JPH032297B2 - - Google Patents
Info
- Publication number
- JPH032297B2 JPH032297B2 JP11519084A JP11519084A JPH032297B2 JP H032297 B2 JPH032297 B2 JP H032297B2 JP 11519084 A JP11519084 A JP 11519084A JP 11519084 A JP11519084 A JP 11519084A JP H032297 B2 JPH032297 B2 JP H032297B2
- Authority
- JP
- Japan
- Prior art keywords
- zinc oxide
- photoconductive layer
- insulating resin
- particles
- oxide particles
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 76
- 239000002245 particle Substances 0.000 claims description 35
- 239000011787 zinc oxide Substances 0.000 claims description 31
- 108091008695 photoreceptors Proteins 0.000 claims description 18
- 229920005989 resin Polymers 0.000 claims description 15
- 239000011347 resin Substances 0.000 claims description 15
- 239000006185 dispersion Substances 0.000 description 7
- 238000000034 method Methods 0.000 description 5
- 238000007639 printing Methods 0.000 description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 206010034972 Photosensitivity reaction Diseases 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000007645 offset printing Methods 0.000 description 3
- 230000036211 photosensitivity Effects 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 229920000178 Acrylic resin Polymers 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000010186 staining Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 229920000297 Rayon Polymers 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 235000012745 brilliant blue FCF Nutrition 0.000 description 1
- UDSAIICHUKSCKT-UHFFFAOYSA-N bromophenol blue Chemical compound C1=C(Br)C(O)=C(Br)C=C1C1(C=2C=C(Br)C(O)=C(Br)C=2)C2=CC=CC=C2S(=O)(=O)O1 UDSAIICHUKSCKT-UHFFFAOYSA-N 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
- G03G5/02—Charge-receiving layers
- G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
- G03G5/08—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor characterised by the photoconductive material being inorganic
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Photoreceptors In Electrophotography (AREA)
Description
本発明は電子写真用感光体、更に詳細には表面
硬度のすぐれた光導電層を設けた電子写真用感光
体に関する。
従来より電子写真に用いられている感光体は、
導電処理した紙、プラスチツクフイルム等の支持
体上に、酸化亜鉛粉末および絶縁性樹脂を主成分
としてなる厚さ約10μの光導電層を設けてなる。
上記光導電層を形成する酸化亜鉛粉末は1μ以
下通常は0.2〜0.5μの粒径を有し、嵩密度0.3〜
0.45g／cm3の粉末であり、絶縁性樹脂としてはシ
リコーン樹脂、アクリル樹脂、アルキツド樹脂等
が使用されている。
光導電層を形成するに当つては絶縁性樹脂の有
機溶剤溶液に、重量比で酸化亜鉛粉末対絶縁性樹
脂の割合が約４〜７：１となるように酸化亜鉛悪
塩粉末を分散させ、この分散液を支持体に塗布す
ることによつて製造している。
酸化亜鉛感光体を例えばオフセツト印刷用に使
用して印刷する場合、印刷枚数として少なくとも
3000枚、好ましくは5000枚以上の印刷ができる耐
性を有することが要求されているが、上述した如
き従来の酸化亜鉛光導電層を塗布した感光体は、
光導電層の表面硬度が充分でないため摩耗し易
く、製版印刷時の地の汚れや、画像不鮮明を生ず
る原因となつている。その原因は種々考えられる
が、その一つは感光体上に画像を形成した光導電
層は印刷を繰返す中に結合剤たる絶縁性樹脂が摩
耗され、離脱または剥離されて、酸化亜鉛粉末自
体も脱落し画像を不鮮明にしたり、あるいは酸化
亜鉛が露出し、ここに現像液もしくはトナーが付
着し、印刷された画面を汚したりするのである。
このため光導電層の表面硬度を向上させる一つ
の手段として絶縁性樹脂として硬質樹脂例えばポ
リエステル樹脂を使用すると、光導電層の光感度
の低下を生じたり、あるいは光導電層の可撓性が
劣るようになり、光導電層に亀裂を生じ易く、斑
を生ずるので好ましくない。
従来の光導電層を作るための酸化亜鉛粉末−絶
縁性樹脂分散液を作るに当つて、酸化亜鉛粉末を
絶縁性樹脂溶液に分散させると、酸化亜鉛粉末は
単一粉末粒子として挙動せず、凝集して凝集体を
形成し、この凝集体は分散液を支持体に塗布し、
乾燥した場合にもそのままの形で存在する。この
凝集体はその中に微細な空洞を有する比較的弱い
凝集力しか有せず、このため感光体を印刷に使用
したとき、光導電層は絶縁性樹脂の摩耗と共に酸
化亜鉛凝集体も摩擦力により破壊され脱落しまた
は陥没し上述した欠点を生ずる。
本発明は上述した従来の酸化亜鉛粉末および絶
縁性樹脂を用いた光導電層を有する感光体の欠点
を克服した表面硬度のすぐれた電子写真用感光体
を提供することにある。
本発明は支持体上に酸化亜鉛および絶縁性樹脂
