CN1632700A - A kind of azo/phthalocyanine composite monolayer organic photoconductor and preparation method thereof - Google Patents

Abstract

This invention is a wide-frequency vibration and high light sensitive azo or phthalocyanine compound single layer organic photoelectricity conductor and its process method, which belongs to organic photoelectricity conductor technique field. The material mainly adopts charge carrier generation material and charge carrier transmission material and resin and conductive base material with certain proportion to form organic photoelectricity coating liquid and adopts the dipping and coating method. And the charge carrier generation material is the compound material of oxazolyl bisazo or metal phthalocyanine and the charge carrier transmission material adopts compounds of triaryl amine and hydrazone compound, and pyrazoline compound.

Description

A kind of azo/phthalocyanine composite monolayer organic photoconductor and preparation method thereof

technical field

The invention belongs to the technical field of organic photoconductors, and specifically relates to an azo/phthalocyanine composite single-layer organic photoconductor with wide frequency response and high photosensitivity and a preparation method thereof.

Background technique

Organic photoconductors are the "heart" components of electrophotography imaging that can form photogenerated carriers and migrate under photoexcitation. At present, the annual output of organic photoconductors in the world is hundreds of millions, which has produced huge economic and social benefits. But there are still many problems to be solved.

In order to obtain organic photoconductors with high photosensitivity and long life, traditional photoconductors use a single organic photogenerated carrier material and an organic carrier transport material for layered compounding to form a functionally separated double-layer organic photoconductor. . Due to multiple coatings, the manufacturing process is complicated, the control is difficult and the cost is high. If the carrier generation material and the carrier transport material are combined to make a single-layer organic photoconductor, not only the process is simple, there is no problem of interlayer peeling, and the generation of ozone can be reduced, but also the tightness between the photogenerated material and the transport material The combination will significantly improve the quantum efficiency and photoconductive performance of photoconductive materials. Therefore, in order to standardize organic photoconductor products, simplify the production process, improve quality, and reduce costs; at the same time, in order to meet the needs of one drum for multiple purposes and overcome the current incompatible limitations of photoconductors for electrostatic printing and laser printing, it is necessary A single-layer organic photoconductor with excellent broadband response and high photosensitivity in the wavelength range from visible light to near-infrared (400nm-1000nm) is produced.

The most critical factor affecting the performance of organic photoconductors is the carrier generation material. Phthalocyanine and azo are currently the most widely used carrier generation materials in industry. Chinese invention patents (88100214.3 88100213.5) disclosed for the first time the method of preparing a double-layer organic photoconductor using a phthalocyanine compound, which opened up a new way to prepare an organic photoconductor using a new method of material blending and compounding, but has not yet involved this type of phthalocyanine blending. Whether the composite has excellent spectral response in the visible region and the near-infrared region, and is a single-layer organic photoconductor. Chinese invention patent (00131902.7) discloses a phthalocyanine/phthalocyanine composite single-layer organic photoconductor and its preparation method, but phthalocyanine only has excellent spectral response in the near-infrared region, so the organic composite photoconductor is only suitable for near-infrared light Laser printers with laser as the light source are also difficult to meet the needs of broadband response. The Chinese invention patent (97113319.0) uses azo/phthalocyanine blend compound as a carrier photogenerated material to prepare single-layer and double-layer organic photoconductors. Although it has excellent spectral response in the range of visible light to near-infrared light, However, the photosensitivity of single-layer structure photoconductors is still much lower than that of double-layer structure photoconductors.

Contents of the invention

The object of the present invention is to provide an azo/phthalocyanine composite single-layer photoconductor with wide frequency response and high photosensitivity and its preparation method.

