JPS635093A - Bis(trialkylsiloxy)silicone naphtalocyanine and production thereof - Google Patents

Abstract

NEW MATERIAL:A compound expressed by formula I [L is R<1>R<2>R<3>Si-O- (R<1>-R<3> are 1-4C alkyl)]. EXAMPLE:Bis(triethylsiloxy)siliconenaphthalocyanine. USE:An electrophotographic photosensitive material (electric charge-generating substance) for electrophotographic photosensitive body and a recording material for optical discs. PREPARATION:Dihydroxysiliconenaphthalocyanine expressed by formula II is reacted with a compound (e.g. triethylsilanol, etc.) expressed by formula R<1>R<2>R<3>SiX (X is OH or halogen), preferably in an organic solvent such as quinoline, tetralin, etc., at 150-200 deg.C. 0.1-1wt% catalyst such as tri-n- butylamine, etc., may be used therewith as necessary.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to a novel bis(trialkylsiloxy)silicon naphthalocyanine and a method for producing the same.

(Prior art) Conventionally, naphthalocyanine derivatives include various metal compounds of naphthalocyanine and naphthalene ring having 4 carbon atoms at position 6.
- Various metals of tetra-6-alkylnaphthalocyanine substituted with 12 alkyl groups (however, the metals include copper, zinc, aluminum, tin, vanadium, manganese, cobalt, nickel, palladium, lead, and magnesium) , some have two hydrogen atoms bonded instead of a metal). [Zhurmal Obshchei Khimii]
, Vol. 42, p. 696.

1972, U.S. Patent No. 4,492,7509
Mol, Crys
t.

Liq, Cryst, ) Vol. 112, p. 345, 198
4 years.

JP-A-60-23451, JP-A-60-1845
Publication No. 65] Also. Regarding silicon naphthalocyanine derivatives, those having the following general formula (11) in which R is an n-hexyl group are known (Journal Op.
American Chemical Society (J, Am,
Chem, Soc, Volume 106, Page 7404, 198
4 years).

(Problems to be Solved by the Invention) However, in conventional naphthalocyanine, various metals such as alkyl-substituted tetra-6-alkylna-7-lycyanine are soluble in aromatic and... Although it is possible to purify them by methods such as crystallization, in the vacuum evaporation method, which is one of the thin film production methods for applying organic materials to electronic devices, various metal products of these 7-thalocyanines cannot be purified. There is a problem that it decomposes and cannot be deposited.

- On the other hand, various metal products of unsubstituted thalocyanine.

Although vacuum evaporation is possible, it is insoluble in most solvents and there is a problem in improving its purity by recrystallization or the like. In addition, in the following general formula (11), where the middle group is an n-hexyl group, arsiliconina 7 talocyanine is used.

It is soluble in aromatic and...logenic solvents, its purity can be increased by recrystallization, etc., and vacuum deposition is also possible, but the yield of charged flux molecules of its thin film is extremely low.

The present invention is intended to solve these problems.It is an object of the present invention to solve these problems.

The present invention provides a novel silicon naphthalocyanine derivative that can be vacuum evaporated and has a high charge flow rate particle yield.

(Means for Solving the Problems) The first invention is based on the general formula +11 [However, in formula 2, R'R''R3Si O- (where tR''eR2 and R3 each independently have a carbon number of 1 to The present invention relates to a bis(trialkylsiloxy)silicon naphthalocyanine represented by 4).

-Bis(trialkylsiloxy)silicon naphthalocyanine represented by the general formula (1) is soluble in aromatic s-agents and halogenated solvents, can be easily recrystallized, and can improve purity. can. In addition, when performing vacuum evaporation, the boat temperature of the vacuum evaporation equipment should be set to 320 to 470.
At such temperatures, this can be easily done by increasing the temperature.

Do not disassemble.

Examples of the aromatic solvents include benzene, toluene, xylene, chlorobenzene, dichloro, lobenzene, 1,2.
4-trimethylbenzene, 1. Examples of such solvents include 3-trimethylbenzene, 1-chloronaphthalene, and quinoline. Examples of the above-mentioned chlorine-based solvents include methylene chloride, chloroform, and carbon tetrachloride.