からなる光導電層を設けた電子写真用感光体にお
いて、上記酸化亜鉛が少なくとも0.6ｇ／cm3の嵩
密度および2.0mm以下の粒径を有する酸化亜鉛で
あるオフセツト印刷用感光体にある。
本発明で使用する酸化亜鉛は上述した如き少な
くとも0.6ｇ／cm3、通常0.6〜1.5ｇ／cm3、好ましく
は0.7〜1.2ｇ／cm3を嵩密度および２mm以下、好ま
しくは0.3〜1.0mmの粒径を有する酸化亜鉛粒子で
ある。
かかる酸化亜鉛粒子は次の如くして製造するこ
とができる。即ち従来より電子写真用感光体の光
導電層の形成に使用されている酸化亜鉛粉末を、
少なくとも20Kg／cm2の圧力で圧縮し、圧縮体を破
砕することによつて作ることができる。
上記圧縮には任意の圧縮機例えばモザイクタイ
ル素地成型用油圧プレスを使用できる。酸化亜鉛
粉末を圧縮するに当つては少なくとも20Kg／cm2好
ましくは150Kg／cm2以下、更に好ましくは40Kg／
cm2〜100Kg／cm2の圧力を使用する。20Kg／cm2より
小さい圧力では続いて圧縮体を破砕して得られる
粒子の結合力が充分でなく、絶縁性樹脂溶液に分
散させるとき粒子が更に破砕されることがあり、
またこれを用いて形成される光導電層の表面硬度
が充分でなくなり好ましくない。また圧力が150
Kg／cm2より大となると、光導電層の光感度を低下
させることがあり好ましくない。またあまり大き
すぎると圧縮体の破砕に手間がかかり、また圧縮
機の性能からも不必要に大にするのは実用的でな
い。
次に上述した如くして得られた圧縮体を破砕す
る。破砕に当つては圧縮体を篩工程を通すことで
達成でき回転ふるい、平面ふるいが用いられるが
振動ふるいが好ましい。また別法として酸化亜鉛
粉末を上記圧力を付与しうるよう調整した二本ロ
ールのニツプに導入し、圧縮をすることにより、
酸化亜鉛粒子の圧縮と破砕を同時に行なうことも
できる。
次に破砕して得られた酸化亜鉛粒子を要すれば
篩分けして粒径２mm以下、好ましくは0.3〜1.0mm
の粒子とする。これらの粒子は一般に少なくとも
0.6ｇ／cm3、通常0.7〜1.2ｇ／cm3の嵩密度を有す
る。
上記粒径が2.0mmより大となると酸化亜鉛粒子
の分散液を製造するとき、その分散に長時間を要
し好ましくない。粒径の下限には厳密な規制はな
い。また製造された酸化亜鉛粒子は、一つの測度
として、次の方法で測定して2.0〜10.0ｇ特に3.0
〜6.0ｇの硬さを有するのが好ましい。この範囲
であると、本発明による酸化亜鉛粒子を用いて作
つた感光体の表面硬度が良好で、耐性を改良する
ことができることが判つた。硬さの測定は次の如
くして行なつた。即ち直径0.84mm（20メツシユ）
〜1.7mm（10メツシユ）の粒子をとり、感量（読
みとり限度）0.5ｇのバネ式秤量機を乗せ、粒子
を圧縮し、粒子がくずれたときの表示重量を硬さ
の表示とした。
上述した本発明による酸化亜鉛粒子を用いる
と、前述した従来の酸化亜鉛粉末を用いた場合と
異なり、表面硬度のすぐれた光導電層を形成する
ことができる。
本発明方法で製造した酸化亜鉛粒子は従来より
知られている通常の方法で絶縁性樹脂の有機溶剤
溶液に分散させて公知の支持体に塗布し、乾燥す
ることにより電子写真用感光体とすることができ
る。
以下に参考例および実施例をあげて本発明を説
明する。
参考例 １
通常の電子写真用の粒径0.2〜0.5μの酸化亜鉛
粉末をモザイクタイル素地用油圧プレスを用い、
40Kg／cm2に圧縮し、形成された圧縮体を次いで振
動ふるいで破砕しつつ篩分けし、粒径１mm以下の
酸化亜鉛粒子50ｇを得た。
参考例２および３
参考例１と同様にして、それぞれ圧力80Kg／cm2
および100Kg／cm2を使用して粒径１mm以下の酸化
亜鉛粒子をそれぞれ55ｇを得た。
実施例
上記参考例１，２および３で作つた各酸化亜鉛
粒子を用い、下記の処方の酸化亜鉛分散液を作つ
た。
酸化亜鉛粒子 35.0ｇ
アクリル樹脂LR−637（三菱レーヨン社製、商
品名） 17.5ｇ
ブロムフエノールブル１％メタノール溶液
0.5c.c.
トルエン 80c.c.
上記各成分をボールミルで４時間分散させて分
散液を製造した。裏面を高分子導電剤（ダウケミ
カル社製ECR−77）で導電処理した紙の表面に、
上記分散液を塗布し、100℃で５分間乾燥し、酸
化亜鉛感光紙を作つた。塗布量は22ｇ／m2（固形
分）とした。
比較例として上記分散液に用いた酸化亜鉛粒子
の代りに、通常の光導電性酸化亜鉛粉末を35.0ｇ
を用いて、同様に酸化亜鉛感光紙を作つた。塗布
量は同じく22ｇ／m2（固形分）とした。
これらの感光紙の特性は次のとおりであつた。
The present invention relates to an electrophotographic photoreceptor, and more particularly to an electrophotographic photoreceptor provided with a photoconductive layer having excellent surface hardness. Photoreceptors traditionally used in electrophotography are
A photoconductive layer having a thickness of approximately 10 μm and consisting mainly of zinc oxide powder and an insulating resin is provided on a support such as electrically conductive treated paper or plastic film. The zinc oxide powder forming the photoconductive layer has a particle size of 1μ or less, usually 0.2 to 0.5μ, and a bulk density of 0.3 to 0.5μ.
It is a powder of 0.45g/cm 3 , and silicone resin, acrylic resin, alkyd resin, etc. are used as the insulating resin. To form the photoconductive layer, zinc oxide bad salt powder is dispersed in an organic solvent solution of an insulating resin so that the weight ratio of zinc oxide powder to insulating resin is about 4 to 7:1. , is produced by coating this dispersion on a support. When printing using a zinc oxide photoreceptor, for example, for offset printing, the number of printed sheets is at least
