthio) naphthalocyanine.

FIG. 25 is a diagram of an IR spectrum of bis (tri-n-propylsiloxy) silicone-tetra (n-tetradecylthio) naphthalocyanine.

FIG. 26 is a diagram of an NMR spectrum of bis (tri-n-propylsiloxy) silicone-tetra (n-hexadecylthio) naphthalocyanine.

FIG. 27 is a diagram showing an electron spectrum of bis (tri-n-propylsiloxy) silicon-tetra (n-hexadecylthio) naphthalocyanine.

28 is an IR spectrum of bis (tri-n-propylsiloxy) silicone-tetra (n-hexadecylthio) naphthalocyanine.

FIG. 29 shows NMR spectra of bis (tri-n-propylsiloxy) silicone-tetra (n-decylthio) naphthalocyanine.

30 shows electron spectra of bis (tri-n-propylsiloxy) silicone-tetra (n-decylthio) naphthalocyanine.

FIG. 31 shows the IR spectrum of bis (tri-n-propylsiloxy) silicone-tetra (n-decylthio) naphthalocyanine.

32 is a diagram for NMR spectra of bis (tri-n-butylsiloxy) silicone-tetra (n-dodecylthio) naphthalocyanine.

33 is a diagram of an electron spectrum of bis (tri-n-butylsiloxy) silicone-tetra (n-dodecylthio) naphthalocyanine.

34 is an IR spectrum of bis (tri-n-butylsiloxy) silicone-tetra (n-dodecylthio) naphthalocyanine.

FIG. 35 shows an electron spectrum of bis (tri-n-propylsiloxy) silicon- (n-dodecylthio) naphthalocyanine.

36 shows electron spectra of bis (tri-n-propylsiloxy) silicone-tetra (n-dodecylthio) naphthalocyanine in acetone.

FIG. 37 shows the electron spectrum of bis (tri-n-propylsiloxy) silicon-tetra (n-dodecylthio) naphthalocyanine in toluene.

FIG. 38 is a diagram of an electron spectrum of bis (tri-n-propylsiloxy) silicone-tetra (n-dodecylthio) naphthalocyanine in hexane.

FIG. 39 is a diagram of a transmission spectrum of a spin-coated film of bis (tri-n-propylsiloxy) silicon-tetra (n-dodecylthio) naphthalocyanine.

FIG. 40 is a plot of the 5 ° specular reflection spectra of a spin-ripped film of bis (tri-n-propylsiloxy) silicone-tetra (n-dodecylthio) naphthalocyanine.

FIG. 41 shows electron spectra of vanadil-tetra (tert-butyl) naphthalocyanine in a chloroform solution of (a) 2.37 × 10 ⁻⁶ M and (b) 1.89 × 10 ⁻⁵ M.

42 is a view of an electron spectrum of vanadil-tetra (tert-butyl) naphthalocyanine in a benzene solution (9.5 × 10 ⁻⁶ M).

FIG. 43 is a diagram of a transmission spectrum of a spin-coated film of vanadil-tetra (tert-butyl) naphthalocyanine.

FIG. 44 is a diagram of the 5 ° specular reflection spectrum of a spin-coated film of vanadil-tetra (tert-butyl) naphthalocyanine.

45 shows the transmission spectra of the spin-coated film of bis (triethyloxy) silicone-tetra (n-decylthio) naphthalocyanine [compound 127], bis (tri-n-propylsiloxy) silicone -Transmission spectra (-) of the spin-coated film of tetra (n-decylthio) naphthalocyanine [Compound (99)], and bis (tri-n-butylsiloxy) silicon-tetra (n-decylthio) Transmission spectrum of spin-coated film of naphthalocyanine [Compound (102)] Degrees for).

FIG. 46 shows the 5 ° specular reflectance spectra of the spin-coated film of bis (triethylsiloxy) silicone-tetra (n-decylthio) naphthalocyanine [Compound (127)], bis (tri-n-propylsiloxane 5 ° specular reflectance spectrum (-) of the spin-coated film of silicon-tetra (n-decylthio) naphthalocyanine [Compound (99)], and bis (tri-n-butylsiloxy) silicon-tetra ( 5 ° specular reflection spectrum of spin-coated film of n-decylthio) naphthalocyanine [Compound (102)] Degrees for).

FIG. 47 is a diagram of an NMR spectrum of bis (triethylsiloxy) silicone-tetra (n-decylthio) naphthalocyanine.

48 is a diagram showing an electron spectrum of bis (triethylsiloxy) silicone-detra (n-decylthio) naphthalocyanine.

FIG. 49 is a diagram of an IR spectrum of bis (triethylsiloxy) silicone-detra (n-decylthio) naphthalocyanine.

50 is a diagram for an NMR spectrum of bis (triethylsiloxy) silicone-detra (n-dodecylthio) naphthalocyanine.

FIG. 51 is a diagram showing an electron spectrum of bis (triethylsiloxy) silicone-detra (n-dodecylthio) naphthalocyanine.

FIG. 52 is a diagram of an IR spectrum of bis (triethylsiloxy) silicon-detra (n-dodecylthio) naphthalocyanine.

FIG. 53 is a diagram showing an NMR spectrum of bis (tri-n-butylsiloxy) silicon-detra (n-decylthio) naphthalocyanine.

FIG. 54 is a diagram showing an electron spectrum of bis (tri-n-butylsiloxy) silicon-detra (n-decylthio) naphthalocyanine.

FIG. 55 is a diagram showing an IR spectrum of bis (tri-n-butylsiloxy) silicon-detra (n-decylthio) naphthalocyanine.

Figure 56 is a diagram for an NMR spectrum of bis (tri-n-hexyloxyoxy) silicon-detra (n-dodecylthio) naphthalocyanine.

FIG. 57 is a diagram showing an electron spectrum of bis (tri-n-hexyloxyoxy) silicon-tetra (n-decylthio) naphthalocyanine.

FIG. 58 is a diagram showing an IR spectrum of bis (tri-n-hexyloxyoxy) silicon-tetra (n-decylthio) naphthalocyanine.

FIG. 59 is a diagram showing an NMR spectrum of bis (tri-n-propylsiloxy) silicon-detrakis [2- (2'-ethylhexyloxycarbonyl) ethylthio] naphthalocyanine.

FIG. 60 is a diagram showing an electron spectrum of bis (tri-n-propylsiloxy) silicon-detrakis [2- (2'-ethylhexyloxycarbonyl) ethylthio] naphthalocyanine.

FIG. 61 is a diagram showing an IR spectrum of bis (tri-n-propylsiloxy) silicon-detrakis [2- (2'-ethylhexyloxycarbonyl) ethylthio] naphthalocyanine.

FIG. 62 relates to an NMR spectrum of Bis (tri-n-propylsiloxy) silicon-detrakis [2- (2 ', 2', 4 ', 4'-tetramethylpentyloxycarbonyl) ethylthio] naphthalocyanine Degree.

FIG. 63 relates to an electron spectrum of bis (tri-n-propylsiloxy) silicon-detrakis [2- (2 ', 2', 4 ', 4'-tetramethylpentyloxycarbonyl) ethylthio] naphthalocyanine Degree.

FIG. 64 relates to the IR spectrum of bis (tri-n-propylsiloxy) silicon-detrakis [2- (2 ', 2', 4 ', 4'-tetramethylpentyloxycarbonyl) ethylthio] naphthalocyanine Degree.

The present invention relates to an optical recording medium using a naphthalocyanine derivative and a method for producing the optical recording medium.

Recently, it has been proposed to use diode laser beams for writing and decoding in compact discs, video discs, liquid crystal displays, optical decoders and the like, and as light sources for electrophotography. A material capable of absorbing the diode laser beam, i.e. near infrared rays, is indispensable for writing or decoding by use of the diode laser beam.

As organic dyes absorbing near infrared rays, cyanine dyes are best known to date, and metal complexes and aminated quinone derivatives of oxime and thiols are also known as near infrared absorbing dyes. See Yuki Gosei Kagaku Kyokai Shi, 43, p. 334 (1985), Shikizai Kyokai Shi, vol. 53, p. 197 (1980), and Shikizai Kyokai Shi, vol. 58, p. 220 (1985)].

However, cyanine dyes have a very low stability to light, which leads to various obstacles in their use. Metal complexes of oximes and thiols have the disadvantage that the metal dissociates from the complex in a particular medium and loses the ability to absorb near infrared rays. Aminated quinone derivatives have very poor near infrared absorption capacity.

On the other hand, naphthalocyanine derivatives have recently been known as substances capable of solving these problems, but conventional unsubstituted metal naphthalocyanines (Zhurnal Obshchei Khimii, vol. 39, p. 2554 (1969) and Mol. Crist. Liq , Cryst. 112, 345 (1984)] are insoluble in organic solvents and are very difficult to purify. Recently, a method for synthesizing naphthalocyanine derivatives dissolved in an organic solvent has been reported (see Japanese Patent Application Laid-Open Nos. 60-23451, 60-184565, 61-215662 and 61-215663), but these naphthalocyanine derivatives have the following disadvantages. Have Their absorption varies greatly depending on the type of solvent, concentration, temperature, etc., and the absorption ability of their diode laser beam in the form of a high concentration solution or solid film is greatly reduced and furthermore the reflected light decodes the information recorded on the optical disc. The critical reflectance when used is very low in the diode laser range (780-830 mm).

Only two compounds were reported in Japanese Patent Application Laid-Open No. 61-235188 as naphthalocyanine with high reflectivity, and the concept of synthesis of these compounds was reported in Japanese Patent Application Laid-Open Nos. 61-177287 and 61-177288. In this specification, only a few examples will be described, and in some examples, the compounds may be synthesized according to the methods described herein. For example, in the case of Scheme I described in the first row of the top right corner of page 8 of Japanese Patent Application Laid-Open No. 61-177288, when the long-chain alkyl group or similar compound contains Xn,

The solubility of is too high and the synthesis of this material makes the separation of the material from the reaction solution impossible, and furthermore, starting materials for the abovementioned starting materials:

It is difficult to separate and purify the compound from the reaction system in which the reaction mixture is complicated in the reaction step. Therefore, it is impossible to use starting materials to synthesize the desired naphthalocyanine. Scheme II, described in the third row at the top right of page 8 of Japanese Patent Application Laid-Open No. 61-177288, shows a nucleophilic reaction of a naphthalocyanine ring similar to the Friedel-Craft reaction, and alkoxyl groups, alkylti It is not suitable for the introduction of thio and amino groups into the naphthalocyanine ring. Furthermore, in the case of Scheme III described in the fifth column of the top right of page 8 of Japanese Patent Application Laid-Open No. 61-177288, purification of the starting material is impossible, and the product is obtained in the form of a very complex mixture and difficult to purify. Therefore, this scheme is not suitable for separating high purity products, and furthermore, the reaction itself is inhibited by the influence of hydroxyl groups bonded to Si of the starting material, which does not allow the reaction to proceed in the desired direction. Therefore, there is a problem that the synthesis method has been found independently in synthesizing preferred naphthalocyanine having a long chain alkyl group in a naphthalocyanine ring which is substantially soluble in an organic solvent and has excellent properties as an optical recording medium.

The present invention provides a naphthalocyanine derivative represented by the following general formula (I).

Wherein k, l, m and n may be the same or different and are an integer of 0 or 1 to 4, and k + l + m + n is an integer of 1 or more; R ¹ in the number of 4 (k + l + m + n) may be the same or different and is an alkyl group, a substituted alkyl group or an aryl group; M is Si, Ge, or Sn; The two Y's may be the same or different and are an aryloxyl group, an alkoxy group, a trialkyloxyl group, a triaryloxyl group, a trialkoxyoxyl group, a triaryloxyoxyl group, a trityloxyl group, or an acyloxyl group.

The present invention relates to naphthalocyanine derivatives of the following general formula (II), chlorosilanes of the following general formula (III), silanes of the following general formula (IV), alcohols of the following general formula (V), or general formula (VI) Also provided is a method for preparing a naphthalocyanine derivative of the general formula (I), which is characterized by reacting with a compound of.

Wherein k, l, m and n may be the same or different and are an integer of 0 or 1 to 4, and k + l + m + n is an integer of 1 or more; M is Si, Ge, or Sn. R ² and R ³ are each an alkyl group, an aryl group, an alkoxyl group, or an aryloxyl group, R ⁴ is an alkyl group or an aryl group, R ⁵ is an alkyl group, and X is a halogen atom, a hydroxyl group or an acyloxyl group.

The present invention also provides a method for producing a naphthalocyanine derivative of the general formula (I), wherein the naphthalocyanine derivative of the general formula (VII) is reacted with copper (I) thiolate of the general formula (VII).

Wherein k, l, m and n may be the same or different and 0 degrees is an integer of 1 to 4, and k + l + m + n is an integer of 1 or more; M is Si, Ge, or Sn; The two Y's may be the same or different and are an aryloxyl group, alkoxyl group, trialkyloxyloxy group, triaryloxyloxy group, trialkoxyoxyloxy group, triaryloxyoxyloxy group, trityloxyl group, or acyloxyl group. R ¹ is an alkyl group, a substituted alkyl group or an aryl group.

The present invention also provides an optical recording medium consisting of a substrate and a recording layer mainly composed of naphthalocyanine derivatives of general formula (I) formed on the surface of the substrate.

The present invention relates to a method for producing an optical recording medium, wherein a recording film or a recording layer is formed on a substrate using a solution prepared by dissolving a naphthalocyanine derivative of formula (I) as a main component in an organic solvent. to provide.

The present invention provides naphthalocyanine derivatives of the general formula (I):

Wherein k, l, m and n may be the same or different and are an integer of 0 or 1 to 4, and k + l + m + n is 1 or more; R ¹ in the number of 4 (k + l + m + n) may be the same or different and is an alkyl group, a substituted alkyl group or an aryl group; M is Si, Ge, or Sn; The two Y's may be the same or different and are an aryloxyl group, an alkoxyl group, a trialkyloxyl group, a triaryloxyloxy group, a trialkoxyoxyloxy group, a triaryloxysiloxyl group, a trityloxyl group, or an acyloxyl group.