The azo/phthalocyanine composite single-layer organic photoconductor with broadband response and high photosensitivity provided by the present invention is mainly composed of carrier generation material, carrier transport material, resin and conductive matrix, wherein:

(1) The carrier generating material is an oxazolyl disazo/metal phthalocyanine composite material, and the chemical structural formulas of oxazolyl disazo and metal phthalocyanine are respectively:

Among them, R ₁ and R ₂ can be C ₁ ~ C ₁₂ aliphatic hydrocarbon groups, C ₁ ~ C ₁₂ alkoxy groups, halogen groups, hydroxyl groups, nitro groups, carboxylic acid groups, etc.; M can be copper, cobalt, nickel, aluminum, Titanium oxide or vanadium oxide, etc.

(2) The carrier transport material is triarylamine, hydrazone, pyrazoline, triarylmethane or tetraphenylbenzidine compound.

(3) Its composition is counted as:

                                                                                                     

                                                                                                     

                                                                                                        80-300

Resin 100-300 parts

                                                                                               

Additives 0.1-0.5

The preparation method of the azo/phthalocyanine composite single-layer organic photoconductor with broad frequency response and high photosensitivity is as follows:

(1) Stir and disperse the azo/phthalocyanine blend compound, resin and carrier transport material in an organic solvent according to the dosage ratio, so that the solid content of the solution is 10% to 50% (by weight), and the organic photoconductive material is obtained. coating liquid;

(2) The organic photoconductive solution is coated on the conductive substrate by the dip coating method. The drying time is 3.5 hours, and the thickness of the dried organic photoconductive coating layer is 15-45 μm.

The present invention is characterized in that: 1. the introduction of oxazolyl improves the dissolubility of disazo, making oxazolyl disazo also have good dispersion in common solvents such as tetrahydrofuran, toluene, chloroform or dioxane, etc. properties, thus increasing its recombination effect with metal phthalocyanine and carrier transport materials; ② From the perspective of electronic structure, oxazolyl disazo has a high degree of conjugation and strong electron delocalization, and azo/ Phthalocyanines are easier to compound, and theoretically they can have high photogeneration efficiency, thereby obtaining higher photoconductive properties; ③ In order to obtain higher photosensitive properties of oxazolyl disazo/metal phthalocyanine composite photoconductors, On the amide aromatic ring of oxazolyl disazo, the -Cl or -NO _substituent with strong electron-withdrawing ability can be preferentially selected; ④ Due to the oxazolyl disazo/metal phthalocyanine complex and the hole The photoinduced charge interaction between the transport materials is further enhanced, which promotes the separation of photogenerated electron/hole pairs and improves the photosensitivity of the photoconductor.

Using the oxazolyl disazo/metal phthalocyanine compound as the carrier generation material to prepare a single-layer composite organic photoconductor can be prepared by solution dip coating, which has the characteristics of simple process, high efficiency, low cost and reduced environmental pollution. . The single-layer composite organic photoconductor has the advantages of broadband effect and high photosensitivity, and can be used not only in electrostatic copiers with visible light as light source, but also in laser printers with near-infrared laser as light source.

Description of drawings

Fig. 1 is a scanning electron micrograph of an oxazolyl disazo/phthalocyanine titanyl composite single-layer photoconductor.

Fig. 2 is the ultraviolet-visible light absorption spectrum of the oxazolyl disazo/phthalocyanine titanium compound.

Fig. 3 shows the variation of the photosensitivity of single-layer photoconductors based on pure oxazolyl disazo, pure phthalocyanine titanyl and oxazolyl disazo/phthalocyanine titanyl complexes with the light source wavelength.