Although it is required to have a durability capable of printing 3000 sheets, preferably 5000 sheets or more, the conventional photoreceptor coated with a zinc oxide photoconductive layer as described above is
Since the surface hardness of the photoconductive layer is not sufficient, it is easily abraded, which causes staining of the background and blurred images during plate making and printing. There are various possible causes for this, but one of them is that the insulating resin that acts as a binder in the photoconductive layer that forms an image on the photoreceptor is worn away during repeated printing, and the zinc oxide powder itself is also removed. The zinc oxide can fall off and make the image unclear, or the zinc oxide can be exposed and developer or toner can adhere to it, staining the printed screen. For this reason, if a hard resin such as polyester resin is used as an insulating resin as a means of improving the surface hardness of the photoconductive layer, the photosensitivity of the photoconductive layer may decrease or the flexibility of the photoconductive layer may be poor. This is undesirable because the photoconductive layer tends to crack and cause spots. When preparing a conventional zinc oxide powder-insulating resin dispersion for making a photoconductive layer, when zinc oxide powder is dispersed in an insulating resin solution, the zinc oxide powder does not behave as a single powder particle; agglomerates to form aggregates, which aggregates are applied to a support by applying the dispersion;
It remains in its original form even when dried. This aggregate has only a relatively weak cohesive force with fine cavities in it, and therefore when the photoreceptor is used for printing, the photoconductive layer is affected by friction as well as the abrasion of the insulating resin. This causes the above-mentioned defects to occur due to destruction, falling off, or caving in. An object of the present invention is to provide an electrophotographic photoreceptor having excellent surface hardness, which overcomes the drawbacks of the conventional photoreceptor having a photoconductive layer using zinc oxide powder and an insulating resin. The present invention provides an electrophotographic photoreceptor in which a photoconductive layer made of zinc oxide and an insulating resin is provided on a support, wherein the zinc oxide has a bulk density of at least 0.6 g/cm 3 and a particle size of 2.0 mm or less. Found in photoreceptors for offset printing, which are zinc oxide. The zinc oxide used in the present invention has a bulk density of at least 0.6 g/cm 3 , usually 0.6 to 1.5 g/cm 3 , preferably 0.7 to 1.2 g/cm 3 as described above, and a bulk density of 2 mm or less, preferably 0.3 to 1.0 mm. Zinc oxide particles having a particle size. Such zinc oxide particles can be produced as follows. That is, zinc oxide powder, which has been conventionally used to form the photoconductive layer of electrophotographic photoreceptors,
It can be made by compressing at a pressure of at least 20 kg/cm 2 and crushing the compressed body. Any compressor, such as a hydraulic press for forming mosaic tile substrates, can be used for the compression. When compressing zinc oxide powder, the compression ratio is at least 20Kg/ cm2 , preferably 150Kg/ cm2 or less, and more preferably 40Kg/cm2.