The naphthalocyanine derivatives of formula (I) are dissolved in aromatic solvents, halogenated solvents, ether solvents, ketone solvents and saturated hydrocarbon solvents and can be easily purified to improve purity. In addition, the absorbency does not change depending on the type and concentration of the solvent, and the absorption capability of the diode laser beam is also excellent.

Aromatic solvents include benzene, toluene, xylene, chlorobenzene, dichlorobenzene, trimethylbenzene, 1-chloronaphthalene, quinoline and the like. Halogenated solvents include methylene chloride, chloroform, carbon tetrachloride, trichloroethane and the like. Examples of the ether solvent include diethyl ether, dibutyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, and the like. Ketone solvents include acetone, methyl ethyl ketone, methyl propyl ketone, cyclopentanone, cyclohexanone, acetone alcohol and the like. Saturated hydrocarbon solvents include hexane, heptane, octane, nonane, decane, undecane, dodecane and the like.

Examples of the allyl group for R ¹ in the general formula (I) include methyl group, ethyl group, n-propyl group, secondary-propyl group, n-butyl group, secondary-butyl group, tert-butyl group, n- Amyl, tertiary-amyl, 2-amyl, 3-amyl, hexyl, heptyl, octyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, eicosyl, doco Practical skills; Examples of the substituted alkyl group for R ¹ include an alkyl group having an ester group, an alkyl group having an amide group, an alkyl group having a hydroxyl group, an aralkyl group, an alkoxyalkyl group, a haloalkyl group, and the like; Examples of the aryl group for R ¹ include a phenyl group, tolyl group, anylyl group, halophenyl group, furyl group, tenyl group, pyridyl group and the like.

In general formula (I), M has Si, Ge, and Sn, and with respect to Y, an aryloxyl group has a phenoxyl group, a tolyloxyl group, an anoxyloxyl group, etc .; Examples of the alkoxyl group include amyloxyl, hexyloxyl, octyloxyl, decyloxyl, dodecyloxyl, tetraoxylyl, hexadecyloxyl, octadecyloxyl, eicosyloxyl and docosyloxyl; Trialkyloxyl group, triethyl oxyl group, tripropyl oxyl group, tributyl oxyl group, etc. are mentioned as a trialkyl oxyl group; Triaryl oxyl group includes triphenyl oxyl group, trianisyl oxyl group, and trityl oxyl group; Trialkoxy trimethyloxysiloxyl group, triethoxyoxyloxy group, tripropoxyoxyoxyl group, tributoxyoxyoxyl group, etc .; Examples of the triaryloxyoxyoxyl group include a triphenoxyoxyoxyl group, a trianylsiloxyoxyoxyl group, and a tritolyloxyoxyoxyl group; The acyloxyl group includes an aceoxyl group, propionyloxyl group, butyryloxyl group, valeryloxyl group, pivaloyloxyl group, hexanoyloxyl group, and octanonyloxyl group.

The length of the alkyl group of these groups is formed by dissolving the compound in the organic solvent and the melting point of the naphthalocyanine derivative of formula (I) in an organic solvent, and by spin-coating the resulting solution on a suitable substrate such as a glass plate. It also greatly affects the absorption spectrum, transmission spectrum and reflection spectrum of the amorphous film.

In particular, the alkyl group length of the substituent Y bonded to the central metal M has a great influence on the spectra of the spin-coated film. Therefore, the alkyl chain length of Y can vary depending on the output wavelength of the laser used.

On the other hand, when the alkyl chain length of Y changes, the alkyl chain length of R ¹ contributes to controlling the solubility and melting point of the compound in the organic solvent.

For example, when Y is a trialkyloxyl group, the length of its alkyl group greatly influences the spectrum of the spin-coated film; Shorter alkyl chain lengths shift each absorption maximum, minimum transmission, and maximum reflectance over a longer wavelength range. Therefore, compounds particularly preferred as diode lasers used in view of maximum reflectance can be obtained by changing the alkyl group length of the trialkyloxylyl group, and R ¹ can be appropriately selected so that the solubility and melting point of the naphthalocyanine derivative are most appropriate. .

Preferred are naphthalocyanine derivatives of formula (I) wherein M is Si or Ge.

Preferred are naphthalocyanine derivatives of formula (I) in which k, l, m and n are all 1.

Preference is given to naphthalocyanine derivatives of formula (I) wherein both Y are trialkyloxyloxy groups.

Preference is given to naphthalocyanine derivatives of general formula (I) in which all R ¹ have from 1 to 22 carbon atoms.

Preference is given to naphthalocyanine derivatives of the general formula (I) in which all R ¹ are substituted alkyl groups.

Specific examples of the naphthalocyanine derivatives of the present invention are given below. In general formulas, Ph represents a phenyl group.

Furthermore, in the present invention, the naphthalocyanine derivative of the following general formula (II) may be substituted with chlorosilane of the following general formula (III), silane of the following general formula (IV), alcohol of the following general formula (V), or the following general formula ( It provides a process for the preparation of naphthalocyanine derivatives of the following general formula (I) characterized by reacting with the compound of VI).

Wherein k, l, m and n may be the same or different and are an integer of 0 or 1 to 4, and k + l + m + n is an integer of 1 or more: R ¹ is as defined above; Two Y's may be the same or different and are an aryloxyl group, an alkoxyl group, a trialkyloxyloxy group, a triaryloxyloxyl group, a trialkoxyoxyloxyl group, a triaryloxyoxyloxyl group, a trityloxyl group or an acyloxyl group; M is Si, Ge, or Sn; R ² and R ³ are each an alkyl group, an aryl group, an alkoxyl group, or an aryloxyl group; R ⁴ is an alkyl group or allyl group, and R ⁵ is an alkyl group; X is a halogen atom, a hydroxyl group, or an acyloxyl group.

The naphthalocyanine derivatives of formula (I) can be obtained by heating a compound of formula (II) with an excess of the compound of formula (III), (IV), (V) or (VI). In this case, the reaction temperature is preferably 80 to 250 ° C, and the reaction time is preferably 30 minutes to 10 hours. This reaction is carried out without solvents or, if necessary, in the presence of aliphatic amines such as triethylamine, tripropylamine, tributylamine, tripentylamine, trihexylamine and the like, such as benzene, toluene, xylene, tripentylamine, trihexylamine and the like. Carried out using solvents such as benzene, toluene, xylene, trimethylbenzene, chlorobenzene, dichlorobenzene, trichlorobenzene, 1-chloronaphthalene, tetralin, pyridine, β-picolin, quinoline and the like in the presence of aliphatic amines It is preferable.

The naphthalocyanine derivatives of formula (I) can be isolated and purified from the reaction mixture, for example by separating off the reaction mixture by chromatography and then by recrystallization.

The naphthalocyanine derivative of the general formula (II) can be obtained by hydrolyzing the naphthalocyanine derivative of the following general formula (iii) with heating.

Wherein k, l, m and n may be the same or different and are an integer of 0 or 1 to 4, and k + l + m + n is an integer of 1 or more; R ¹ in the number of 4 (k + l + m + n) may be the same or different and is an alkyl group, a substituted alkyl group, or an aryl group; M is Si, Ge, or Sn; The two Xs may be the same or different and are halogen atoms. In this case, the reaction temperature is preferably 50 to 150 ° C, and the reaction time is preferably 30 minutes to 10 hours. According to these conditions, it is preferable to carry out the reaction in a mixed solvent such as pyridine / water, pyridine / aqueous ammonia, methanol / aqueous ammonia, ethanol / aqueous ammonia, propanol / aqueous ammonia and the like.

The naphthalocyanine derivative of formula (VII) is a 1,3-diiminobenz- [f] isoindolin derivative of formula (XII) or a metal halide of formula (XII) 1,3-diiminobenz- [f] isoindolin derivative of the following general formula (X) or 2,3-dicyonanaphthalene derivative of the following general formula (XI) together with the 2,3-dicyanonaphthalene derivative of This is obtained by heating and reacting with an amount of 0.1 to 1 mol of a metal halide of the following general formula (XII).

Wherein X is a halogen atom; p is a positive integer representing a plurality of Xs bonded to the metal M; M is Si, Ge, or Sn; R ¹ is the same or different alkyl group, substituted alkyl group or aryl group; n is an integer of 1 to 4, the same or different. In this case, the reaction temperature is preferably 150 to 300 ° C, and the reaction time is preferably 30 minutes to 10 hours. This reaction is carried out without solvent or by using solvents such as urea, tetralin, quinoline, 1-chloronaphthalene, 1-bromonaphthalene, trimethylbenzene, dichlorobenzene, trichlorobenzene and the like. This reaction is preferably carried out in the presence of an amine. Amines include triethylamine, tripropylamine, tributylamine, tripentylamine, trihexylamine, and the like. By the above-mentioned metal halide is _{SiCl 4, SiBr 4, SiI 4} , GeCl 4, GeBr 4, SnCl there are _2, SnI _2, etc.

1,3-Diiminobenz [f] isoindolin of general formula (X) is ammonia via 2,3-dicyanonaphthalene derivative of the following general formula in methanol in the presence of sodium methoxide as catalyst Obtained by refluxing for 1 to 10 hours while bubbling gas.

The 2,3-dicyanonaphthalene derivative of general formula (XI) can be manufactured mainly by the following two methods.

One of the methods was carried out by heating the o-xylene derivative of the general formula (XIII) and N-bromosuccinimide of the general formula (XIV) to obtain a compound of the general formula (XV), It is characterized by the synthesis of 2,3-cyanonaphthalene of the general formula (XI) by reacting with fumaronitrile of the general formula (XVI) with heating.

Wherein R ¹ is the same or different alkyl group, substituted alkyl group or aryl group; n is an integer of 1-4.

Reactions of o-xylene derivatives of general formula (XIII) with N-bromosuccinimide of general formula (XIV) are typically 0.2 mol of o-xylene derivatives under irradiation with high pressure mercury arc or the like in a solvent inert to the irradiation; 0.8 mol of N-bromosuccinimide is carried out at reflux for 4-12 hours. This reaction requires the addition of peroxides which can generate radicals as reaction initiators. Peroxides include benzoyl peroxide, octanoyl peroxide, cyclohexanone peroxide, isobutyryl peroxide, 2,4-dichlorobenzoyl peroxide, methylethylketone peroxide, and the like. The solvent inert to the irradiation is suitably selected from halogenated solvents such as chloroform, carbon tetrachloride, or aromatic solvents such as benzene, chlorobenzene and the like.

The next reaction of the compound of formula (XV) with fumaronitrile of formula (XVI) is carried out in combination with the compound of formula (XVI) per mol of the compound of formula (XV) with the compound of formula (XV). It is carried out by heating to an amount of 1 to 2 mol of fumaronitrile of formula (XVI). The reaction temperature is preferably 70 ° to 100 ° C, and the reaction time is preferably 5 to 10 hours. As the solvent, polar organic solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, N, N-diethylformamide, N, N-diethylacetamide and the like are preferable.

In another method, the 2,3-dicyanonaphthalene derivative is subjected to a substitution reaction of bromo-2,3-dicyanonaphthalene of the general formula (X ') with an excess copper (I) thiolate of the general formula (X). It can be obtained by performing.

Wherein n is an integer of 1 to 4, and R ¹ is an alkyl group, a substituted alkyl group or an aryl group. In this case, the reaction temperature is preferably 80 to 250 ° C, and the reaction time is preferably 1 to 30 hours.

As the solvent for the present invention, benzene, toluene, xylene, trimethylbenzene, chlorobenzene, dichlorobenzene, trichlorobenzene, 1-chloronaphthalene, tetralin, pyridine, β-picolin, quinoline and the like alone or in combination thereof Used as a solvent.

Bromo-2,3-dicyonanaphthalene of the general formula (X ') is, for example, by the method described in Zhurnal Organicheskoi Khimii, vol. 7, p369 (1971). Can be synthesized.

Specifically, bromo-o-xylene (X ') and N-bromosuccinimide of the following general formula (XIV) are irradiated with light while heating to bromo of bis (dibromomethyl) bromobenzene (X'). Obtain -2,3-dicyonanaphthalene:

Typically, the reaction of bromo-o-xylene of general formula (X ') with N-bromosuccinimide of general formula (XIV) is bromo-o under irradiation with high pressure mercury arc or the like in a solvent inert to the irradiation. 0.2 mol xylene and 0.8 mol N-bromosuccinimide are carried out at reflux for 4 to 12 hours. This reaction requires the addition of peroxides which can generate radicals as reaction initiators. Peroxides include benzoyl peroxide, octanoyl peroxide, cyclohexanone peroxide, isobutylyl peroxide, 2,4-dichlorobenzoyl peroxide, methylethylketone peroxide, and the like. Peroxides are typically used in amounts of 500 mg to 2 g per 500 ml of solvent. The solvent inert to the irradiation is suitably selected from halogenated solvents such as chloroform, carbon tetrachloride, or aromatic solvents such as benzene, chlorobenzene and the like.

The following reaction of the compound of general formula (X ') with the fumaronitrile of general formula (XVI) is combined with the compound of general formula (XVI) per mol of the compound of general formula (X') It is carried out by heating to an amount of 1 to 2 mol of formula (XVI). The reaction temperature is preferably 70 to 100 ° C, and the reaction time is preferably 5 to 10 hours. As the solvent, polar organic solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, N, N-diethylformamide, N, N-diethylacetamide and the like are preferable.

The present invention also provides a method for producing a naphthalocyanine derivative of the general formula (I), characterized in that the naphthalocyanine derivative of the general formula (I) reacts with the thiolate of copper (I) of the general formula (I). to provide.

Wherein k, l, m and n may be the same or different and are an integer of 0 or 1 to 4, and k + l + m + n is an integer of 1 or more; R ¹ is an alkyl group, a substituted alkyl group, or an aryl group; M is Si, Ge, or Sn; The two Y's may be the same or different and are an aryloxyl group, an alkoxyl group, a trialkyloxyloxy group, a triaryloxyloxyl group, a trialkoxyoxyloxyl group, a triaryloxyoxyloxyl group, a trityloxyl group or an aryloxyl group.