Detailed ways

The above-mentioned oxazolyl bis-azo/metal phthalocyanine blend compound is prepared by purifying and drying the two materials of azo and phthalocyanine at room temperature with a weight ratio of 0.1-9.9:9.9-0.1 Grinding and blending with a solvent in a sand mill or a ball mill for 4 to 12 hours, after the grinding is completed, filtering and drying to obtain the azo/phthalocyanine blend compound. The carrier transport materials used are triarylamines, hydrazones, pyrazolines, triarylmethanes and tetraphenylbenzidines. The solvent used is tetrahydrofuran, dioxane, toluene, xylene, butanone, cyclohexanone, methylene chloride, chloroform, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether, N, N-di Methylformamide or N,N-dimethylacetamide, or a mixed solvent composed of any two of the above solvents. The resin used is polycarbonate, polyvinyl butyral, polystyrene, polymethyl methacrylate, polyvinyl chloride, polyvinylidene chloride, polyacrylonitrile, vinylidene chloride-polyacrylonitrile copolymer or polyvinyl acetate resin. The conductive substrate used is conductive metal sheet, ITO glass or polyester sheet coated with conductive medium, or drum-shaped, strip-shaped conductive metal and conductive alloy. The organic photoconductive solution is coated on the conductive substrate by dip coating, the coating speed is 4.0-7.0mm/s, the viscosity of the coating solution is 300-500cp, the drying temperature is 80-120°C, and the drying time The time is 3.5 hours, and the thickness of the dried organic photoconductive coating layer is 15-45 μm.

The present invention will be described in detail below in conjunction with the examples. Unless otherwise stated, the photoconductive performance data given are all obtained on the GDT-II photoconductive tester developed by the Zhejiang University Test Center. The monochromatic light is obtained with a color filter, and the light intensity is 30μw.

Example 1

The chemical structural formula is respectively:

The oxazolyl disazo and titanium phthalocyanine (in which, R ₁ = OH, R ₂ = Cl, M = TiO), mixed in a ratio of 1:1 (by wt.), added tetrahydrofuran and sanding medium, Sand mill at room temperature for 6 hours, and distill off the solvent to obtain the oxazolyl bis-azo and phthalocyanine-titanium complex. The oxazolyl disazo/phthalocyanine titanium complex, N, N'-diethyl-4-aminobenzaldehyde-1-phenyl-1'-α-naphthylhydrazone (α-naphthylphenylhydrazone) Stir and disperse in dioxane with polycarbonate at a ratio of 1:75:82 (weight ratio) to obtain an organic photoconductive coating solution. The above-mentioned coating solution is coated on the aluminum alloy drum base by dip coating, the coating speed is 5.5mm/s, the viscosity of the coating solution is 450cp, the drying temperature is 90°C, and the drying time is 3.5 hours. The dried organic The thickness of the photoconductive coating layer was 30 μm.

The photoconductive data of the single-layer organic composite photoconductor are shown in Table 1.

Example 2

The same as in Example 1, but the ratio of the oxazolyldisazo/phthalocyanine titanyl complex, α-naphthylphenylhydrazone and polycarbonate was changed to 1:70:76 (weight ratio).

The photoconductive data of the single-layer organic composite photoconductor are shown in Table 1.

Example 3

The same as in Example 1, but the ratio of the oxazolylbisazo/phthalocyanine titanyl complex, α-naphthylphenylhydrazone and polycarbonate was changed to 1:80:80 (weight ratio).

The photoconductive data of the single-layer organic composite photoconductor are shown in Table 1.

Example 4

The same as in Example 1, but the ratio of the oxazolylbisazo/phthalocyanine titanyl complex, α-naphthylphenylhydrazone and polycarbonate was changed to 1:68:68 (weight ratio).

The photoconductive data of the single-layer organic composite photoconductor are shown in Table 1.

Example 5

The same as in Example 1, but the ratio of the oxazolylbisazo/phthalocyanine titanyl complex, α-naphthylphenylhydrazone and polycarbonate was changed to 1:80:90 (by weight).

The photoconductive data of the single-layer organic composite photoconductor are shown in Table 1.

Example 6

The same as in Example 1, but the ratio of the oxazolylbisazo/phthalocyanine titanyl complex, α-naphthylphenylhydrazone and polycarbonate was changed to 1:60:60 (weight ratio).

The photoconductive data of the single-layer organic composite photoconductor are shown in Table 1.