The second invention is dihydroxysilicon naphthalocyanine represented by formula 2 (1ll) and general formula (III) 几"R"R3Si
However, among the 9 types, 几1. R'' and R3 are each independently an alkyl group having 1 to 4 carbon atoms, and X represents a hydroxyl group or a halogen) to form a trialkyl silicon naphthalocyanine represented by the general formula ill above. This invention relates to a method for producing bis(trialkylsiloxy)silicon naphthalocyanine, which comprises the steps of synthesizing bis(trialkylsiloxy)silicon naphthalocyanine.

-4 Bis(trialkylsiloxy) silicone represented by formula (1) 7 talocyanine, dihydroxy silicone naphthalocyanine, and the compound represented by the above general formula (III) can be heated and reacted. In this case, 9 reaction temperature is preferably 150 to 200°C, and for this purpose, organic solvents such as tetralin, chlorobenzene, quinoline, 1-tricl-lunaphthalene, 1,2,4-)limethylbenzene, 1. Equivalent values of λ3-trimethylbenzene, xylene, toluene, benzene, dichlorobenzene, β-picoline, etc. are preferably used. Also, - general formula + III)
Among them, when X is halogen, trin-
It is preferable to use bases such as butylamine, tri-n-propylamine, tri-hexylamine, pyridine, etc., and these are preferably used in an amount of 0.1 to 1% by weight based on the dihydroxysilicon naphthalocyanine.

In addition, to produce bis(triethylcimixi)silicon naphthalocyanine, the yield is better when triethylsilanol is used than when triethylcurosilicon is used.

Isolation and purification of bis(trialkylsiloxy)silicon naphthalocyanine from the reaction mixture are as follows: 1. Concentrating the reaction mixture to dryness and then recrystallizing it 9. This can be carried out by pouring into a poor solvent of phthalocyanine, collecting the resulting precipitate, and recrystallizing it.

Recrystallization can be carried out using the above-mentioned aromatic solvent or halogen solvent.

Dihydroxysilicon naphthalocyanine represented by formula (II) is a known compound, 9 for example, published in the Journal of the American Chemical Society (J. Am.
Chem, Soc, ) Vol. 106, p. 7404 (19
It can be produced by the route of the following formula (A) using the method described in 1984).

(V)
(M-NH (■) That is, α, α, α', α'-tetrabromo-〇-xylene [formula (V)] 0.1 mol tofumaronitrile 0.173 mo/sodium iodide 0.67 mo
The mixture is reacted in anhydrous N,N-dimethylformamide at 75° C. for 7 hours in the presence of λ3-dicyanonaphthalene [formula (W)]. Next, 57.3 mmol of 2.3-dicyanocattalin! 1,3-diiminobenzo(f)isoindoline [formula (■]) is obtained by heating and reacting with ammonia in methanol in the presence of sodium methoxide for 3 hours.In addition, 1,3-diiminobenzo(f)isoindoline 30 .6 mmoJ is treated with 47.1 mmol of silicon tetrachloride in anhydrous tetralin and anhydrous tri-n-butylamine under reflux for about 3 hours. The metal is treated with concentrated sulfuric acid and then with concentrated aqueous ammonia. Bis(trialkylsiloxy) silicon naphthalocyanine is useful for electrophotographic photosensitive materials (charge generating materials) for electrophotographic photoreceptors, recording materials for optical disks, etc. The manufacturing process is as follows.

That is, a single layer containing a bis(trialkylsiloxy)silicon naphthalocyanide charge transport substance represented by the general formula +1) can be formed as a photoconductor layer on a conductor layer. Also.

It is also possible to form the charge-generating material and the charge-transporting material as separate layers and construct a so-called two-layer structure as a photoconductor layer on top of the conductor layer.