The naphthalocyanine derivative of general formula (I) can be obtained by performing a substitution reaction, heating the compound of general formula (IV) with the excess copper (I) thiolate of general formula (IX). In this case, the reaction temperature is preferably 80 to 250 ° C, and the reaction time is preferably 1 to 30 hours. As a solvent for this reaction, benzene, toluene, xylene, trimethylbenzene, chlorobenzene, dichlorobenzene, trichlorobenzene, 1-chloronaphthalene, tetralin, pyridine, β-picolin, quinoline and the like alone or in combination thereof Used as a solution.

In order to produce naphthalocyanine derivatives of the general formula (I) wherein R ¹ are different substituents, various copper (I) compounds of the general formula (I) having naphthalocyanine derivatives of the general formula (Ⅶ) having substituents corresponding to different substituents It is necessary to react with thiolates.

Naphthalocyanine derivatives of general formula (I) can be isolated and purified from the reaction mixture, for example by column chromatography or thin membrane chromatography to separate the reaction mixture and then by recrystallization.

The naphthalocyanine derivative of the general formula (VII) is a chlorosilane of the following general formula (III) and the silane of the following general formula (IV) in excess of the naphthalocyanine derivative of the following general formula (XX). It is obtained by reacting with an alcohol or a compound of the following general formula (VI) while heating.

Wherein k, l, m and n may be the same or different and are an integer of 0 or 1 to 4, and k + l + m + n is an integer of 1 or more; M is Si, Ge, or Sn. R ² and R ³ are each an alkyl group, an aryl group, an alkoxyl group, or an aryloxy group. R ⁴ is an alkyl group or an aryl group. R ⁵ is an alkyl group, X is a halogen atom, a hydroxyl group or an acyloxyl group. In this case, the reaction temperature is preferably 80 to 250 ° C, and the reaction time is preferably 30 minutes to 10 hours. This reaction is carried out in the presence of aliphatic amines, such as triethylamine, tripropylamine, tributylamine, tripentylamine, trihexylamine, etc., without solvents or when necessary, benzene, toluene, xylene, trimethylbenzene, chlorobenzene, dichlorobenzene, Preference is given to using solvents such as trichlorobenzene, 1-chloronaphthalene, tetralin, pyridine, β-picolin, quinoline and the like.

Naphthalocyanine derivatives of the general formula can be separated and purified from the reaction mixture by chromatography and then purified by recrystallization.

The naphthalocyanine derivative of formula (XX) is treated with the naphthalocyanine derivative of formula (XXI) below with concentrated sulfuric acid for 1 to 10 hours at room temperature and then refluxed in concentrated liquid ammonia for 30 minutes to 10 hours, or It can be obtained by refluxing in pyridine / water, pyridine / aqueous ammonia, methanol / aqueous ammonia, ethanol / aqueous ammonia or propanol / aqueous ammonia for 30 minutes to 10 hours.

Wherein k, l, m and n may be the same or different and are an integer of 0 or 1 to 4, and k + l + m + n is an integer of 1 or more; M is Si, Ge, or Sn; The two Xs may be the same or different and are halogen atoms.

The naphthalocyanine derivative of the general formula (XXI) is a metal halide of the general formula (XII) together with the bromo-1,3-diiminobenz [f] isoindolin of the general formula (XXII) XXII), obtained by heating in an amount of 0.1 to 1 mol of the metal halide of the general formula (XII) per 1 mol of bromo-1,3-diiminobenz [f] isoindolin.

Wherein X is a halogen atom; p is a positive integer indicating the number of X bonded to the metal M; M is Si, Ge, or Sn. n is an integer of 1-4. In this case, the reaction temperature is preferably 150 to 300 ° C, and the reaction time is preferably 30 minutes to 10 hours. This reaction can be carried out without solvent or using solvents such as urea, tetralin, quinoline, 1-chloronaphthalene, 1-bromonaphthalene, trimethylbenzene, dichlorobenzene, trichlorobenzene and the like. This reaction is preferably carried out in the presence of an amine. Amines include triethylamine, tripropylamine, tributylamine, tripentylamine, trihexylamine, and the like. The above-mentioned metal halide has a _{SiCl 4, SiBr 4, SiI 4} , GeCl 4, GeBr 4, SnCl 2, SnI 2 , etc.

Bromo-1,3-diiminobenz [f] isoindolin of formula (XXII) is bromo-2,3-dicyonanaphthalene of formula (X ') in methanol in the presence of sodium methoxide as catalyst It is obtained by refluxing for 1 to 10 hours while bubbling ammonia gas therethrough.

In said formula, n is an integer of 1-4.

In the above-mentioned second and third aspects of the present invention, I in which M in formulas (II), (I), (IX), (XII), (IX), (XIX) and (XXI) is Si or Ge, Preference is given to a method for producing a phthalocyanine derivative.

In the second and third aspects of the invention, general formulas (II), (I), (IX), (X), (XI), (XIII), (XV), (X '), (X'), (X ') A method for producing a naphthalocyanine derivative in which k, l, m and n are all 1 in (Xi), (XX), (XXI) or (XXII) is preferred.

In the second and third aspects of the invention, each of R ² and R ³ in formulas (III) and (IV) is an alkyl group, and naphthalocyanine wherein two Y in formulas (I) and ( ⁱⁱⁱ ) are trialkyloxyoxyl groups Preference is given to the preparation of the derivatives.

In the second and third aspects of the invention, all of R ¹ in general formulas (II), (I), (IX), (X), (XI), (XIII), (XV) and (iii) have 1 to The manufacturing method of the naphthalocyanine derivative which is an alkyl group which has 22 is preferable.

In the second and third aspects of the invention, alkyl groups wherein all R ¹ in general formulas (I), (II), (IX), (X), (XI), (XIII), (XV) and (iii) are substituted Preferred is a method for producing a phosphorus naphthalocyanine derivative.

Furthermore, the present invention provides an optical recording medium composed of a substrate and a recording layer formed on the surface of the substrate, which recording layer is mainly composed of a naphthalocyanine derivative of general formula (I).

Wherein k, l, m, n, R ¹ , M and Y are as defined above.

The optical recording medium of the present invention is composed of a recording layer mainly composed of a substrate and a naphthalocyanine derivative represented by the general formula (I) of the present invention formed thereon. If necessary, other layers, such as a primer layer, a protective layer, etc. can be formed.

The base materials used are known to those skilled in the art and may be transmissive or impermeable to the laser beam used. However, when writing and reading is performed using a laser beam from the substrate surface, the substrate material must be transparent to the laser beam. On the other hand, when writing and reading is performed using a laser beam from the opposite side of the substrate, that is, from the recording layer surface, the substrate material need not be transparent to the laser beam used. Substrate material is a substance such as glass, quartz, mica, ceramic, metal in the form of a plate or thin film; Paper, polycarbonate, polyester, cellulose acetate, nitrocellulose, polyethylene, polypropylene, polyvinyl chloride, vinylidene chloride copolymer, polyamide, polystyrene, polymethylmethacrylate, methylmethacrylate copolymer, etc. There is a plate of the same organic macromolecular material. The base material is not limited thereto. The base material is preferably a support made of an organic polymer having low thermal conductivity, in order to reduce heat loss during recording and to enhance sensitivity, and guide grooves may be formed in the downward and upward forms on the substrate if necessary. Can be.

If necessary, a primer layer may be formed on the substrate.

Preference is given to an optical recording medium having a recording layer composed mainly of naphthalocyanine derivatives of general formula (I) wherein M is Si or Ge.

Preference is given to an optical recording medium having a recording layer mainly composed of naphthalocyanine derivatives of general formula (I) wherein k, l, m and n are all one.

Preference is given to an optical recording medium having a recording layer composed mainly of naphthalocyanine derivatives of general formula (I) in which two Y's are trialkyloxylyl groups.

Preference is given to an optical recording medium having a recording layer mainly composed of naphthalocyanine derivatives of the general formula (I) in which all R ¹ are alkyl groups having 1 to 22 carbon atoms.

Also preferred is an optical recording medium having a recording layer composed mainly of naphthalocyanine derivatives of general formula (I) in which all of R ¹ are substituted with alkyl groups.

In addition, the present invention provides a method for producing an optical recording medium comprising forming a recording film or a layer on the surface of a substrate using a solution prepared by dissolving a naphthalocyanine derivative of the general formula (I) in an organic solvent as a main component. To provide.

(Wherein k, l, m, n, R ¹ , M and Y are as defined above).

The organic solvent is selected from the group of the aforementioned aromatic solvents, halogenated solvents, ether solvents, ketone solvents and saturated hydrocarbon solvents capable of dissolving naphthalocyanine derivatives of general formula (I). These solvents may be used alone or as mixed solvents thereof. Preference is given to using a solvent which does not attack the substrate used.

As a method of forming a recording film using a solution of naphthalocyanine derivative of general formula (I) dissolved in an organic solvent, there are a coating method, a printing method and a immersion method. In particular, in forming the recording medium in which the dye is dissolved in the above-described solvent, and the recording film is formed by spraying, roller coating, spin coating or dipping, a binder such as a polymer binder, a stabilizer, or the like can be added if necessary. . The binder may be a polyamide resin, a polyamide resin, a polystyrene resin, an acrylic resin, but is not limited thereto.

The recording layer material is used alone or in combination of two or more thereof. When blending two or more, a laminate structure or a mixture of single layer structures can be used. As for the thickness of a recording layer, 50-10000 micrometers, especially 100-5000 micrometers are preferable.

When reading the recorded information, the reflected light may be used. In this case, the following method is effective for increasing the control. When writing and reading are performed from the substrate surface, a metal layer having high reflectivity can be formed on the surface of the recording layer in the reverse direction to the substrate. When writing and reading are performed from the opposite side of the substrate, that is, from the recording layer surface, a metal layer having high reflectivity can be formed between the substrate and the recording layer. Al, Cr, Au, Pt, Sn, etc. are used as a metal with high reflectivity. Films of these metals can be formed by known thin film forming techniques such as vacuum deposition, sputtering, plasma deposition and the like, the thickness of which is selected in the range of 100 to 10000 mm 3.

However, since naphthalocyanine itself has high reflectivity, it does not require formation of a metal reflective layer.

When there is a problem with the surface smoothness of the substrate itself, it is desirable to form a uniform film of organic polymer on the substrate. As the polymer, commercially available polymers such as polyester, polyvinyl chloride and the like can be used.

Furthermore, a protective layer can be formed as the outermost layer to increase stability and protection. It is also possible to form layers for increasing sensitivity by reducing surface reflectivity. The materials used in these protective layers are polyvinylidene chloride, polyvinylchloride, copolymers of vinylidene chloride and acrylonitrile, polyvinylacetate, polyimide, polymethylmethacrylate, polystyrene, polyisoprene, polybutadiene, poly Urethane, polyvinyl butyral, fluororubber, polyester, epoxy resin, silicone resin, cellulose acetate and the like. These materials may be used alone or in mixtures thereof. In order to improve the characteristic of a film, it is preferable to exist silicone oil, an antistatic agent, a crosslinking agent, etc. in a protective layer. The protective layer may be composed of two layers overlapping each other. The aforementioned materials for the protective layer can be coated in the form of a solution dissolved in a suitable solvent or laminated in the form of a thin film. The thickness of the protective layer is adjusted to 0.1 to 10 µm, preferably 0.1 to 2 µm.

A method for producing an optical recording medium using a naphthalocyanine derivative of formula (I) wherein M is Si or Ge is preferred.

Also preferred is a method of manufacturing an optical recording medium using a naphthalocyanine derivative of formula (I) wherein k, l, m and n are all one.

Also preferred is a method of producing an optical recording medium using a naphthalocyanine derivative of formula (I) wherein two Ys are trialkyloxylyl groups.

Also preferred is a method for producing an optical recording medium using a naphthalocyanine derivative of the general formula (I) in which all R ¹ are alkyl groups having 1 to 22 carbon atoms.

Also preferred is a method of producing an optical recording medium using all substituted naphthalocyanine derivatives of general formula (I).

The invention is illustrated by the following examples, which do not limit the invention.

Synthesis Example 1

[Synthesis of 3,4-bis (dibromomethyl) bromo benzene)

1 g of a solution of 37 g (0.2 mol) of 4-bromo-o-xylene (75%) (Aldrich Chemical) and 142.4 g (0.8 mol) of N-bromosuccinimide dissolved in 500 ml of carbon tetrachloride Benzoyl peroxide is added and the resulting mixture is irradiated with 100-W high pressure mercury arc or the like for 8-12 hours under reflux in an internal irradiation tube (manufactured by Ushio Corporation). After cooling the mixture, the precipitated white crystals were collected by filtration and the carbon tetrachloride solution, ie the mother liquor, was concentrated under reduced pressure. The solid thus obtained is recrystallized from hexane 1methylene chloride to give 64 g of 3,4-bis (dibromomethyl) bromobenzene as colorless crystals. Physical properties of 3,4-bis (dibromomethyl) bromobenzene are as follows:

(1) Melting Point: 108.5˚ ~ 110.5 ℃

(2) Elemental Analysis Values:

Calculated (%): C; 19.19, H; 1.01, Br; 79.80

Found (%): C; 19.12, H; 0.88, Br; 79.84

(3) NMR spectral value: CDCl ₃

δ value: 7.81 (1H, br-s), 7.57 (1H, d, J = 8.54 Hz), 7.50 (1H, dd, J = 8.54, 1.83 Hz), 7.06 (1H, s), 7.02 (1H, s )

(4) The IR spectrum KBr is shown in FIG.

