DE2260540A1 - NEW BISAZO PIGMENTS - Google Patents

Description

The present invention relates to new bisazo pigments and their Use.

In the German patent application P 22 15 068.1 is the use certain bisazo pigments described in electrophotography.

The present invention now relates to new bi- and terphenylenebiouao bonds ₃ which have proven useful as photoconductors and photoconductive sensitizers, in particular in the field of electrophotography.

The new compounds according to the invention correspond to the general one formula

N = N

0 = 0 OH

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N = N

BADORfGlNAU ^

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in which η represents the value 2 or 3, X represents a hydrogen or halogen atom and R and R ^{1 represent} hydrogen atoms or alkyl or aryl radicals. It has been found that these compounds are valuable as photoconductors.

The methods for making these new compounds are shown in the examples below. Change invention / lts compounds can be prepared by methods described below the analog, the suitable substitutability th Ausgangsniaterialien be prepared by using.

The compounds according to the invention have proven useful as photoconductive sensitizers. In particular, the compounds according to the invention , when present in an electrophotographic plate with a particle size of a few times than about 5 microns in diameter, are very effective photoconductors.

There are several electrophotographic reproduction methods currently in use. They differ in the particular way in which they are carried out, in particular the sequence in which the electrical charging (usually by means of corona discharge) and the exposure are carried out. All electrophotographic reproduction processes, however, include the process step of making parts of a photoconductor selectively electrically conductive by selective exposure. The pigments according to the invention are detectable in all such experiments.

It should be noted that the pigment particles are not dissolved, that is to say that they are not present as individual molecules in a solution. Rather, they exist as polymolecular aggregates. The use of Wox ^ ts pigment to describe the materials is in agreement with this, since the word pigment is usually used to describe a colored particle that is not in solution, in contrast to Woi 't Fai'stoff, which is used to describe a colored material that is in solution, is used.

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As already stated above, the pigment size should be less than 5 microns in diameter! Be ^1. Preferably the pigment size is less than about 1 micron in diameter. In addition, it can be advantageous, at least in certain cases, for the particle sizes to be approximately uniform.

According to the invention, the pigments can be used in the form of a thin layer on a conductive substrate. The layer can be covered with a charge transport layer. Systems of this type are described in German patent application P 17 97 306.7.

Alternatively, the pigments can be present in a binder medium, which can be either self photoconductive or itself non-photoconductive. There are many binders as useful in the event known in the manufacture of photoconductive plates. These include numerous resins and the like. Many such materials are named, for example Mylar adhesive 49,000 (registered trademark of duPont), which is a βθΜθ copolymer of Ethylene terephthalate and ethylene isophthalate act. It.are also Polyketones can be used, for example PK 252 (trademark of. Union Carbide), which is a polyketone. However, it is not necessary that the binder be a resin. So in U.S. Patent 3 * J06,063 are non-polymeric coating composition materials which can also be used in the present invention.

The binder material can also be photoconductive itself. A particularly useful photoconductive binder is that described in US Pat Photoconductors described in U.S. Patent 3,484,237. In this Patent is described a photoconductive material that is formed from polyvinyl carbazole and trinitrofluorenone (TNF).

To increase the photoconductivity of some of the above Photoconductive pigments can be added to the pigment either a sensitizer or an activator, which is also known as an electron acceptor known, or in certain cases when the photoconductor

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ter is an electron acceptor, introduce an electron donor. Examples of such dye sensitizers and activators see U.S. Patents 3,037,861, 3,169 ΟβΟ and 3,287,113. If desired, a photoconductive one To have material that shows persistent conductivity, dye sensitizer and activator "combinations, as described in U.S. Patent 3,512,966 in which Manufacture of such photoconductive materials can be used.

The following examples serve to further illustrate the invention.

example 1

4,4 '- (4 ", 4"' -terphenylenebisazo) -bis-3-hydroxy-2-naphthamide

A solution of 0.4 g of 4,4'-terphenyltetrazonium fluorate in 30 ml of dimethyl sulfoxide (DMSO) was obtained by diazotizing the corresponding amine / I. Org. Chem., 2_1, 1154 (195627 prepared in the usual way with 5n-MaNOp in hydrochloric acid. The diazo compound was isolated as fluoborate and recrystallized from ethanol-water (1: 1). The above solution was converted into a solution of 1, 0 g of 3-hydroxy-2-naphthamide and 0.3 g of sodium acetate in 30 ml of DMSO were added. The reaction mixture was stirred at room temperature for 1-1 / 2 hours. The dark precipitate was filtered off, washed with acetone and in vacuo at 100 dried to 120 ^{0 C.}

Analysis C ₁₁₀ H ₂₈ NgO ₁₁

Calculated: C = 72.9 H = 4.26 N = 12.7 % Found: 72.57 4.26 13.20 %

Example 2

4,4 '- (4 ", 4"' -terphenylenebisazo) -bis-3-hydroxy-2-naphthanilio

This color center] was made in the same way as that in Example

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described using 1.8 g of tetrazonium fluorate, 4.5 g 3-Hydroxy-2-naphthanilide and 1 g of sodium acetate made in DMSO. The dark precipitate was filtered off and recrystallized from nitrobenzene.