When adopting a single layer structure, the amount of the charge transport material to be mixed with the charge generation material is 1 part by weight for the former and 1 to 50 parts by weight for the latter. Volume parts are common. Further, the total thickness of the photoconductor layer is generally 5 to 100 μm. - direction, 21
When adopting this structure, the thickness of the charge generation layer is 0.1 to 5 μm,
The thickness of the charge transport layer is generally in the range of 5 to 100 μm. However, in any case, it is desirable that the final determination be made with consideration given to not impairing the photosensitivity, that is, the charging characteristics. Care must be taken because if the thickness of the photoconductive layer becomes too thick, the flexibility of the layer itself may decrease.

Examples of the charge transport substance include pyrazoline derivatives, hydrazone derivatives, triphenylmethane derivatives, oxadiazole derivatives, oxazole derivatives, carbazole derivatives, stilbene derivatives, and the like. Known binders can be applied to the photoconductor layer. Binders include linear saturated polyester resins, polycarbonate resins, acrylic resins, phthalate resins, polyketone resins, polyurethane resins, poly-N-vinylcarbazole, poly-(p
-vinylphenyl)anthracene, etc. The amount of binder used is ! It is appropriate to use 1 to 50 parts of heavy protein per 1 part of weight-generating substance.

In addition, in the case of a photoconductor with a two-layer structure, it should be added to at least the layer consisting of a charge transport material), in which case the charge transport material 11 and the binder should be suitably 1 to 50 parts by weight. . The conductor layer is made of aluminum, X-Tsum, and copper.

Gold is used.

The bis(trialkyl70xy)silicon naphthalocyanine according to the present invention can be used in a recording medium that is recorded and read by irradiation with electromagnetic energy such as a semiconductor laser beam.
It can be used as a recording layer material. In other words, when the silicon naphthalocyanine amorphous layer is provided on a suitable substrate, when electromagnetic energy of suitable intensity, for example, semiconductor laser light, is focused and irradiated in a spot, the amorphous silicon naphthalocyanine layer will not open due to thermal deformation. Although this does not occur, only that part crystallizes after cooling, causing changes in concentration such as reflectance and absorption, so information can be written using these phenomena.

Reading can be performed. Furthermore, when strong electromagnetic energy is used, holes can be formed in the irradiated area to cause changes in concentration such as reflectance and absorption.

As a method for forming such a recording layer, any of the conventional and well-known methods can be used; for example, a spin-coating method, a dip coating method, etc. may be used. Vacuum deposition is the most preferred method for forming an amorphous thin film. During vacuum deposition, an amorphous thin film can easily be formed if the substrate temperature is lower than room temperature, and the deposition rate is preferably as fast as possible. The recording layer material is AA21! Alternatively, a combination of two or more types may be used, and in the case of a combination of two or more types, a laminated structure or a mixed single layer structure may be used. The thickness of the recording layer is preferably in the range of 50 to 10,000×, particularly preferably in the range of 100 to 5,000×.

Supports for recording media include glass, mica, and metal.

In addition to inorganic materials such as alloys, polyester, cellulose acetate, nitrocellulose, and polyethylene.

Examples include, but are not limited to, films and plates of organic polymer materials such as polypropylene, polyvinyl chloride, vinylidene chloride copolymer, polyamide, polystyrene, polymethyl methacrylate, and methyl methacrylate copolymer. A support made of an organic polymer with low thermal conductivity is desirable because it causes less heat loss during recording and increases sensitivity.

Also, when optically reproducing the formed recorded image.

Often uses reflected light. In this case, as an effective method to increase the contrast, between the support and the recording layer,
It is preferable to provide a metal exhibiting high reflectance in advance. AJ is a metal with this high reflectance.

Cr s Au + P te Sn or the like is used. These films can be formed using known thin film forming techniques such as vacuum deposition, sputtering, and plasma deposition.

The film thickness is selected within the range of 100 to 100 OOA. Further, when the surface smoothness of the substrate itself is a concern, it is preferable to provide a uniform film of an organic polymer on the substrate. These polymers include polyester.

Commercially available polymers such as polyvinyl chloride are applicable. Furthermore, it is preferable to provide a protective layer mainly composed of an organic polymer compound as the outermost layer, thereby increasing stability and protection, and further providing a layer for the purpose of increasing sensitivity by reducing one surface reflectance. Such organic polymer compounds include polyvinylidene chloride, polyvinyl chloride, vinylidene chloride and acrylonitrile copolymer, polyvinyl acetate, polyimide polymethyl methacrylate, polystyrene, polyisoprene, polyphtadiene, polyurethane, polyvinyl butyral, fluororubber, polyester.

Epoxy resins, silicones JUL cellulose acetate, etc. are used alone or in blends.

It is preferable to include silicone oil, an antistatic agent, a crosslinking agent, etc. in the protective layer from the viewpoint of enhancing membrane performance. Moreover, the protective layer can also be stacked in two layers. The organic polymer compound can be applied by dissolving it in a suitable solvent and applying it, or by laminating it as a thin film. The thickness of such a protective layer is set at 0.1 to 10 μm, but
Preferably, the thickness is 0.1 to 2 μm.

(Example) Production Example 1 Production of dihydroxy silicone naphthalocyanine α, α,
α′, d-tetrabromo〇-xylene 4Z2 g (0,
1mo/), fu? O nitrile 13.59 (0,173
100 g (0.67 mo!) of sodium iodide was added to a 400 mJ solution of anhydrous N,N-dimethymo/l/mo/) with thorough stirring, and the mixture was stirred at 75°C under a nitrogen atmosphere for about 7 hours. . After reaction.

The reaction mixture was poured into about 2 kg of ice. Gradually added sodium bisulfite until the red aqueous solution turned pale yellow. Added a slight excess of sodium bisulfite. After stirring for a while, the solution was stirred for a while at room temperature. I installed it in the evening. The precipitated pale yellow solid was suction-filtered, thoroughly washed with water, and then air-dried. The pale yellow solid was recrystallized from a mixed solvent of ethanol/chloroform to yield λ3-dicyanonaphthalene 13G (73%) as colorless crystals. The melting point of this crystal is 25
6.5-257.5℃ (literature value, melting point 256℃
).

Next, 10.29 g of 2,3-dicyanonaphthalene (57,
3 mmol! While thoroughly stirring the mixture, anhydrous ammonia gas was slowly bubbled into the mixture at room temperature for about 1 hour. The mixture was refluxed for about 3 hours while bubbling anhydrous ammonia gas.

After cooling, the precipitated yellow solid was filtered, thoroughly washed with methanol, and dried under reduced pressure to yield 1,3-diiminopentyl.
] Isoindoline as a yellow solid about 9.59 (86%
) obtained. This 1,3-diiminobenzo(f)isoindoline was used unpurified in the next reaction.

Under a nitrogen atmosphere, 20 grams of anhydrous trilobylamine was added to a suspension of 40 grams of anhydrous tetralin containing 6 g (30.6 mmo/) of 1,3-diiminobenzo["f]isoindoline, and then 5.4 grams of silicon tetrachloride ( 47.1 mmol
and refluxed for about 3 hours. Methanol after cooling 30
Add the gourd and leave it overnight. The reddish-brown reaction mixture was filtered, thoroughly washed with methanol, and dried under reduced pressure to yield about 49 (64
%) obtained.

This dichlorosilicon naphthalocyanine was used unpurified in the next reaction.

Dichlorosilicon naphthalocyanine 5.89 (7,1
Add 5 mmol to 200 ml of concentrated sulfuric acid! In addition, the mixture was stirred for about 2 hours. The reaction mixture was poured into approximately 600 g of ice and left overnight. The deposited precipitate was filtered and diluted with water three times in acetone/
After washing three times with water (1/1) mixed solvent.

This precipitate was refluxed in 150 g of concentrated ammonia for about 1 hour. After cooling, filter, wash thoroughly with water, and dry under reduced pressure.
Approximately 49 (72%) of dihydroxysilicon naphthalocyanine was obtained as a dark green solid.