Synthesis Example 2

[Synthesis of 6-bromo-2,3-dicyano naphthalene]

With sufficient stirring in a solution of 100.2 g (0.2 mol) of 3,4-bis (dibromomethyl) bromobenzene and 27 g (0.346 mol) of fumaronitrile dissolved in 800 ml of anhydrous N, N-dimethylformamide 200 g (0.67 mol) of sodium iodide are added and the resulting mixture is stirred at about 75 ° C. for about 7 hours under nitrogen. After completion of the reaction, the reaction mixture is poured on about 4 kg of ice. Sodium hydrogen sulfate is slowly added until the resulting reddish brown aqueous solution becomes light yellow. A small amount of sodium hydrogen sulfite is added and stirred for a while. The resulting mixture is left overnight at room temperature. The precipitated pale yellow solid is filtered off and washed thoroughly with water and methanol. The light yellow solid is recrystallized from acetone / methanol to give 33 g of colorless needles. This crystal is confirmed to be 6-bromo-2,3-dicyano naphthalene from the following analysis result.

(1) Melting Point: 254.5˚-255.5 ℃

(2) Elemental Analysis Values:

Calculated (%): C; 56.06, H; 1.96, N; 10.90, Br; 31.08

Found (%): C; 55.99, H; 1.67, N; 10.87, Br; 30.74

(3) NMR spectral value: CDCl ₃ (NMR spectrum is shown in FIG. 2).

δ value: 8.34 (1H, s), 8.27 (1H, s), 8.17 (1H, br-s), 7.88 (2H, m)

(4) IR spectrum (KBR) is shown in FIG.

Synthesis Example 3

[Synthesis of 6-bromo-1,3-diiminobenz [f] isoindolin]

Under nitrogen, 44.1 g (0.172 mol) of 6-bromo-2,3-dicyanonaphthalene was added to a sodium methoxide solution in methanol prepared by adding 1.92 g (84 mmol) of metallic sodium to 270 ml of anhydrous methanol. Anhydrous ammonia gas is bubbled slowly for 1 hour. The mixture is refluxed for about 3 hours with bubbling anhydrous ammonia gas therethrough. After cooling, the yellow solid precipitate is filtered and the residue is washed with methanol and dried under reduced pressure to yield 45 g of 6-bromo-1-3-diiminobenz [f] isoindolin, a yellow solid. IR spectrum of 6-bromo-1,3-diiminobenz [f] isoindolin is shown in FIG. This 6-bromo-1,3-diiminobenz [f] isoindolin is used in subsequent reactions without further purification.

Synthesis Example 4

[Synthesis of Dichlorosilicon-tetrabromo naphthalocyanine (Formula (XXI): M is Si; S is a chlorine atom: k, l, m and n are all 1)]

54 ml of anhydrous tri-n-butylamine was added to a suspension of 22.5 g (81.8 mmol) of 6-bromo-1,3-diiminobenz [f] isoindolin in 110 ml of anhydrous tetralin under nitrogen, and silicon tetrachloride 14.4 ml (0.126 mol) was added and the resulting mixture was refluxed for 3 hours. After cooling, 700 ml of methanol is added and the resulting mixture is left overnight.

The reddish brown reaction mixture was filtered, the residue was washed sufficiently with methanol and dried under reduced pressure to give dichloro silicon-tetrabromonaphthalocyanine (formula (XXI): M is Si, X is chlorine atom, and k, l, m) And n are all 1) 20 g are obtained as a dark green solid. This dichlorosilicon-tetrabromonaphthalocyanine is used in the subsequent reaction without further purification. The IR spectrum of dichlorosilicon-tetrabromonaphthalocyanine is shown in FIG. Its electron spectrum is shown in FIG.

Synthesis Example 5

[Synthesis of Dihydroxysilicone-tetrabromonaphthalocyanine (General Formula (XX): M is Si; k, l, m and n are all 1)]

To 250 ml of concentrated sulfuric acid, 9.7 g (8.6 mmol) of dichlorosilicone-tetrabromonaphthalocyanine are added and stirred for about 2 hours. The reaction mixture is poured into 800 g of ice and the resulting mixture is left overnight. The resulting precipitate is filtered off, washed well with water and then with methanol, and then the precipitate is refluxed in 180 ml of concentrated aqueous ammonia for about 1 hour. After filtration and cooling, the residue was washed thoroughly with water, methanol and acetone in order and dried under reduced pressure to give dihydroxy silicon-tetrabromonaphthalocyanine (formula (XX): M is Si, k, l, m and n are both 1.) 8.7 g is obtained as a dark green solid. This dihydroxy silicone-tetrabromonaphthalocyanine is used in subsequent reactions without further purification. The IR spectrum of dihydroxysilicone-tetrabromonaphthalocyanine is shown in FIG. Its electron spectrum is shown in FIG.

Synthesis Example 6

[Bis- (tri-n-propylsiloxy) silicone-tetrabromonaphthalocyanine (formula (VII): M is Si; k, l, m and n are all 1 and Y is tri-n-propyl silane) Synthesis]

Under nitrogen, 8 ml (33.6 m mol) of anhydrous tri-n-butylamine was added to a suspension of 2.82 g (2.6 m mol) of dihydroxysilicone-tetrabromonaphthalocyanine in 280 ml of anhydrous β-picolin, and tri-n-propyl After adding 7.2 ml (32.8 mmol) of chlorosilanes, the resulting mixture is refluxed for about 2 hours. After cooling, the mixture is poured into 600 ml of ethanol / mole (1/1), and the resulting mixture is stirred well and left overnight. The resulting precipitate is filtered off, washed with water and then with methanol.

Only soluble material in the precipitate was extracted with hot chloroform, purified by silica gel column chromatography and recrystallized from chloroform to yield 0.82 g of dark green crystals. Dark green crystals are bis (tri-n-propylsiloxy) silicone-tetrabromonaphthalocyanine (formula: M is Si; k, l, m and n are all 1; Y is tri-n-propyl siloxane It is confirmed from the following analysis result.

(1) Melting Point: 300 ℃ or higher

(2) Elemental Analysis Values:

Calculated (%): C; 56.50, H; 4.45, N; 7.99, Br; 22.78

Found (%): C; 56.28, H; 4.39, N; 8.04, Br; 22.45

(3) NMR spectral values (NMR spectra are shown in FIG. 9). : CDCl ₃

δ value; 10.08 (4H, br-s), 10.01 (4H, br-s), 8.83 (4H, br-s), 8.54 (4H, dd, J = 8.85, 3.05 Hz), 8.00 (4H, d, J = 8.85 Hz), -0.29 (18H, t, J = 7.17 Hz), -0.90 (12H, 6-line like m), -2.08 (12H, triple-line like m)

(4) The electron spectrum (CHCl ₃ solution) is shown in FIG.

(5) The IR spectrum KBr is shown in FIG.

Synthesis Example 7

[Bis- (tri-n-butylsiloxy) silicone-tetrabromonaphthalocyanine (General Formula: M is Si; 0k, l, m and n are all 1; Y is a tri-n-butyloxyl group Synthesis of

8 ml (33.6 m mol) of anhydrous tri-n-butylamine was added to a suspension of 2.82 g (2.6 m mol) of dihydroxysilicone-tetrabromonaphthalocyanine in 280 ml of anhydrous β-picolin, and tri-n-butylchlorosilane 8.8 ml (32.8 mmol) was added to reflux the resulting mixture for about 2 hours. After cooling, the reaction mixture was treated in the same manner as in Synthesis Example 6 and recrystallized from chloroform to give 0.75 g of dark green crystals. Dark green crystals are bis (tri-n-butylsiloxy) silicone-tetrabromonaphthalocyanine (formula: M is Si; k, l, m and n are all 1; and Y is tri-n- Butyloxyoxy group).

(1) Melting Point: 300 ℃ or higher

(2) Elemental Analysis Values:

Calculated (%): C; 58.14, H; 5.02, N; 7.53, Br; 21.49

Found (%): C; 58.36, H; 5.11, N; 7.51, Br; 21.03

(3) NMR spectrum value (NMR spectrum is shown in FIG. 12). :

δ value: 10.09 (4H, br-s), 10.02 (4H, br-s), 8.85 (4H, br-s), 8.55 (4H, dd, J = 8.85, 3.05 Hz), 8.01 (4H, d, J = 8.85 Hz), 0.02 (30H, m), -0.99 (12H, 6-line like m), -2.07 (12H, triple-line like m)

(4) The electron spectrum (CHCl ₃ solution) is shown in FIG.

(5) The IR spectrum Br is shown in FIG.

Synthesis Example 8

[Bis- (tri-n-hexyloxyoxy) silicone-tetrabromonaphthalocyanine (General Formula: M is Si; k, l, m and n are all 1; Y is tri-n-hexyloxyl Synthesis]

8 ml (33.6 m mol) of anhydrous tri-n-butylamine was added to a suspension of 2.82 g (26 m mol) of dihydroxysilicone-tetrabromonaphthalocyanine in 280 ml of anhydrous β-picoline, followed by 12 ml of tri-n-hexylchlorosilane. (32.8 mmol) is added and the resulting mixture is refluxed for about 2 hours. After cooling, the reaction mixture was treated in the same manner as in Synthesis Example 6 and recrystallized from hexane / chloroform to give 0.78 g of dark green crystals. Dark green crystals are bis (tri-n-hexyloxy) silicone-tetrabromonaphthalocyanine (formula: M is Si; k, l, m and n are all 1; Y is tri-n-hexyl Oxyl group) can be confirmed from the following analysis results.

(1) Melting Point: 298˚ ~ 300 ℃ or higher

(2) Elemental Analysis Values:

Calculated (%): C; 60.94, H; 5.97, N; 6.77, Br; 19.30

Found (%): C; 60.77, H; 5.71, N; 6.65, Br; 19.02

(3) NMR spectral values (the NMR spectrum is shown in FIG. 15). : CDCl ₃

δ value: 10.06 (4H, br-s), 10.00 (4H, br-s), 8.83 (4H, br-s), 8.53 (4H, dd, J = 8.85, 2.44 Hz), 7.99 (4H, d, d, J = 8.85 Hz), 0.63 (12H, hexadecimal, J = 7.32 Hz), 0.45 (18H, t, J = 7.32 Hz), 0.22 (12H, quartet, J = 7.32 Hz), 0.05 (12H, Quadruple, J = 7.32 Hz), -1.02 (12H, quadruple-like m), -2.10 (12H, triplet-like m)

(4) The electron spectrum (CHCl ₃ solution) is shown in FIG.

(5) IR spectrum (KBR) is shown in FIG.

Synthesis Example 9

[Synthesis of bis (triethylsiloxy) silicone-tetrabromonaphthalocyanine (formula: M is Si; k, l, m and n are all 1 and Y is triethyloxyl group)]

In 10 ml of quinoline, 10 ml (65 mmol) of triethylsilanol was added to a suspension of 2.82 g (2.6 mmol) of dihydroxysilicone-tetrabromonaphthalocyanine and the resulting solution was refluxed for about 3 hours. After cooling, the reaction mixture is poured into 500 ml of ethanol / water (1/1), after sufficient stirring, the resulting mixture is left overnight. The resulting precipitate is filtered off and the residue is washed sufficiently with methanol followed by chloroform. The crystals thus obtained were washed with chloroform by a soxhlet extraction method to yield 2.1 g of dark green crystals. The dark green crystals are bis (triethylsiloxy) silicone-tetrabromonaphthalocyanine (formula: M is Si; k, l, m and n are all 1; Y is triethyloxyl group) from the following analysis. Check that it is.

(1) Melting Point: 300 ℃ or higher

(2) Elemental Analysis Values:

Calculated (%): C; 54.64, H; 3.82, N; 8.50, Br; 24.23

Found (%): C; 54.18, H; 3.62, N; 8.81, Br 23.94

(3) NMR spectral value: CDCl ₃

δ value: 10.07 (4H, br-s), 10.00 (4H, br-s), 8.83 (4H, br-s), 8.54 (4H, dd, J = 8.85, 3.05 Hz), 8.01 (4H, d, J = 8.85 Hz), -1.04 (18H, t, J = 7.32 Hz), -2.05 (12H, q, J = 7.32 Hz)

(4) The electron spectrum (CHCl ₃ solution) is shown in FIG.

(5) The IR spectrum KBr is shown in FIG.

Example 1

[Synthesis of bis (tri-n-propylsiloxy) silicon-tetra (n-dodecylthio) naphthalocyanine [Compound (100)]]

In a solution of 140 mg (0.1 mmol) of bis (tri-n-propylsiloxy) silicone-tetrabromonaphthalocyanine in a mixture of 3.2 ml of pyridine and 10 ml of quinoline, the method described in Organic Synthesis Vol. 42, p.22], 2.33 g (8.8 m mol) of copper (I) n-dodecylthiolate synthesized according to the method described in the above was added, and the resultant mixture was refluxed at 160 to 170 ° C for 8 hours. After cooling, the resultant mixture is poured into 200 ml of methanol, the resultant mixture is sufficiently stirred, and left at room temperature overnight. The resulting precipitate is filtered off, washed sufficiently with methanol and only the material soluble in benzene is extracted from the precipitate with benzene. The benzene solution is concentrated, separated by alumina column chromatography and recrystallized with chloroform / ethanol to give 138 mg (73%) of yellow green crystals. The yellow green crystals were identified as bis (tri-n-propylsiloxy) silicone-tetra (n-dodecylthio) naphthalocyanine) [Compound (100)] from the following analysis.

(1) Melting Point: 145 ~ 149 ℃

(2) Elemental Analysis Values:

Calculated (%): C; 72.48, H; 8.64, N; 5.93

Found (%): C; 72.61, H; 8.65, N; 5.87

(3) NMR spectrum value (NMR spectrum is shown in FIG. 20). : CDCl ₃

δ value: 9.94 (4H, br-s), 9.89 (4H, br-s), 8.45 (4H, d, J = 8.85 Hz), 8.37 (4H, br-s), 7.72 (4H, d, J = 8.85 Hz), 3.23 (8H, t, J = 7.33 Hz), 1.86 (8H, quadruple, J = 7.33 Hz), 1.56 (8H, m), 1.22 (64H, m), 0.81 (12H, triplet similar m), -0.33 (18H, t, J = 7.33 Hz), -0.92 (12H, hexadecimal barn m), -2.13 (12H, triplet like m)

(4) The electron spectrum (CHCl ₃ solution) is shown in FIG.