Analysis C ₁ - «H, ^ Nz-O ,,

j (L JÖ OH

Calculated: C = 77.21 H = 4.48 N = 10.38 %
Found: 76.40 4.48 9.74 %

Example 3

4,4 '- (4 ", 4"' - terphenylenebisazo) -bis-N-propyl-3-hydroxy-2-naphthanilide

The preparation was carried out in a manner analogous to that of the compound in Example 1, starting from 2.1 g of N-propyl-3-hydroxy-2-naphthanilide and 0.5 g of sodium acetate in 50 ml of DMSO and 0.6 g of the tetrazonium compound in 50 ml DMSO. The dark plague substance was
recrystallized from a mixture of nitrobenzene, ligroin and acetone. The analysis was carried out after drying at 100 ° C. in vacuo.

Analysis C ^ rH ,, pN ^ O ,. ·

Calculated: C = 78 03 H = 5 , 38 N = 9 , 42 % Found: 77 23 5 , 42 9 , 94 % Example 4

4,4'-A ^II , 4 " ^t - (3,3'-dichlorobiphenylene) -bisa25o7-bis-N-propyl-3- hydroxy-2-naphthamide

N-propyl-3-hydroxy-2-naphthamide was made by adding the acid chloride made to an excess of propylamine. The exothermic reaction was over in about 1/2 hour and that was not converted Te propylamine was removed in vacuo. Diluted hydrochloric acid was used added to the reaction mixture and stirring for a few minutes

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continued, after which the pests were filtered off, washed with water and recrystallized from ethanol. The amide melted at 13O ⁰ C and was obtained in 70 / Siger yield.

Analysis ^c i4 ^H ₁ 5 ^NO ₂

Calculated: C = 73.3 ² JH = 6.59 N = 6.10 % Found: 72.73 6.56 6.10 %

4 g of this amide were dissolved in 150 ml of DMSO with 1 g of sodium acetate. A solution of 2 g of the tetrazonium fluorate of 3,3 * -dichlorobenzidine in 50 ml of DMSO was added to the amide and the reaction mixture was stirred at room temperature for about 15 minutes. A dark pest substance weighing 1.4 g was filtered off from the reaction mixture and recrystallized from nitrobenzene.

analysis ^C 4O ^H 34 ^C1 2 ^N 6 O ₁₄ H β ' 4th , 67 N = 11 , 45 Cl = 9.66 Calculated : C = 65 4th , 61 11 , 02 10.16 Found: 65 , 01 example 5

4,4'-A ", 4"'-(3,3'-dichlorobiphenylene) -bisazo7-bis-N, N-dipropyl- 3-hydroxy-2-naphthamide

N, N-Dipropyl-3-hydroxy-2-naphthamide was made in the same way like the N-propylamide used in Example 4 from the acid chloride and dipropylamine. The reaction with the diazonium compound to form the colorant was carried out in the same manner as in Example 4, but this product was not recrystallized. However, the analysis showed that this was the right one Connection was.

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Analysis ^ Lf ^ hf ^ fpii

N = 10.27 Cl = 8.67 %

9.67 8.71 %

Calculated: C. = 67, 55 H = 5 , 67 Found: 67, 48 5 , 68 Example 6

4,4 '- / ξ ", 4"' - (3,3'-dichlorobiphenylene) -bisazoT-bis-N-propyl-S- hydroxy-2-naphthanilide

N-propyl-3-hydroxy-2-naphthanilide _a P = I89 to 190 ⁰ C from ethanol, was prepared from the acid chloride and N-propylaniline as described in Example 4. FIG. The condensation of this amide with the tetrazonium salt took place in DMSO in the catfish already described. This compound was not recrystallized, but combustion analysis showed it was pure.

Analysis C ₅₂ H ₁₁₂ Cl ₂ NgO ₄

Calculated: C = 69.68 H = 4.91 N = 9.75 Cl = 8.22 % Found: 69.45 4.82 8.92 8.20 %

Example 7

4,4 '-A ", 4"' - (3,3. '-Dichlorobiphenylene) -bisazoT-bis 1-hydroxy-4- naphthamide ; ; __

This pigment was made in the usual way from 3 ~ hydroxy-2-naphthamide, P = 318 to 32O ° C from ethanol-Wasöer, "made .. The product obtained was recrystallized from nitrobenzene and, as the combustion analysis showed, was pure.

Analysis C ₃₄ H ₃₂ Cl ₂ NgO ₄

Calculated: 62, 87 H = 3 , 41 .N =. 12th , 93 Cl = 10 »■ 91 Found: 62, 40 3 , 43 12th , 05 10 , 82

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Claims (8)

Claims 1. Compounds of the formula N = N HO .C = O in which η is 2 or 3, _s X is a hydrogen or halogen atom and R and R ^{1 are} hydrogen atoms or alkyl or aryl radicals. 2. 4,4 '- (4 ", 4"' -Terphenylenbisazo) -bis ^ -hydroxy - ^ - naphthamide. 3. 4,4 '- (4 ", 4"' - terphenylenebisazo) -bis-N-propyl-3-hydroxy-2-naphthanilide. 4. 4,4 "- / Tf", 4 "'- (3,3' -dichlorobiphenylene) -bisazo7-bis-N-propy 1-3-hydroxy-2-naphthamide. 5. 4,4 · -A ", 4" '- (3,3'-dichlorobiphenyleny-bisazoT-bis-N, N'-dipropyi 3-hydroxy-2-naphthamide. 6.4 ^! -A ", 4" ^l - (3.3 ^t -dichlorobiphenylene) -bisazo7-bis-N-propyl-3-hydroxy-2-naphthanilide. 7. Electrophotographic reproduction process in which parts of a photoconductor are selectively eüe'c- 309827/1003 BATH ORIGINAL trically conductive, characterized in that the photoconductor has a connection according to one of claims 1 to 6 includes. 8. Use of the compounds according to any one of claims 1 to β in electrophotographic reproduction processes. 309327/1003