Example 1 Dihydroxynaphthalocyanine 774 mg (1 mmol
) of quinoline 35d @ triethylsilanol 3 in suspension
．． 5 ml (23 mmol) was added and refluxed for about 3 hours. After cooling, the two reaction mixtures were diluted with ethanol/water (1/1).
200ml! Pour into a bowl, stir well, and leave overnight. The deposited precipitate was filtered and washed with methanol. About 600 ml of hot chloroform was used to dissolve only the soluble part of the precipitate, and the chloroform solution was concentrated to about 50 ml. The concentrated chloroform solution was cooled, and the precipitated crystals were filtered and washed with chloroform. When the obtained crystals were recrystallized using chloroform, dark green crystal 3 was obtained.
60 mg (36%) was obtained. According to the analysis results below, this dark green crystal is bis(triethylsiloxy)silicon naphthalocyanine [in the above -ff formula (I), L is -0
-8i+CaHs)].

(1) Melting point 300℃ or higher (2) Elemental analysis value: HN Calculated value (chi) 71.82 5.42 11.1
7 Actual measurement value (regret) 70.45 5.34 10.
92+31 NMR value (NMR spectrum shown in Figure 1): CDCl5 solvent δ value 10.13 (8H, s) 8.68 (8H, dd, J=6.10.3.05
Hz) 7.93 (8H, dd, J=6.10.3.0
5 H2)-1,02(12H,tt J=7.93
Hz)-2,07 (18H, q, J=7.93 Hz)
+4) The UV spectrum (CHC/s solution) is shown in FIG.

Example 2 Dihydroxysilicon naphthalocyanine 3g (3.9m
12 ml of anhydrous tri-n-butylamine in a nitrogen atmosphere to 420 m of mol of anhydrous β-picoline/suspension! (
Add 50.4 mmol and then add 13.2 m of tri-n-butyl silane (add 49.2 mmol).

The mixture was refluxed for about 2 hours. After cooling, the mixture was diluted with ethanol/water (
1/1) was poured into a 60 ml bottle, stirred well, and then left to stand overnight. The deposited precipitate was filtered and washed with water.

Only the soluble part of this precipitate was dissolved using about 600 m/m of hot chloroform, and the chloroform solution was dried over anhydrous sulfuric acid (IJ) and concentrated to about 50 m/m. The concentrated chloroform solution was cooled, and the precipitated crystals were filtered and washed with chloroform.

The mother liquor was concentrated and subjected to alumina column chromatography using cybenzene as the eluent as a developing solvent.The green benzene solution was concentrated, hexane was added, and the precipitated crystals were filtered and thoroughly washed with hexane. All the obtained crude crystals were collected and recrystallized using chloroform to obtain dark green crystalline 29 (44%). The dark green crystals were confirmed to be Sibis(tri-n-butylsiloxy)silicon naphthalocyanine based on the analysis results below.

(1) Melting point >300℃ (2) Elemental analysis value: HN Calculated value (%) 73.81 6.71 9.5
0 Actual value (%) 73.71 6.73 9.
40 (31 NMR value (NMR spectrum shown in Figure 3) 20D C1s δ value 10.11 (8H, s) 8.67 (8H, dd, J=6.10.3.35
Hz) 7.92 (8H, dd, J=6.10.3.
35 Hz) -0,1~0.1 (30H, m) -0,97 (12H, quintet, J=7.32
Hz)-2[7(] 2H,t, J = 7.32H
z) (41UV spectrum (CHCl!s solution)
As shown in the figure.・Example 3 Dihydroxysilicon naphthalocyanine 3g (3.9m
mol ) of anhydrous β-picoline in 420 ml suspension of anhydrous tri-n-butylamine (12 ml (50.4 mmol)
! 3 then tri-n-propylchlorosilane 10.8r
nl! (49.2 mmo/) and refluxed for about 2 hours9. After cooling, the reaction mixture was treated as in Example 2, and dark green crystals were obtained by recrystallization from chloroform.
．． 459 (34 chi) was obtained. This dark green crystal is the result of the analysis below.
It was confirmed that it was silicon naphthalocyanine.

(1) Melting point >300℃ (2) Elemental analysis value: HN Calculated value (%) 7289 6.12 10.30
Actual value (chi) 72.706.13 10.28 (31N
MR value (NMR spectrum is shown in Figure 5): CD
Cl! 3 δ value 10.03 (8H, s) a68 (8H, dd, J=6.10.103 Hz
)7.93 (8H, dd, J=6.10.3.03
Hz)-0,28(18H,t, J=7.32H
z)-0,85(12H,5extet J=7.3
2 Hz)-2[6(12H,te J=-7,32H
z) (41 U V Shek) k (CHCb solution) is shown in FIG.

Example 4 Dihydroxysilicon naphthalocyanine 1g (1.3m
moI) of anhydrous β-picoline 140 rM! Anhydrous tri-n-butylamine (16,8 mmol) was added to the M suspension, followed by 2.1 ml (16,4 mmol) of trimethylchlorosilane.
mmo/ ) was added and refluxed for about 2 hours. After cooling, the nine reaction mixtures were treated in the same manner as in Example 2 to obtain bis(trimethylsiloxy)silicon naphthalocyanine as dark green crystals. The UV spectrum (CHC/s solution) is shown in FIG.

Comparative Example 1 Dihydroxysilicon naphthalocyanine 1g (1.3m
Mol of anhydrous β-picoline 140rrd! Add 4 ml of anhydrous tri-n-butylamine to the suspension! (16,8 mmol
6 ml of Ritsude Tori-Hexilc1cI silane
(16,4 mmol was added and refluxed for 1.5 hours.

After cooling, insoluble impurities were removed by filtration, and the filtrate was poured into 200ml of ethanol/water (1/1).

The deposited precipitate was filtered to obtain a product. This product was thoroughly washed with water, dried in vacuum, and subjected to alumina column chromatography using toluene-hexane (3:1) as a developing solvent.The resulting dark green solution was concentrated and reconstituted from hexane/chloroform. It was crystallized to obtain 0.529 (30 cm) of green needle-like crystals. This compound was confirmed to be bis(tri-n-hexylsiloxy)silicon naphthalocyanine by comparing the analysis results described in the literature with the analysis results below.

(1) Melting point 277-278℃ (literature value, melting point 278℃
) (21HMR value (NMR spectrum is shown in Figure 8)
: CDC15 δ value 10.11 (8H, s) 8.67 (8H, dd, J=6.21.3.35
Hz) 7.91 (8H, dd, J = 6.21.3
．． 35 Hz) 0.63 (12H, 5extet,
J=7.32 Hz)0.42 (18H,tt J=
7.32 Hz) 0.23 (12H, quintet
, J-7, 32Hz) 0.07 (12H, quin
te t, J = 7.32 Hz) - 0,98 (1
2H, quintet, J-7,32Hz)-2,0
6 (12H, t, J=7.32 Hz) [3) U
V (CHCl!s solution) is shown in FIG.

Test Example 1 A sandwich cell for measuring charging current shown in FIGS. 10 and 11 was prepared as follows. In addition.

FIG. 10 is a plan view of the sandwich cell.

FIG. 11 is a screen view taken along line a-a' in FIG.

A glass plate 2 having a Nesa film 1 was placed in a vacuum evaporation apparatus at a predetermined position, and 10 m9 of bis(triethylsiloxy)silicon naphthalocyanine was placed in a tungsten evaporation boat and heated at 3 x 10-6 Torr (410 to 47 m).
A photoconductive layer 3 was deposited under conditions of 0° C. so as to cover a portion of the Nesa film 1. On top of this, AJ was deposited across the photoconductive layer 3 to a thickness of about 300''A to form an At! layer 4.

Lead wires were connected to the Nesa film and the L' layer of the sandwich cell using silver paste, and photoelectric measurements were performed as follows. A 300 W logen lamp was used as a light source, and the sandwich cell was irradiated with light that was separated by a monochromator (manufactured by Ritsu Applied Optics Co., Ltd.) through an optical chopper (manufactured by NFF Roadblock Co., Ltd.). The phototactic current generated by light irradiation was measured using a lock-in amplifier (NF circuit clock 2 company 1M).

The measurement wavelength range was 500 to 840 nm, and measurements were made every 10 nm. Photocurrent, Ip, obtained for each wavelength.