(5) IR spectrum (KBR) is shown in FIG.

Example 2

[Synthesis of bis- (tri-n-propylsiloxy) silicon-tetra (n-tetradecylthio) naphthalocyanine [Compound (101)]]

In a solution of 140 mg (0.1 m mol) of bis (tri-n-propylsiloxy) silicone-tetrabromonaphthalocyanine in a mixture of 10 ml of quinoline and 3.2 ml of pyridine is described in Organic Synthesis Vol. 42, p.22], 2.53 g (8.8 m mols) of copper (I) n-tetradecylthiolate synthesized according to the method described in the above was added, and the resultant mixture was refluxed at 160 to 170 ° C for 8 hours. After cooling, the reaction mixture was treated in the same manner as in Example 1 to yield 126 mg (63%) of yellow green crystals. The yellow green crystals were identified as bis (tri-n-propylsiloxy) silicon-tetra (n-tetradecylthio) naphthalocyanine) (Compound (101)) from the following analysis.

(1) Melting Point: 141˚ ~ 143 ℃

(2) Elemental Analysis Values:

Calculated (%): C; 73.21, H; 8.97, N; 5.60

Found (%): C; 73.36, H; 8.99, N; 5.58

(3) NMR spectral values (the NMR spectrum is shown in FIG. 23). : CDCl ₃

δ value: 10.01 (4H, br-s), 9.96 (4H, br-s), 8.53 (4H, d, J = 8.85 Hz), 8.45 (4H, br-s), 7.80 (4H, d, J = 8.85 Hz), 3.30 (8H, t, J = 7.17 Hz), 1.94 (8H, quadruple, J = 7.17 Hz), 1.64 (8H, m), 1.27 (80H, m), 0.81 (12H, triplet similar m), -0.26 (18H, t, J = 7.17 Hz), -0.85 (12H, triplet like m), -2.06 (12H, triplet like m)

(4) The electron spectrum (CHCl ₃ solution) is shown in FIG.

(5) The IR spectrum KBr is shown in FIG.

Example 3

[Synthesis of bis- (tri-n-propylsiloxy) silicon-tetra (n-hexadecylthio) naphthalocyanine [Compound (105)]]

In a solution of 140 mg (0.1 m mol) of bis (tri-n-propylsiloxy) silicone-tetrabromonaphthalocyanine in a mixture of 10 ml of quinoline and 3.2 ml of pyridine is described in Organic Synthesis Vol. 42, p.22], 2.82 g (8.8 m mol) of copper (I) n-hexadecylthiolate synthesized according to the method described in the above was added, and the resultant mixture was refluxed at 160 to 170 ° C for 8 hours. After cooling, the resulting mixture was treated in the same manner as in Example 1 to yield 144 mg (68%) of yellow green crystals. The yellow green crystals were identified as bis (tri-n-propylsiloxy) silicone-tetra (n-hexadecylthio) naphthalocyanine) (Compound 105) from the following analysis.

(1) Melting Point: 130.5˚ ~ 132.5 ℃

(2) Elemental Analysis Values:

Calculated (%): C; 73.87, H; 9.25, N; 5.30

Found (%): C; 73.91, H; 9.33, N; 5.35

(3) NMR spectral values (NMR spectra are shown in FIG. 26). : CDCl ₃

δ value: 10.02 (4H, br-s), 9.97 (4H, br-s), 8.52 (4H, d, J = 8.85 Hz), 8.45 (4H, br-s), 7.80 (4H, d, J = 8.85 Hz), 3.30 (8H, t, J = 7.33 Hz), 1.94 (8H, quadruple, J = 7.33 Hz), 1.64 (8H, m), 1.26 (96H, m), 0.87 (12H, triplet similar m), -0.25 (18H, t, J = 7.33 Hz), -0.84 (12H, triplet like m), -2.05 (12H, triplet like m)

(4) The electron spectrum (CHCl ₃ solution) is shown in FIG.

(5) The IR spectrum KBr is shown in FIG.

Example 4

[Synthesis of Bis (tri-n-propylsiloxy) silicone-tetra (n-decylthio) naphthalocyanine [Compound (99)]

A solution of 140 mg (0.1 mmol) of bis (tri-n-propyloxy) silicone-tetrabromonaphthalocyanine in a mixture of 10 ml of quinoline and 3.2 ml of pyridine was described in Organic Synthesis Vol. 42, p.22], 2.08 g (8.8 mmol) of copper (I) n-decylthiolate synthesized according to the method described above was added, and the resulting mixture was refluxed at 160 to 170 ° C for 8 hours. After cooling, the reaction mixture was treated in the same manner as in Example 1 to yield 121 mg (68%) of yellow green crystals. The yellow green crystals were identified as bis (tri-n-propylsiloxy) silicon-tetra (n-decylthio) naphthalocyanine) [Compound (99)] from the following analysis.

(1) Melting Point: 166˚ ~ 169 ℃

(2) Elemental Analysis Values:

Calculated (%): C; 71.65, H; 8.28, N; 6.31

Found (%): C; 71.81, H; 8.31, N; 6.28

(3) NMR spectral values (the NMR spectrum is shown in FIG. 29). : CDCl ₃ δ value 10.02 (4H, br-s), 9.97 (4H, br-s), 8.52 (4H, d, J = 8.55 Hz), 8.45 (4H, br-s), 7.80 (4H, d, J = 8.55Hz), 3.30 (8H, t, J = 7.32Hz), 1.94 (8H, Quad, J = 7.32Hz), 1.64 (8H, m), 1.32 (48H, m), 0.90 (12H, 3 Midline like m), -0.26 (18H, t, J = 7.32 Hz), -0.85 (12H, hexaline like m), -2.05 (12H, triple like line m)

(4) The electron spectrum (CHCl ₃ solution) is shown in FIG.

(5) The IR spectrum KBr is shown in FIG.

Example 5

[Synthesis of bis (tri-n-butylsiloxy) silicon-tetra (n-dodecylthio) naphthalocyanine (compound (103))]

A solution of 142 mg (0.1 mmol) of bis (tri-n-butylsiloxy) silicone-tetrabromo naphthalocyanine in a mixture of 10 ml of quinoline and 3.2 ml of pyridine was described in Organic Synthesis Vol. 42, p.22] copper (I) n-dodecylthiolate synthesized according to the method described in the following, and the resulting mixture was refluxed at 160 to 170 ℃ for 8 hours. After cooling, the reaction mixture was treated in the same manner as in Example 1 to yield 114 mg (58%) of yellow green crystals. The yellow green crystals were identified to be bis (tri-n-butylsiloxy) silicone-tetra (n-dodecylthio) naphthalocyanine) (Compound (103)) according to the following analysis results.

(1) Melting Point: 103˚ ~ 106 ℃

(2) Elemental Analysis Values:

Calculated (%): C; 73.04, H; 8.89, N; 5.68

Found (%): C; 73.21, H; 8.82, N; 5.71

(3) NMR spectral value (NMR spectrum is shown in FIG. 29): δ value 10.00 (4H, br-s), 9.95 (4H, br-s), 8.53 (4H, d, J = 8.85 Hz), 8.45 (4H, br-s), 7.80 (4H, d, J = 8.85 Hz), 3.31 (8H, t, J = 7.33 Hz), 1.93 (8H, quadruple, J = 7.33 Hz), 1.64 (8H, m ), 1.30 (64H, m), 0.88 (12H, triplet similar m), 0.02 (30H, m), -0.96 (12H, triplet similar m), -2.06 (12H, triplet similar m)

(4) The electron spectrum (CHCl ₃ solution) is shown in FIG.

(5) The IR spectrum KBr is shown in FIG.

[Test Example 1]

Bis (tri-n-propylsiloxy) silicone-tetra (n-dodecylthio) naphthalocyanine [Compound (100)] is dissolved in various solvents and its electron spectrum is measured. The electron spectra in chloroform, tetrahydrofuran, acetone, toluene and hexane are shown in FIGS. 21, 35, 36, 37 and 38 degrees, respectively. The absorption waveform does not change at all depending on the type of solvent or the concentration of the solution.

[Test Example 2]

Spin coating of a solution composed of 2 parts by weight of bis (tri-n-propylsiloxy) silicone-tetra (n-dodecylthio) naphthalocyanine [Compound (100)] and 98 parts by weight of 1,1,2-trichloroethane Coated on a glass plate and dried at about 80 ° C. for about 15 minutes to form an organic film. The transmission spectrum and the 5 ° specular reflection spectrum of the organic film of the compound are shown in FIGS. 39 and 40 degrees, respectively. It was confirmed that the organic film had high reflectance (˜39%) and high absorbance in the diode laser range (780 to 830 mm).

Comparative Example 1

Zhurnal Obshchei Khimii, Vol. 42, p. 696 (1972), vanadil-tetra (tert-butyl) -naphthalocyanine synthesized in the method described in the above is dissolved in each of chloroform and benzene to measure its electron spectrum. The electron spectra in chloroform and benzene are shown in FIGS. 41 and 42 degrees, respectively. As shown in FIGS. 41 and 42, for the prepared compounds, the absorption waveform changes depending on the solvent type and the concentration of the solution. The higher the density, the weaker the absorption at around 800 nm and the stronger the absorption at 720 to 730 nm.

Comparative Example 2

An organic film of vanadil-tetra (tert-butyl) naphthalocyanine, which is the same as that used in Comparative Example 1, was formed on a glass plate in the same manner as in Test Example 2, and the transmission spectrum (Fig. 44) of the organic film was measured. The organic film does not have very high absorbance and reflectance (20% or less) in the diode laser range (780 to 830 nm).

[Test Example 3]

A solution containing 1 part by weight of the illustrated naphthalocyanine derivatives 127, 99 and 102 and 99 parts by weight of tetrahydrofuran, respectively, was coated on the glass plate by a spin coating method and dried at about 80 ° C. for about 15 minutes. To form an organic film. The transmission spectrum and the 5 ° specular reflection spectrum of the organic film of the formed naphthalocyanine derivative are summarized in FIGS. 45 and 46 degrees, respectively. It is found that this organic film has high absorbance and high reflectance (740%) in the diode laser region 780 to 830 mm.

[Test Example 4]

The solubility of bis (tri-n-triphylsiloxy) silicone-tetra (n-decylthio) naphthalocyanine [Compound (99)] is measured by the following method. 100 ml of bis (tri-n-propylsiloxy) silicone-tetra (n-decylthio) naphthalocyanine and 0.5 ml of solvent are added to the 2 ml sample tube, and the sample tube is tightly sealed and ultrasonically stirred at 40 ° C. for 15 minutes. The sample tube is then left overnight at room temperature and the contents filtered. The residue from the filter paper is collected, dried under reduced pressure and the solubility from the residue is calculated by subtracting the residue from the initial amount of the compound.

Solubility of Bis (tri-n-propylsiloxy) silicon-tetra (n-decylthio) naphthalocyanine in various solvents

Example 6

[Synthesis of bis- (triethylsiloxy) silicon-tetra (n-decylthio) naphthalocyanine compound (127)]

In 132 mg (0.1 mmol) of bis (triethylsiloxy) silicone-tetrabromonaphthalocyanine solution dissolved in 10 ml of 3.2 ml of quinoline and a pyridine mixture, Organic Synthesis vol. 42, p.22], 2.08 g (8.8 m mol) of copper (I) n-decylthiolate synthesized by the method described in the above is added, and the obtained mixture is refluxed at 160 to 170 ° C. for 8 hours. After cooling, the reaction mixture was treated in the same manner as in Example 1 to yield 126 mg (75%) of yellowish green crystals. The obtained yellow green crystals were identified as bis (triethylsiloxy) silicone-tetra (n-decylthio) naphthalocyanine [Compound (127)] from the following analysis:

(1) Melting Point: 278˚ ~ 280 ℃

(2) Elemental Analysis Values:

Calculated (%): C; 70.95, H; 7.98, N; 6.62

Found (%): C; 70.68, H; 7.82, N; 6.75

(3) NMR spectral value (NMR spectrum is shown in FIG. 47): CDCl ₃ δ value 10.02 (4H, br-s), 9.97 (4H, br-s), 8.53 (4H, d, J = 8.85 Hz) , 8.45 (4H, br-s), 7.81 (4H, d, J = 8.85, 1.83 Hz), 3.29 (8H, t, J = 7.33 Hz), 1.93 (8H, quadruple, J = 7.33 Hz), 1.64 (8H, m), 1.33 (48H, m), 0.90 (12H, triplet-like m), -1.01 (18H, t, J = 7.94 Hz), -2.07 (12H, q, J = 7.94 Hz)

(4) The electron spectrum (CHCl ₃ solution) is shown in FIG.

(5) The IR spectrum KBr is shown in FIG.

Example 7

[Synthesis of bis (triethylsiloxy) silicone-tetra (n-dodecylthio) naphthalocyanine (compound (95))]

In 132 mg (0.1 mmol) of bis (triethylsiloxy) silicone-tetrabromonaphthalocyanine solution dissolved in a mixture of 10 ml quinoline and 3.2 ml pyridine, Organic Synthesis vol. 42, p. 22], 2.33 g (8.8 m mol) of copper (I) N-dodecylthiolate synthesized by the method described in the above is added, and the obtained mixture is refluxed at 160 to 170 ° C for 8 hours. After cooling, the reaction mixture was treated in the same manner as in Example 1 to yield 93 mg (52%) of yellowish green crystals. The obtained yellow green crystals were confirmed to be bis (triethylsiloxy) silicon-tetra (n-dodecylthio) -naphthalocyanine [Compound (95)] from the following analysis.