Example 7

The same as in Example 1, but the ratio of the oxazolylbisazo/phthalocyanine titanyl complex, α-naphthylphenylhydrazone and polycarbonate was changed to 1:90:100 (weight ratio).

The photoconductive data of the single-layer organic composite photoconductor are shown in Table 1.

Example 8

Same as Example 1, but R ₁ =OCH ₃ , R ₂ =C ₅ H ₆ .

The photoconductive data of the single-layer organic composite photoconductor are shown in Table 1.

Example 9

Same as Example 1, but R ₁ =NO ₂ , R ₂ =CN.

The photoconductive data of the single-layer organic composite photoconductor are shown in Table 1.

Example 10

Same as Example 1, but R ₁ =COOH, R ₂ =NH ₂ .

The photoconductive data of the single-layer organic composite photoconductor are shown in Table 1.

Example 11

Same as Example 1, but α-naphthylphenylhydrazone becomes N, N'-diethyl-4-aminobenzaldehyde-1,1'-diphenylhydrazone (α-diphenylhydrazone)

The photoconductive data of the single-layer organic composite photoconductor are shown in Table 1.

Example 12

Same as Example 1, but α-naphthylphenylhydrazone was changed to α-naphthylphenylhydrazone/trinitrofluorenone (100/1, weight ratio) complex.

The photoconductive data of the single-layer organic composite photoconductor are shown in Table 1.

Comparative Example 1

The chemical structural formula is:

The oxazolyl disazo is added into tetrahydrofuran and a sand milling medium, sand milled at room temperature for 4 to 8 hours, and the solvent is evaporated to obtain oxazolyl disazo dispersed particles. Stir and disperse oxazolyl disazo dispersed particles, α-naphthylphenylhydrazone, and polycarbonate in dioxane at a ratio of 1:75:82 (weight ratio) to obtain an organic photoconductive coating solution. The above-mentioned coating solution is coated on the aluminum alloy drum base by dip coating, the coating speed is 5.5mm/s, the viscosity of the coating solution is 450cp, the drying temperature is 90°C, and the drying time is 3.5 hours. The dried organic The thickness of the photoconductive coating layer was 30 μm.

The photoconductive data of the single-layer organic composite photoconductor are shown in Table 1.

Comparative Example 2

The chemical structural formula is:

The titanium phthalocyanine is added into tetrahydrofuran and a sanding medium, sanded at room temperature for 4 to 8 hours, and the solvent is evaporated to obtain titanium phthalocyanine dispersed particles. Stir and disperse titanium phthalocyanine dispersed particles, α-naphthalene phenylhydrazone, and polycarbonate in dioxane at a ratio of 1:75:82 (weight ratio) to obtain an organic photoconductive coating solution. The above-mentioned coating solution is coated on the aluminum alloy drum base by dip coating, the coating speed is 5.5mm/s, the viscosity of the coating solution is 450cp, the drying temperature is 90°C, and the drying time is 3.5 hours. The dried organic The thickness of the photoconductive coating layer was 30 μm.

The photoconductive data of the single-layer organic composite photoconductor are shown in Table 1.

Table 1 Photoconductivity data of single-layer organic composite photoconductors

Photosensitivity S

(lux·s) ^-1       Charging potential Dark decay Residual potential

λ＝ λ＝ λ＝ λ＝ (V) (V/s) (V)

          454nm   570nm   679nm   76nm

Example 1 0.185 0.42 0.666 0.95 714 29 22

Example 2 0.175 0.33 0.55 0.90 756 28 25

Example 3 0.167 0.303 0.513 0.88 751 31 45

Example 4 0.152 0.303 0.476 0.87 673 38 55

Example 5 0.15 0.279 0.44 0.87 733 42 56

Example 6 0.147 0.238 0.42 0.85 616 48 44

Example 7 0.175 0.279 0.42 0.84 628 51 62

Example 8 0.15 0.238 0.44 0.84 658 46 68

Example 9 0.201 0.624 0.666 1.19 622 26 44

Example 10 0.147 0.303 0.44 0.87 700 51 60

Example 11 0.14 0.25 0.333 0.84 596 46 77

Example 12 0.196 0.48 0.55 1.11 714 19 22

Compare Implementation 0.126 0.225 0.15 0.11 647 40 63

example 1

Compare Implementation 0.12 0.20 0.33 0.833 752 44 34

Example 2

Claims (6)