By dividing by the light irradiation intensity Io of that wavelength, the charge flow rate molecular yield, η (η=Ip/Io) was determined. The action spectrum plotted against wavelength is shown in FIG.

Test Example 2 A measurement sandwich cell was prepared and measured in exactly the same manner as in Test Example 1 for bis(tri-n-propylsiloxy)silicon naphthalocyanine. The action spectrum is shown in FIG.

Test Example 3 A sandwich cell was prepared and measured in the same manner as in Test Example 1 for bis(trilobylsiloxy)silicon naphthalocyanine. The action spectrum is the first
It is shown in Figure 4.

Test Example 4 A sandwich cell was prepared in the same manner as in Test Example 1 for bis(IJ-n-hexylsiloxy)silicon naphthalocyanine, and measurements were performed.

The action spectrum is shown in FIG.

When compared with FIG. 12, it can be seen that the charge flow rate η at a wavelength of 800 nm is 50 to 100 times higher.

(Effects of the Invention) The bis(trialkylsiloxy)silicon naphthalocyanine represented by the general formula (1) according to the present invention is a novel compound with a high charge flow rate molecular yield.

[Brief explanation of the drawing]

FIG. 1 U is an NMR spectrum of bis(triethylsiloxy)silicon naphthalocyanine. Figure 2 i
j, UV spectrum of His()IJethylsiloxy)silicon naphthalocyanine. Figure 3 Ha, hiss (
1J-NMR spectrum of n-butyloxy2silicon naphthalocyanine. Figure 4 shows the UV of bis(tri-n-butylsiloxy)silicon naphthalocyanine.
It is a spectrum. FIG. 5 is an NM spectrum of bis(trilowpropylsiloxy)silicon naphthalocyanine. FIG. 6 is a UV spectrum of bis(tri-n-propylsiloxy)silicon naphthalocyanine. Figure 7 shows the U of bis(trimethylsiloquine) silicon naphthalocyanine.
V spectrum. Figure 8 shows the NMR of bis(tri-n-hexylsiloxy)silicon naphthalocyanine.
It is a spectrum. FIG. 9 is a UV spectrum of bis(tIJ-n-hexylsiloxy)silicon naphthalocyanine. FIG. 10 is a plan view of the sandwich cell for measuring charging current, and FIG. 11 is a sectional view taken along the line aa' in FIG. 10. Figure 12 shows bis(triethylsiloxy)
This is the action spectrum of silicon naphthalocyanine. Figure 13 shows the action spectrum of bis(t17-n-propylsiloxy) silicon naphthalocyanine (
solid line), and the dashed line is its UV spectrum. 1st
Figure 4C is the action spectrum of His(IJ-11-butylsiloxy) silicon naphthalocyanine. Figure 1d is the action spectrum (solid line) of bis()IJ-n-hexylsiloxy) silicon naphthalocyanine, and the dashed line is its UV spectrum.゛--n''; l-cho (ru town → 100 Z Figure J nest (compensation/K) - summer 4 Figure 6 Figure shi anti-four-bi 1 (914 pieces 1-) → Tomi 7 Tsuzawa-cho (simmered dish → γ) q Fig. S length (π generation) → Te 13 Fig. 5 Reverse length ($ Qi ji No. 74

Claims (1)

[Claims] 1. General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) [However, in the formula, L is R^1R^2R^3Si-O- (here, R^1 , R^2 and R^3 each independently represent an alkyl group having 1 to 4 carbon atoms]. 2. Formula (II) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (II) Dihydroxysilicon naphthalocyanine represented by and general formula (III) R^1R^2R^3SiX (III) (However, in the formula, R^ 1, R^2 and R^3 are each independently an alkyl group having 1 to 4 carbon atoms, and X represents a hydroxyl group or a halogen) to form the general formula (I) ▲ Formula, There are chemical formulas, tables, etc.▼(I) [However, in the formula, L is R^1R^2R^3Si-O-
(wherein R^1, R^2 and R^3 are the same as the general formula (III))] Method for producing (trialkylsiloxy) silicon naphthalocyanine.