(1) Melting Point: 261˚ ~ 263 ℃

(2) Elemental Analysis Values:

Calculated (%): C; 71.86, H; 8.38, N; 6.21

Found (%): C; 71.92, H; 8.13, N; 6.09

(3) NMR spectral value (NMR spectrum is shown in FIG. 50): CDCl ₃ δ value 10.02 (4H, br-s), 9.97 (4H, br-s), 8.53 (4H, d, J = 8.85 Hz) , 8.45 (4H, br-s), 7.81 (4H, d, d, J = 8.85, 1.83 Hz), 3.29 (8H, t, J = 7.33 Hz), 1.93 (8H, quadruple, J = 7.33 Hz) , 1.64 (8H, m), 1.30 (64H, m), 0.88 (12H, triple-like m), -1.02 (18H, t, J = 7.94Hz), -2.07 (12H, q, J = 7.94Hz)

(4) The electron spectrum (CHCl ₃ solution) is shown in FIG.

(5) The IR spectrum KBr is shown in FIG.

Example 8

[Synthesis of bis (tri-n-butylsiloxy) silicon-tetra (n-decylthio) naphthalocyanine (compound (102))]

In 142 mg (0.1 mmol) of bis (tri-n-butylsiloxy) silicone-tetrabromonaphthalocyanine solution dissolved in a mixture of 10 ml quinoline and 3.2 ml pyridine, Organic Synthesis vol. 42, p.22], 2.08 g (8.8 mmol) of copper (I) n-decylthiolate synthesized by the method described in the above is added, and the obtained mixture is refluxed at 160 to 170 ° C for 8 hours. After cooling, the reaction mixture was treated in the same manner as in Example 1 to yield 112 mg (63%) of yellowish green crystals. The yellow green crystals obtained were identified to be bis (tri-n-butylsiloxy) silicon-tetra (n-decylthio) naphthalocyanine [Compound 102] from the following analysis:

(1) Melting Point: 122˚ ~ 123 ℃

(2) Elemental Analysis Values:

Calculated (%): C; 72.28, H; 8.56, N; 6.02

Found (%): C; 72.07, H; 8.32, N; 6.28

(3) NMR spectral value (NMR spectrum is shown in FIG. 53): CDCl ₃ δ value 10.00 (4H, br-s), 9.95 (4H, br-s), 8.53 (4H, d, J = 8.55 Hz) , 8.45 (4H, br-s), 7.80 (4H, dd, J = 8.55, 1.53 Hz), 3.31 (8H, t, J = 7.33 Hz), 1.93 (8H, quadruple, J = 7.33 Hz), 1.64 (8H, m), 1.33 (48H, m), 0.90 (12H, triplet-like m), 0.02 (30H, m), -0.96 (12H, triplet-like m), -2.06 (12H, triplet-like m )

(4) The electron spectrum (CHCl ₃ solution) is shown in FIG.

(5) The IR spectrum KBr is shown in FIG.

Example 9

[Synthesis of bis (tri-n-hexylsiloxy) silicon-tetra (n-dodecylthio) naphthalocyanine (compound (167))]

In 166 mg (0.1 mmol) of bis (tri-n-hexylsiloxy) silicone-tetrabromonaphthalocyanine solution dissolved in a mixture of 10 ml quinoline and 3.2 ml pyridine, Organic Synthesis vol. 42, p. 22], 2.33 g (8.8 mmol) of copper (I) n-dodecylthiolate synthesized by the method described in the above is added, and the obtained mixture is refluxed at 160 to 170 ° C for 8 hours. After cooling, the reaction mixture was treated in the same manner as in Example 1 to yield 89 mg (63%) of green oil. The obtained green oil was confirmed to be bis (tri-n-hexylsiloxy) silicone-tetra (n-dodecylthio) naphthalocyanine [Compound (167)] from the following analysis:

(1) Elemental Analysis Values:

Calculated (%): C; 74.03, H; 9.32, N; 5.23

Found (%): C; 73.91, H; 9.18, N; 5.46

(2) NMR spectral value (NMR spectrum is shown in FIG. 56): CDCl ₃ δ value 10.00 (4H, br-s), 9.95 (4H, br-s), 8.52 (4H, d, J = 8.85 Hz) , 8.46 (4H, br-s), 7.81 (4H, d, d, J = 8.85, 1.52 Hz), 3.29 (8H, t, J = 7.32 Hz), 1.92 (8H, quadruple, J = 7.32 Hz) , 1.63 (8H, m), 1.30 (64H, m), 0.88 (12H, triplet-like m), 0.63 (12H, hexaline, J = 7.32 Hz), 0.44 (18H, t, J = 7.32 Hz), 0.44 (18H, t, J = 7.32Hz), 0.23 (12H, quadruple, J = 7.32Hz), 0.07 (12H, quadruple, J = 7.32Hz), -0.99 (12H, quadruple-like m),- 2.07 (12H, triplet like m).

(3) The electron spectrum (CHCl ₃ solution) is shown in FIG. 57.

(4) The IR spectrum KBr is shown in FIG.

Example 10

Synthesis of [bis (tri-n-propylsiloxy) silicone-tetrakis- [2- (2'-ethylhexyloxycarbonyl) ethylthio] naphthalocyanine [Compound (143)]]

In 140 mg (0.1 mmol) of bis (tri-n-propylsiloxy) silicone-tetrabromonaphthalocyanine solution dissolved in a mixture of 10 ml quinoline and 3.2 ml pyridine, Organic Synthesis, vol. 42, p.22] was added 2.47 g (8.8 mmol) of copper (I) 2- (2'-ethylhexyloxycarbonyl) ethylthiolate synthesized by the method described in the above, and the mixture obtained was 160-170 占 폚. Reflux for 8 hours at. After cooling, the obtained reaction mixture was treated in the same manner as in Example 1 to yield 46 mg (24%) of yellowish green crystals. The yellowish green crystals obtained were obtained from the following analytical results. Bis- (tri-n-propylsiloxy) silicone-tetrakis- [2- (2'-ethylhexyloxycarbonyl) ethylthio] naphthalocyanine [Compound (143) Is confirmed to be:

(1) Melting Point: 125˚ ~ 127 ℃

(2) Elemental Analysis Values:

Calculated (%): C; 67.65, H; 7.54, N; 5.74

Found (%): C; 67.89, H; 7.42, N; 5.65

(3) NMR spectral value (NMR spectrum is shown in FIG. 59): CDCl ₃ δ value 10.04 (4H, br-s), 10.00 (4H, br-s), 8.57 (4H, d, J = 8.85 Hz) , 8.53 (4H, br-s), 7.84 (4H, d, J = 8.85 Hz), 4.14 (8H, d, J = 5.80 Hz), 3.56 (8H, t, J = 7.33 Hz), 2.93 (8H, t, J = 7.33 Hz), 0.7 to 1.8 (36H, m), 0.94 (24H, m), -0.27 (18H, t, J = 7.33 Hz), -0.87 (12H, hexaline-like m), -2.08 (12H, triplet like m).

(4) The electron spectrum (CHCl ₃ solution) is shown in FIG.

(5) The IR spectrum KBr is shown in FIG.

Example 11

Of {bis (tri-n-propylsiloxy) silicone-tetrakis [2- (2 ', 2', 4 ', 4'-tetramethylpentyloxycarbonyl) ethylthio] naphthalocyanine (compound (146)] synthesis}

140 mg (0.1 mmol) dissolved in a mixture of 10 ml quinoline and 3.2 ml pyridine

In bis (tri-n-propylsiloxy) silicone-tetrabromonaphthalocyanine solution, Organic Synthesis vol. 42, p.22] added 2.59 g (8.8 mmol) of copper (I) 2- (2 ', 2', 4 ', 4'-tetramethylpentyloxycarbonyl) ethylthiolate, The resulting mixture is refluxed at 160-170 ° C. for 8 hours. After cooling, the reaction mixture was treated in the same manner as in Example 1 to yield 52 mg (26%) of yellowish green crystals. The obtained yellow green crystals were obtained from the following analytical results, as follows: bis (tri-n-propylsiloxy) silicon-tetrakis- [2- (2 ', 2', 4 ', 4'-tetramethylpentyloxycarbonyl) ethylthio ] Naphthalocyanine (Compound (146)].

(1) Melting Point: 131˚ ~ 133 ℃

(2) Elemental Analysis Values:

Calculated (%): C; 68.15, H; 7.73, N; 5.58

Found (%): C; 68.13, H; 7.65, N; 5.37

(3) NMR spectral value (NMR spectrum is shown in FIG. 62): CDCl ₃ δ value 10.05 (4H, br-s), 10.01 (4H, br-s), 8.57 (4H, d, J = 8.55 Hz) , 8.54 (4H, br-s), 7.84 (4H, d, J = 8.85 Hz), 4.24 (8H, t, J = 6.56 Hz), 3.57 (8H, t, J = 7.33 Hz), 2.93 (8H, t, J = 7.33Hz), 1.01 (8H, d, J = 5.5Hz), 0.94 (60H, br-s), -0.26 (18H, t, J = 7.33Hz), -0.85 (12H, 5-line similar m), -2.06 (12H, triplet like m).

(4) The electron spectrum (CHCl ₃ solution) is shown in FIG.

(5) The IR spectrum KBr is shown in FIG.

Example 12

A solution containing 1 part by weight of the illustrated naphthalocyanine derivative (I) and 99 parts by weight of chloroform was coated by a spin coating method on a polyethyl methacrylate 2P substrate having a thickness of 1.2 mm and a diameter of 130 mm and at about 80 ° C. for about 15 minutes. Dry to form a recording layer. The thickness of the formed recording layer is about 1000 mm. The optical recording medium thus produced is placed on the turntable with the recording layer facing up, the turntable is rotated at a speed of 900 r.pm and the laser beam is placed under the optical recording medium, i.e. from the substrate surface, on the polymethylmethacrylate resin plate. Using a 6mW output on the substrate and an optical head with a diode layer (830nm) equipped with a diode layer (830nm) while adjusting the focus to a place such as a recording layer, pulse signals of 20 MHz within a radius of 40 to 60 mm from the center are recorded. Next, the recording signal is read by using the same apparatus while performing the above-described operation by adjusting the output of the diode laser on the substrate surface to 0.7 mW. In this case the C / N ratio is 56 dB and the writing and reading of signals can be performed very well.

Example 13

A recording layer coated with a naphthalocyanine derivative (15) in the form of a solution dissolved in chloroform on a polymethylmethacrylate 2P substrate having a thickness of 1.2 mm and a diameter of 130 mm by the spin coating method in the same manner as in Example 12. Form. The thickness of the recording layer is about 1500 mm. When the optical recording medium thus obtained was recorded and read out in the same manner as in Example 12, the C / N ratio was 56 dB, and excellent signal writing and reading was possible.

Example 14

The naphthalocyanine derivative 30 in the form of a solution dissolved in chloroform was coated on the polymethylmethacrylate 2P substrate having a thickness of 1.2 mm and a diameter of 130 mm by spin coating in the same manner as in Example 12 to obtain a recording layer. Form. The thickness of the recording layer is about 1200 mm. When the optical recording medium thus obtained was recorded and read out in the same manner as in Example 12, the C / N ratio was 59 dB, and excellent signal writing and reading was possible.

Example 15

The naphthalocyanine derivative 40 in the form of a solution dissolved in chloroform was coated on the polymethylmethacrylate 2P substrate having a thickness of 1.2 mm and a diameter of 130 mm by spin coating in the same manner as in Example 12 to obtain a recording layer. Form. The thickness of the recording layer is about 1300 mm 3. When the optical recording medium thus obtained was recorded and read out in the same manner as in Example 12, the C / N ratio was 60 dB, and excellent signal writing and reading was possible.

Example 16

The naphthalocyanine derivative 53 in the form of a solution dissolved in chloroform was coated on the polymethylmethacrylate 2P substrate having a thickness of 1.2 mm and a diameter of 130 mm by spin coating in the same manner as in Example 12 to obtain a recording layer. Form. The thickness of the recording layer is about 1100 mm 3. When the optical recording medium thus obtained was recorded and read out in the same manner as in Example 12, the C / N ratio was 57 dB, and excellent signal writing and reading was possible.

Example 17

A naphthalocyanine derivative (79) in the form of a solution dissolved in chloroform was coated on the polymethylmethacrylate 2P substrate having a thickness of 1.2 mm and a diameter of 130 mm by spin coating in the same manner as in Example 12 to obtain a recording layer. Form. The thickness of the recording layer is about 1500 mm. When the optical recording medium thus obtained was recorded and read out in the same manner as in Example 12, the C / N ratio was 59 dB, and excellent signal writing and reading was possible.

Example 18

The naphthalocyanine derivative 87 in the form of a solution dissolved in chloroform was coated on the polymethylmethacrylate 2P substrate having a thickness of 1.2 mm and a diameter of 130 mm by spin coating in the same manner as in Example 12 to obtain a recording layer. Form. The thickness of the recording layer is about 1200 mm. When the optical recording medium thus obtained was recorded and read out in the same manner as in Example 12, the C / N ratio was 55 dB, and excellent signal writing and reading was possible.

Example 19

The naphthalocyanine derivative 94 in the form of a solution dissolved in chloroform was coated on the polymethylmethacrylate 2P substrate having a thickness of 1.2 mm and a diameter of 130 mm by spin coating in the same manner as in Example 12 to obtain a recording layer. Form. The thickness of the recording layer is about 1300 mm 3. When the optical recording medium thus obtained was recorded and read out in the same manner as in Example 12, the C / N ratio was 58 dB, and excellent signal writing and reading can be performed.

Example 20

A naphthalocyanine derivative (95) in the form of a solution dissolved in xylene was coated on the polymethylmethacrylate 2P substrate having a thickness of 1.2 mm and a diameter of 130 mm by spin coating in the same manner as in Example 12 to obtain a recording layer. Form. The thickness of the recording layer is about 600 mm. When the optical recording medium thus obtained was recorded and read out in the same manner as in Example 12, the C / N ratio was 53 dB, and excellent signal writing and reading was possible.