1, the azo of a kind of wideband response and better photosensitivity/phthalocyanine composite single layer organic photoconductor is characterized in that mainly being made up of carrier generation materials, carrier transmission material, resin and conductive matrices, wherein:

(1) chemical structural formula of carrier generation materials Shi oxazolyl bisdiazo/metal phthalocyanine composite material ， oxazolyl bisdiazo and metal phthalocyanine is respectively:

Wherein, R ₁, R ₂Be C ₁～C ₁₂Aliphatic group, C ₁～C ₁₂Alkoxy, halogen radical, hydroxyl, nitro or carboxylic acid group; M is copper, cobalt, nickel, aluminium, oxygen titanium or vanadyl;

(2) carrier transmission material is triaryl amine, hydrazone class, pyrazolines, triarylmethane class or tetraphenyl diphenyl amine compound;

(3) it forms the weight share meter:

Oxazolyl bisdiazo 1-5 part

Metal phthalocyanine 1-5 part

Carrier transmission material 80-300 part

Resin 80-300 part

Organic solvent 80-300 part

Adjuvant 0.1-0.5 part

2, the azo of wideband response according to claim 1 and better photosensitivity/phthalocyanine composite single layer organic photoconductor, it is characterized in that said resin, is the multipolymer or the polyvinyl acetate resins of polycarbonate, polyvinyl butyral, polystyrene, polymethylmethacrylate, Polyvinylchloride, Vingon, polyacrylonitrile, vinylidene chloride-polyacrylonitrile.

3, the azo of wideband response according to claim 1 and better photosensitivity/phthalocyanine composite single layer organic photoconductor, it is characterized in that said solvent, be tetrahydrofuran, dioxane, toluene, dimethylbenzene, butanone, cyclohexanone, methylene chloride, methenyl choloride, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether, N, dinethylformamide, N, N-dimethyl acetamide a kind of, or the mixed solvent of above-mentioned any two kinds of solvent compositions.

4. the azo of wideband response according to claim 1 and better photosensitivity/phthalocyanine composite single layer organic photoconductor, it is characterized in that said conductive matrices, be conduction sheet metal, ito glass or above scribble the polyester sheet of conducting medium, or drum type, banded conducting metal or electrical conductivity alloy.

5, the preparation method of the azo of a kind of wideband response as claimed in claim 1 and better photosensitivity/phthalocyanine composite single layer organic photoconductor is characterized in that concrete steps are:

(1) azo/phthalocyanine blended complex, resin and carrier transmission material are pressed the usage ratio dispersed with stirring in organic solvent, the solid content of solution is 10～50% by weight, promptly gets the organic photoconductive masking liquid;

(2) adopt dip coating that organic photoconductive solution is coated on the conductive matrices, its coating speed is 4.0～7.0mm/s, and coating fluid viscosity is at 300～500cp, and bake out temperature is 80～120 ℃, drying time is 3.5 hours, and dry organic photoconductive coat thickness is 15～45 μ m.

6, the preparation method of the azo of wideband response according to claim 5 and better photosensitivity/phthalocyanine composite single layer organic photoconductor, it is characterized in that: said azo/phthalocyanine blended complex, its preparation method is at normal temperatures with azo and two kinds of materials of phthalocyanine, after purified, the dried, with 0.1～9.9: 9.9～0.1 weight ratio solubilizer grinding and mixing 4～12 hours in sand mill or bowl mill, after grinding end, filter, drying makes azo/phthalocyanine blended complex.

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