A pressure of between cm2 and 100Kg/ cm2 is used. If the pressure is lower than 20Kg/ cm2, the bonding force of the particles obtained by crushing the compressed body will not be sufficient, and the particles may be further crushed when dispersed in an insulating resin solution.
Moreover, the surface hardness of the photoconductive layer formed using this becomes insufficient, which is undesirable. Also the pressure is 150
If it exceeds Kg/cm 2 , the photosensitivity of the photoconductive layer may be lowered, which is not preferable. Moreover, if it is too large, it will take time and effort to crush the compressed body, and it is not practical to make it unnecessarily large from the viewpoint of the performance of the compressor. Next, the compacted body obtained as described above is crushed. Crushing can be accomplished by passing the compressed body through a sieving process, and a rotating sieve or a flat sieve may be used, but a vibrating sieve is preferred. Alternatively, zinc oxide powder is introduced into the nip of two rolls adjusted to apply the above pressure and compressed.
It is also possible to compress and crush the zinc oxide particles at the same time. Next, if necessary, the zinc oxide particles obtained by crushing are sieved to have a particle size of 2 mm or less, preferably 0.3 to 1.0 mm.
Let the particles be . These particles generally have at least
It has a bulk density of 0.6 g/cm 3 , usually 0.7-1.2 g/cm 3 . If the particle size is larger than 2.0 mm, it will take a long time to disperse when producing a dispersion of zinc oxide particles, which is not preferable. There is no strict regulation on the lower limit of particle size. In addition, the produced zinc oxide particles are measured as one measurement using the following method, and are 2.0 to 10.0 g, especially 3.0 g.
Preferably, it has a hardness of ~6.0 g. It has been found that within this range, the surface hardness of the photoreceptor made using the zinc oxide particles according to the present invention is good and the durability can be improved. The hardness was measured as follows. i.e. diameter 0.84mm (20 meshes)
Particles of ~1.7 mm (10 meshes) were taken, and a spring-type weigher with a sensitivity (reading limit) of 0.5 g was placed on the weigher to compress the particles, and the weight displayed when the particles collapsed was used as an indication of hardness. When the zinc oxide particles according to the present invention described above are used, a photoconductive layer with excellent surface hardness can be formed, unlike the case where the conventional zinc oxide powder described above is used. The zinc oxide particles produced by the method of the present invention are dispersed in an organic solvent solution of an insulating resin by a conventionally known method, coated on a known support, and dried to form an electrophotographic photoreceptor. be able to. The present invention will be explained below with reference to reference examples and examples. Reference example 1 Zinc oxide powder with a particle size of 0.2 to 0.5μ for ordinary electrophotography was prepared using a hydraulic press for mosaic tile substrates.