Example 21

The naphthalocyanine derivative 96 in the form of a solution dissolved in xylene was coated on a polymethylmethacrylate 2P substrate having a thickness of 1.2 mm and a diameter of 130 mm by spin coating in the same manner as in Example 12 to obtain a recording layer. Form. The thickness of the recording layer is about 700 mm. When the optical recording medium thus obtained was recorded and read out in the same manner as in Example 12, the C / N ratio was 51 dB, and excellent signal writing and reading was possible.

Example 22

The naphthalocyanine derivative (97) in the form of a solution dissolved in xylene was coated on the polymethylmethacrylate 2P substrate having a thickness of 1.2 mm and a diameter of 130 mm by spin coating in the same manner as in Example 12 to obtain a recording layer. Form. The thickness of the recording layer is about 600 mm. When the optical recording medium thus obtained was recorded and read out in the same manner as in Example 12, the C / N ratio was 52 dB, and excellent signal writing and reading was possible.

Example 23

The naphthalocyanine derivative (98) in the form of a solution dissolved in xylene was coated on a polymethylmethacrylate 2P substrate having a thickness of 1.2 mm and a diameter of 130 mm by spin coating in the same manner as in Example 12 to obtain a recording layer. Form. The thickness of the recording layer is about 600 mm. When the optical recording medium thus obtained was recorded and read out in the same manner as in Example 12, the C / N ratio was 53 dB, and excellent signal writing and reading was possible.

Example 24

The naphthalocyanine derivative 99 in the form of a solution dissolved in xylene was coated on a polymethylmethacrylate 2P substrate having a thickness of 1.2 mm and a diameter of 130 mm by spin coating in the same manner as in Example 12 to obtain a recording layer. Form. The thickness of the recording layer is about 700 mm. When the optical recording medium thus obtained was recorded and read out in the same manner as in Example 12, the C / N ratio was 54 dB, and excellent signal writing and reading was possible.

Example 25

The naphthalocyanine derivative 100 in the form of a solution dissolved in toluene was coated on the polymethylmethacrylate 2P substrate having a thickness of 1.2 mm and a diameter of 130 mm by spin coating in the same manner as in Example 12 to obtain a recording layer. Form. The thickness of the recording layer is about 700 mm. When the optical recording medium thus obtained is recorded and read out in the same manner as in Example 12, the C / N ratio is 50 dB, and excellent signal writing and reading can be performed.

Example 26

The naphthalocyanine derivative 101 in the form of a solution dissolved in toluene was coated on a polymethylmethacrylate 2P substrate having a thickness of 1.2 mm and a diameter of 130 mm by spin coating in the same manner as in Example 12 to obtain a recording layer. Form. The thickness of the recording layer is about 600 mm. When the optical recording medium thus obtained was recorded and read out in the same manner as in Example 12, the C / N ratio was 51 dB, and excellent signal writing and reading was possible.

Example 27

The naphthalocyanine derivative 102 in the form of a solution dissolved in tetrahydrofuran was coated on the polymethylmethacrylate 2P substrate having a thickness of 1.2 mm and a diameter of 130 mm by spin coating in the same manner as in Example 12. Form a layer. The thickness of the recording layer is about 700 mm. When the optical recording medium thus obtained was recorded and read out in the same manner as in Example 12, the C / N ratio was 52 dB, and excellent signal writing and reading was possible.

Example 28

The naphthalocyanine derivative 103 in the form of a solution dissolved in tetrahydrofuran was coated on a polymethylmethacrylate 2P substrate having a thickness of 1.2 mm and a diameter of 130 mm by spin coating in the same manner as in Example 12. Form a layer. The thickness of the recording layer is about 600 mm. When the optical recording medium thus obtained was recorded and read out in the same manner as in Example 12, the C / N ratio was 51 dB, and excellent signal writing and reading was possible.

Example 29

Spin the naphthalocyanine derivative 105 in the form of a solution dissolved in 1,1,2-trichloroethane with polymethylmethacrylate 2P substrate having a thickness of 1.2 mm and a diameter of 130 mm in the same manner as in Example 12. The recording layer is formed by coating by a coating method. The thickness of the recording layer is about 1100 mm 3. When the optical recording medium thus obtained was recorded and read out in the same manner as in Example 12, the C / N ratio was 53 dB, and excellent signal writing and reading was possible.

Example 30

The naphthalocyanine derivative 113 in the form of a solution dissolved in xylene was coated on the polymethyl methacrylate 2P substrate having a thickness of 1.2 mm and a diameter of 130 mm by spin coating in the same manner as in Example 12 to obtain a recording layer. Form. The thickness of the recording layer is about 700 mm. When the optical recording medium thus obtained is recorded and read out in the same manner as in Example 12, the C / N ratio is 50 dB, and excellent signal writing and reading can be performed.

Example 31

The naphthalocyanine derivative 114 in the form of a solution dissolved in xylene was coated on a polymethylmethacrylate 2P substrate having a thickness of 1.2 mm and a diameter of 130 mm by spin coating in the same manner as in Example 12 to obtain a recording layer. Form. The thickness of the recording layer is about 600 mm. When the optical recording medium thus obtained was recorded and read out in the same manner as in Example 12, the C / N ratio was 51 dB, and excellent signal writing and reading was possible.

Example 32

The naphthalocyanine derivative 120 in solution form dissolved in xylene was coated on the polymethylmethacrylate 2P substrate having a thickness of 1.2 mm and a diameter of 130 mm by spin coating in the same manner as in Example 12 to obtain a recording layer. Form. The thickness of the recording layer is about 600 mm. When the optical recording medium thus obtained was recorded and read out in the same manner as in Example 12, the C / N ratio was 51 dB, and excellent signal writing and reading was possible.

Example 33

Spin coating a naphthalocyanine derivative 127 in solution form dissolved in 1,1,2-trichloroethane on a polymethylmethacrylate 2P substrate having a thickness of 1.2 mm and a diameter of 130 mm in the same manner as in Example 12 It coats by a method and forms a recording layer. The thickness of the recording layer is about 1100 mm 3. When the optical recording medium thus obtained was recorded and read out in the same manner as in Example 12, the C / N ratio was 54 dB, and excellent signal writing and reading was possible.

Example 34

The naphthalocyanine derivative 130 in the form of a solution dissolved in xylene was coated on the polymethylmethacrylate 2P substrate having a thickness of 1.2 mm and a diameter of 130 mm by spin coating in the same manner as in Example 12 to obtain a recording layer. Form. The thickness of the recording layer is about 700 mm. When the optical recording medium thus obtained was recorded and read out in the same manner as in Example 12, the C / N ratio was 52 dB, and excellent signal writing and reading was possible.

Example 35

The naphthalocyanine derivative 131 in the form of a solution dissolved in toluene was coated on the polymethyl methacrylate 2P substrate having a thickness of 1.2 mm and a diameter of 130 mm by spin coating in the same manner as in Example 12 to obtain a recording layer. Form. The thickness of the recording layer is about 600 mm. When the optical recording medium thus obtained was recorded and read out in the same manner as in Example 12, the C / N ratio was 51 dB, and excellent signal writing and reading was possible.

Example 36

The naphthalocyanine derivative 132 in the form of a solution dissolved in xylene was coated on the polymethylmethacrylate 2P substrate having a thickness of 1.2 mm and a diameter of 130 mm by spin coating in the same manner as in Example 12 to obtain a recording layer. Form. The thickness of the recording layer is about 600 mm. When the optical recording medium thus obtained was recorded and read out in the same manner as in Example 12, the C / N ratio was 53 dB, and excellent signal writing and reading was possible.

Example 37

The naphthalocyanine derivative 133 in the form of a solution dissolved in xylene was coated on a polymethylmethacrylate 2P substrate having a thickness of 1.2 mm and a diameter of 130 mm by spin coating in the same manner as in Example 12 to obtain a recording layer. Form. The thickness of the recording layer is about 700 mm. When the optical recording medium thus obtained was recorded and read out in the same manner as in Example 12, the C / N ratio was 52 dB, and excellent signal writing and reading was possible.

Example 38

The naphthalocyanine derivative 134 in the form of a solution dissolved in toluene was coated on the polymethylmethacrylate 2P substrate having a thickness of 1.2 mm and a diameter of 130 mm by spin coating in the same manner as in Example 12 to obtain a recording layer. Form. The thickness of the recording layer is about 700 mm. When the optical recording medium thus obtained was recorded and read out in the same manner as in Example 12, the C / N ratio was 52 dB, and excellent signal writing and reading was possible.

Example 39

The naphthalocyanine derivative 136 in solution form dissolved in tetrahydrofuran was coated on the polymethylmethacrylate 2P substrate having a thickness of 1.2 mm and a diameter of 130 mm by spin coating in the same manner as in Example 12. Form a layer. The thickness of the recording layer is about 800 mm. When the optical recording medium thus obtained was recorded and read out in the same manner as in Example 12, the C / N ratio was 53 dB, and excellent signal writing and reading was possible.

Example 40

The naphthalocyanine derivative 139 in the form of a solution dissolved in xylene was coated on the polymethylmethacrylate 2P substrate having a thickness of 1.2 mm and a diameter of 130 mm by spin coating in the same manner as in Example 12 to obtain a recording layer. Form. The thickness of the recording layer is about 700 mm. When the optical recording medium thus obtained was recorded and read out in the same manner as in Example 12, the C / N ratio was 51 dB, and excellent signal writing and reading was possible.

Example 41

The naphthalocyanine derivative 140 in the form of a solution dissolved in toluene was coated on the polymethylmethacrylate 2P substrate having a thickness of 1.2 mm and a diameter of 130 mm by spin coating in the same manner as in Example 12 to obtain a recording layer. Form. The thickness of the recording layer is about 600 mm. When the optical recording medium thus obtained was recorded and read out in the same manner as in Example 12, the C / N ratio was 52 dB, and excellent signal writing and reading was possible.

Example 42

The naphthalocyanine derivative 141 in the form of a solution dissolved in tetrahydrofuran was coated on the polymethylmethacrylate 2P substrate having a thickness of 1.2 mm and a diameter of 130 mm by spin coating in the same manner as in Example 12. Form a layer. The thickness of the recording layer is about 700 mm. When the optical recording medium thus obtained was recorded and read out in the same manner as in Example 12, the C / N ratio was 54 dB, and excellent signal writing and reading was possible.

Example 43

The naphthalocyanine derivative 142 in the form of a solution dissolved in toluene was coated on the polymethylmethacrylate 2P substrate having a thickness of 1.2 mm and a diameter of 130 mm by spin coating in the same manner as in Example 12 to obtain a recording layer. Form. The thickness of the recording layer is about 600 mm. When the optical recording medium thus obtained was recorded and read out in the same manner as in Example 12, the C / N ratio was 52 dB, and excellent signal writing and reading was possible.

Example 44

The naphthalocyanine derivative 145 in the form of a solution dissolved in xylene was coated on a polymethylmethacrylate 2P substrate having a thickness of 1.2 mm and a diameter of 130 mm by spin coating in the same manner as in Example 12 to obtain a recording layer. Form. The thickness of the recording layer is about 800 mm. When the optical recording medium thus obtained was recorded and read out in the same manner as in Example 12, the C / N ratio was 51 dB, and excellent signal writing and reading was possible.

Example 45

The naphthalocyanine derivative 148 in the form of a solution dissolved in tetrahydrofuran was coated on a polymethylmethacrylate 2P substrate having a thickness of 1.2 mm and a diameter of 130 mm by spin coating in the same manner as in Example 12. Form a layer. The thickness of the recording layer is about 600 mm. When the optical recording medium thus obtained is recorded and read out in the same manner as in Example 12, the C / N ratio is 50 dB, and excellent signal writing and reading can be performed.

Example 46

The naphthalocyanine derivative 149 in the form of a solution dissolved in toluene was coated on a polymethylmethacrylate 2P substrate having a thickness of 1.2 mm and a diameter of 130 mm by spin coating in the same manner as in Example 12 to obtain a recording layer. Form. The thickness of the recording layer is about 600 mm. When the optical recording medium thus obtained was recorded and read out in the same manner as in Example 12, the C / N ratio was 52 dB, and excellent signal writing and reading was possible.

Example 47

Spin coating the naphthalocyanine derivative 151 in the form of a solution dissolved in 1,1,2-trichloroethane on a polymethylmethacrylate 2P substrate having a thickness of 1.2 mm and a diameter of 130 mm in the same manner as in Example 12 It coats by a method and forms a recording layer. The thickness of the recording layer is about 1000 mm. When the optical recording medium thus obtained was recorded and read out in the same manner as in Example 12, the C / N ratio was 53 dB, and excellent signal writing and reading can be performed.

Example 48

The naphthalocyanine derivative 154 in the form of a solution dissolved in butanol was coated on a polymethylmethacrylate 2P substrate having a thickness of 1.2 mm and a diameter of 130 mm by spin coating in the same manner as in Example 12 to obtain a recording layer. Form. The thickness of the recording layer is about 800 mm. When the optical recording medium thus obtained was recorded and read out in the same manner as in Example 12, the C / N ratio was 52 dB, and excellent signal writing and reading was possible.

Example 49

The naphthalocyanine derivative 156 in the form of a solution dissolved in butanol was coated on the polymethylmethacrylate 2P substrate having a thickness of 1.2 mm and a diameter of 130 mm by spin coating in the same manner as in Example 12 to obtain a recording layer. Form. The thickness of the recording layer is about 700 mm. When the optical recording medium thus obtained was recorded and read out in the same manner as in Example 12, the C / N ratio was 51 dB, and excellent signal writing and reading was possible.

Example 50

The naphthalocyanine derivative 158 in the form of a solution dissolved in xylene was coated on the polymethylmethacrylate 2P substrate having a thickness of 1.2 mm and a diameter of 130 mm by spin coating in the same manner as in Example 12 to obtain a recording layer. Form. The thickness of the recording layer is about 700 mm. When the optical recording medium thus obtained was recorded and read out in the same manner as in Example 12, the C / N ratio was 53 dB, and excellent signal writing and reading was possible.

Example 51

Spin coating naphthalocyanine derivative 160 in solution form dissolved in 1,1,2-trichloroethane on a polymethylmethacrylate 2P substrate having a thickness of 1.2 mm and a diameter of 130 mm in the same manner as in Example 12 It coats by a method and forms a recording layer. The thickness of the recording layer is about 800 mm. When the optical recording medium thus obtained is recorded and read out in the same manner as in Example 12, the C / N ratio is 50 dB, and excellent signal writing and reading can be performed.

Example 52

The naphthalocyanine derivative 162 in the form of a solution dissolved in toluene was coated on the polymethylmethacrylate 2P substrate having a thickness of 1.2 mm and a diameter of 130 mm by spin coating in the same manner as in Example 12 to obtain a recording layer. Form. The thickness of the recording layer is about 600 mm. When the optical recording medium thus obtained was recorded and read out in the same manner as in Example 12, the C / N ratio was 51 dB, and excellent signal writing and reading was possible.

Example 53

The naphthalocyanine derivative 164 in the form of a solution dissolved in toluene was coated on the polymethylmethacrylate 2P substrate having a thickness of 1.2 mm and a diameter of 130 mm by spin coating in the same manner as in Example 12 to obtain a recording layer. Form. The thickness of the recording layer is about 700 mm. When the optical recording medium thus obtained was recorded and read out in the same manner as in Example 12, the C / N ratio was 52 dB, and excellent signal writing and reading was possible.

Example 54

The naphthalocyanine derivative 165 in the form of a solution dissolved in xylene was coated on a polymethylmethacrylate 2P substrate having a thickness of 1.2 mm and a diameter of 130 mm by spin coating in the same manner as in Example 12 to obtain a recording layer. Form. The thickness of the recording layer is about 600 mm. When the optical recording medium thus obtained is recorded and read out in the same manner as in Example 12, the C / N ratio is 50 dB, and excellent signal writing and reading can be performed.

Example 55

The naphthalocyanine derivative 166 in the form of a solution dissolved in toluene was coated on the polymethylmethacrylate 2P substrate having a thickness of 1.2 mm and a diameter of 130 mm by spin coating in the same manner as in Example 12 to obtain a recording layer. Form. The thickness of the recording layer is about 700 mm. When the optical recording medium thus obtained was recorded and read out in the same manner as in Example 12, the C / N ratio was 53 dB, and excellent signal writing and reading was possible.

Comparative Example 3

OVNc (tC ₄ H ₉ ) ₄ in solution form dissolved in chloroform was coated on a polymethylmethacrylate 2P substrate having a thickness of 1.2 mm and a diameter of 130 mm by spin coating in the same manner as in Example 12. Form a layer. The thickness of the recording layer is about 1000 mm. When the optical recording medium thus obtained was recorded and read out in the same manner as in Example 12, the C / N ratio was 49 dB, and excellent signal writing and reading was possible.

Example 56

The naphthalocyanine derivative 95 was dissolved in xylene to prepare a 1% solution, which was coated on a 1.2 mm thick glass by spin coating to form a 700 두께 thick recording layer. When the recording medium thus formed is irradiated with an anode laser beam having a wavelength of 830 nm from the glass material side and the recording characteristics are evaluated, recording is possible at a line speed of 6.4 mW, 6.5 m / sec and a beam diameter of 1.6 mu m. On the other hand, when repeatedly irradiated with a recording medium such as a read out of 0.5mW to evaluate the safety of the reading light does not cause a change in reflectivity even when repeatedly irradiated 10 ⁶ times.

[Comparative Example 4]

Cyanine dye NK-2905 (manufactured by Nihon Kanko Shikiso Kenkyusho) was dissolved in dichloroethane, and the resulting solution was coated on a glass material by spin coating to form a recording layer having a thickness of 500 kHz. When the recording medium thus obtained was irradiated with a laser beam in the same manner as in Example 56, recording was possible at 4.8 mW. However, evaluating its stability to read light, the repetitiveness begins to decrease after about 4x10 ⁴ irradiations, and after 10 ⁶ repetitions it decreases to 70% of the initial reflectance.

Example 57

The naphthalocyanine derivative 131 is dissolved in xylene, and the resulting solution is coated on the glass material by spin coating to form a recording layer having a thickness of 700 Å. The recording medium thus obtained was irradiated from the glass material side with an anode laser beam having a wavelength of 830 nm, and the recording characteristics were evaluated to find that recording was possible at a line speed of 6.9 mW, 6.5 m / sec and a beam diameter of 1.6 mu m. On the other hand, if the recording medium is repeatedly irradiated with a reading of 0.5 mW or the like in order to evaluate the safety of the read light, even if the irradiation is repeated 10 ⁶ times, no change in reflectivity is caused.

Example 58

The naphthalocyanine derivative 133 is dissolved in xylene, and the resulting solution is coated on the glass material by spin coating to form a recording layer having a thickness of 900 Å. The recording medium thus obtained was irradiated with a laser beam in the same manner as in Example 57 to find that recording was possible at 6.6 mW. When the safety of the read light was evaluated in the same manner as in Example 57, even if the irradiation was repeated 10 ⁶ times, no change in reflectivity was caused.

Example 59

The naphthalocyanine derivative 133 and polystyrene were dissolved in 1: 1 toluene in toluene, and the resulting solution was coated on the glass material by spin coating to form a recording layer having a thickness of 1500 Å. The recording medium thus obtained was irradiated with a laser beam in the same manner as in Example 57 to find that recording was possible at 9.6 mW. When the safety of the read light was evaluated in the same manner as in Example 57, even if the irradiation was repeated 10 ⁶ times, no change in reflectivity was caused.

Example 60

The naphthalocyanine derivative 138 is dissolved in toluene, and the resulting solution is coated on a 1.2 mm thick glass material by spin coating to form a recording layer having a thickness of 700 Å. The recording medium thus obtained was irradiated from the glass material side with an anode laser beam having a wavelength of 830 nm, and the recording characteristics were evaluated. Recording is possible at 4.6 mW, line speed of 7.5 m / sec and beam diameter of 1.6 mu m. On the other hand, if not repeated irradiation to a recording medium such as a read out of 0.5mW, even if the irradiation was repeated 10 ⁶ times the change in the reflectivity it caused not to evaluate the safety of the reading light.

[Comparative Example 5]

The cyanine dye NK-2873 (manufactured by Nihon Kanko Shikiso Kenkyusho) was dissolved in dichloroethane, and the resulting solution was coated on the glass material by spin coating to form a recording layer having a thickness of 500 kHz. When the recording medium thus obtained was irradiated with a laser beam in the same manner as in Example 57, recording was possible at 5.2 mW. However, when evaluating the stability of the read-out light by repeating the irradiation of about 5 × 10 ⁴ and begin to decrease the reflectivity, and 10 after ^six iterations is reduced to 70% of the initial reflectivity.

Example 61

The naphthalocyanine derivative 141 is dissolved in dichloroethane and the resulting solution is coated on the glass material by spin coating to form a recording layer having a thickness of 500 kHz. The recording medium thus obtained was irradiated with a laser beam in the same manner as in Example 57 to find that recording was possible at 4.4 mW. In evaluating the safety of the read light, even if the irradiation is repeated 10 ⁶ times, no change in reflectivity is caused.

Example 62

The naphthalocyanine derivative 144 is dissolved in toluene, and the resulting solution is coated on the glass material by spin coating to form a recording layer having a thickness of 500 kHz. The recording medium thus obtained was irradiated with a laser beam in the same manner as in Example 57 to find that recording was possible at 4.9 mW. In evaluating the safety of the read light, even if the irradiation is repeated 10 ⁶ times, no change in reflectivity is caused.

Example 63

The naphthalocyanine derivative 147 is dissolved in toluene and the resulting solution is coated on the glass material by spin coating to form a recording layer having a thickness of 400 kHz. The recording medium thus obtained was irradiated with a laser beam in the same manner as in Example 57 to find that recording was possible at 4.2 mW. In evaluating the safety of the read light, even if the irradiation is repeated 10 ⁶ times, no change in reflectivity is caused.

Example 64

A solution of the naphthalocyanine derivative 150 dissolved in toluene was coated by spin coating on a 1.2 mm thick polycarbonate material having a Ti chelate surface-protection layer having a thickness of 10 nm to form a recording layer having a thickness of 600 kHz. In the same manner as in Example 57, recording characteristics were evaluated at a line speed of 5 m / sec to find that recording was possible at 7.4 mW. At the same time, when evaluating the stability to the read light, even if the irradiation is repeated 10 ⁶ times, no change in reflecting power is caused.

Example 65

A mixture of the naphthalocyanine derivative 152 and polystyrene in a 2: 1 ratio is dissolved in methyl ethyl ketone, and the resulting solution is made into a recording layer of 600 mm thick on a glass material. Evaluation was carried out in the same manner as in Example 57, to obtain the following result: recording sensitivity of 4.8 mW, deterioration by 10 ⁶ or more repetitions.

Example 66

The naphthalocyanine derivative 154 was dissolved in butanol to prepare a 0.8 wt% solution, and the solution was coated on a 1.2 mm thick glass material by spin coating to form a recording layer having a thickness of 400 kHz. When the recording medium thus obtained is irradiated toward the glass material with an anode laser beam having a wavelength of 830 nm and the recording characteristics are evaluated, recording is possible at 7.8 mW, a line speed of 7.6 m / sec and a 1 / e ² beam diameter of 1.6 mu m. On the other hand, if not repeated irradiation to a recording medium such as a read out of 0.5mW, even if the irradiation was repeated 10 ⁶ times the change in the reflectivity it caused not to evaluate the safety of the reading light.

Example 67

The naphthalocyanine derivative 156 was dissolved in butanol to prepare a 1.0 wt% solution, and the solution was coated on a 1.2 mm thick glass material by spin coating to form a recording layer having a thickness of 600 kHz. When the recording medium thus obtained is irradiated from the glass material side with an anode laser beam having a wavelength of 830 nm and the recording characteristics are evaluated, recording is possible at 8.6 mW, a line speed of 7.6 m / sec and a 1 / e ² beam diameter of 1.6 μm. . On the other hand, if not repeated irradiation to a recording medium such as a read out of 0.5mW, even if the irradiation was repeated 10 ⁶ times the change in the reflectivity it caused not to evaluate the safety of the reading light.

Example 68

A mixture of the naphthalocyanine derivative 158 and polystyrene in a 2: 1 ratio was dissolved in 1,1,2-trichloroethane, and the resulting solution was coated on a 1.2 mm thick glass by spin coating to obtain a thickness of 800 kPa. A recording layer is formed. When the recording medium thus obtained is irradiated from the material side using an anode laser beam having a wavelength of 830 nm, and its recording characteristics are evaluated, recording is possible at a line speed of 8 m / sec and 6 mW. Even if the recording medium is repeatedly irradiated with a reading of 0.5 mW or the like, even if the irradiation is repeated 10 ⁶ times, no change in reflecting power is caused.

The present invention provides novel naphthalocyanine derivatives, which are useful, for example, as optical recording media, light conductive materials, liquid crystal display materials and the like.

Claims (11)

Base material; And a recording layer in which a solution containing a naphthalocyanine derivative of the general formula (I) as a main component is formed on a substrate by printing, spin coating, coating, or dipping. Wherein k, l, m and n may be the same or different and are an integer of 0 or 1 to 4, and k + l + m + n is an integer of 1 or more; R ¹ in the number of 4 (k + l + m + n) may be the same or different and is an alkyl group, a substituted alkyl group or an aryl group; M is Si, Ge, or Sn; The two Y's may be the same or different and are an aryloxyl group, an alkoxy group, a trialkyloxyloxy group, a triaryloxyl group, a trialkoxyoxyloxy group, a triaryloxysiloxyl group, a trityloxyl group, or an acyloxyl group. The optical recording medium according to claim 1, wherein the recording layer is mainly composed of a naphthalocyanine derivative of formula (I) in which M is Si or Ge. An optical recording medium according to claim 1, wherein the recording layer is mainly composed of naphthalocyanine derivatives of general formula (I) in which k, l, m and n are all one. An optical recording medium according to claim 1, wherein the recording layer is mainly composed of a naphthalocyanine derivative of formula (I) wherein two Y's are trialkyloxylyl groups. The optical recording medium according to claim 1, wherein the recording layer is mainly composed of a naphthalocyanine derivative of formula (I) in which all R ¹ are alkyl groups having 1 to 22 carbon atoms. The optical recording medium according to claim 1, wherein the recording layer is mainly composed of a naphthalocyanine derivative of the general formula (I) in which all R ¹ are substituted alkyl groups. An optical recording comprising forming a recording layer on the surface of a substrate by printing, spin coating, coating, or immersing a solution obtained by dissolving a naphthalocyanine derivative of the following general formula (I) in an organic solvent as a main component: Method of Making Media. Wherein k, l, m and n may be the same or different and are an integer of 0 or 1 to 4, and k + l + m + n is an integer of 1 or more; R ¹ in the number of 4 (k + l + m + n) may be the same or different and is an alkyl group, a substituted alkyl group or an aryl group; M is Si, Ge, or Sn; The two Y's may be the same or different and are an aryloxyl group, an alkoxy group, a trialkyloxyl group, a triaryloxyl group, a trialkoxyoxyl group, a triaryloxyoxyl group, a trityloxyl group, or an acyloxyl group. The method for producing an optical recording medium according to claim 7, wherein the naphthalocyanine derivative is a compound of formula (I) wherein M is Si or Ge. The method for producing an optical recording medium according to claim 7, wherein the naphthalocyanine derivative is a compound of formula (I) wherein k, l, m and n are all 1. The method for producing an optical recording medium according to claim 7, wherein the naphthalocyanine derivative is a compound of formula (I) wherein two Y are trialkyloxyoxyl groups. The method for producing an optical recording medium according to claim 7, wherein the naphthalocyanine derivative is a compound of formula (I) wherein all R ¹ are alkyl groups having 1 to 22 carbon atoms.