It was compressed to 40 kg/cm 2 and the formed compact was then crushed and sieved using a vibrating sieve to obtain 50 g of zinc oxide particles having a particle size of 1 mm or less. Reference Examples 2 and 3 Same as Reference Example 1, each with a pressure of 80Kg/cm 2
and 100 Kg/cm 2 to obtain 55 g of zinc oxide particles each having a particle size of 1 mm or less. Example Using each of the zinc oxide particles produced in Reference Examples 1, 2, and 3 above, a zinc oxide dispersion having the following formulation was produced. Zinc oxide particles 35.0g Acrylic resin LR-637 (manufactured by Mitsubishi Rayon Co., Ltd., trade name) 17.5g Bromophenol blue 1% methanol solution
0.5 cc toluene 80 c.c. Each of the above components was dispersed in a ball mill for 4 hours to prepare a dispersion liquid. On the surface of paper whose back side has been conductively treated with a polymeric conductive agent (ECR-77 manufactured by Dow Chemical Company),
The above dispersion was applied and dried at 100°C for 5 minutes to produce zinc oxide photosensitive paper. The coating amount was 22 g/m 2 (solid content). As a comparative example, 35.0 g of ordinary photoconductive zinc oxide powder was used instead of the zinc oxide particles used in the above dispersion.
Zinc oxide photosensitive paper was also made using the same method. The coating amount was also 22 g/m 2 (solid content). The characteristics of these photosensitive papers were as follows.
【表】
上記表１のデータから明らかな如く、本発明の
酸化亜鉛粒子を用いて作つた感光紙は、従来例で
ある比較例に比し、帯電特性、光感度とも大差な
く、しかも感光層の硬度が向上している。このた
めこれらはオフセツト印刷用原版および転写用原
版等の電子写真用感光体としてすぐれている。[Table] As is clear from the data in Table 1 above, the photosensitive paper made using the zinc oxide particles of the present invention has no significant difference in charging characteristics and photosensitivity compared to the conventional comparative example, and moreover, the photosensitive paper The hardness has been improved. For this reason, these are excellent as photoreceptors for electrophotography such as original plates for offset printing and original plates for transfer.
Claims (1)
る光導電層を設けた電子写真用感光体において、
上記酸化亜鉛が少なくとも0.6ｇ／cm3の嵩密度お
よび2.0mm以下の粒径を有する酸化亜鉛粒子であ
ることを特徴とする電子写真用感光体。 ２ 酸化亜鉛粒子が2.0〜10.0ｇの荷重で破砕さ
れる硬さを有する特許請求の範囲第１項記載の電
子写真用感光体。[Scope of Claims] 1. An electrophotographic photoreceptor in which a photoconductive layer made of zinc oxide and an insulating resin is provided on a support,
An electrophotographic photoreceptor, wherein the zinc oxide is zinc oxide particles having a bulk density of at least 0.6 g/cm 3 and a particle size of 2.0 mm or less. 2. The electrophotographic photoreceptor according to claim 1, wherein the zinc oxide particles have a hardness that can be crushed under a load of 2.0 to 10.0 g.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11519084A JPS60257451A (en) | 1984-06-04 | 1984-06-04 | Electrophotographic sensitive body improved in surface hardness |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11519084A JPS60257451A (en) | 1984-06-04 | 1984-06-04 | Electrophotographic sensitive body improved in surface hardness |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60257451A JPS60257451A (en) | 1985-12-19 |
| JPH032297B2 true JPH032297B2 (en) | 1991-01-14 |
Family
ID=14656577
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11519084A Granted JPS60257451A (en) | 1984-06-04 | 1984-06-04 | Electrophotographic sensitive body improved in surface hardness |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60257451A (en) |
-
1984
- 1984-06-04 JP JP11519084A patent/JPS60257451A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS60257451A (en) | 1985-12-19 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |