JPH0359431B2 - - Google Patents
Info
- Publication number
- JPH0359431B2 JPH0359431B2 JP18370584A JP18370584A JPH0359431B2 JP H0359431 B2 JPH0359431 B2 JP H0359431B2 JP 18370584 A JP18370584 A JP 18370584A JP 18370584 A JP18370584 A JP 18370584A JP H0359431 B2 JPH0359431 B2 JP H0359431B2
- Authority
- JP
- Japan
- Prior art keywords
- protective layer
- surface protective
- phthalate
- electrophotographic photoreceptor
- photoreceptor
- 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
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 or to electrons; Manufacture thereof; Selection of materials therefor
- G03G5/14—Inert intermediate or cover layers for charge-receiving layers
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Photoreceptors In Electrophotography (AREA)
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は電子写真用感光体、更に詳しくは光導
電層の表面に保護層を有する電子写真用感光体に
おける上記表面保護層の改良に関するものであ
る。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to an electrophotographic photoreceptor, and more particularly to an improvement in the surface protective layer of an electrophotographic photoreceptor having a protective layer on the surface of a photoconductive layer. It is.
帯電、露光、現像、転写、クリーニング等のプ
ロセスを含む電子写真方式において用いられる感
光体としては、例えば米国特許第2297619号にも
開示されているように多くのものが実用化されて
いる。例えば適当な導電性基板上に有機光導電材
料を塗布あるいは蒸着などにより直接設けたも
の、あるいは上記材料を適当な有機バインダーと
ともに設けたもの、あるいはバインダー中に
ZnO，CdS，TiO2等の無機光導電材料を分散さ
せたもの、あるいは無定形セレン又はその合金な
どを蒸着したものなどが用いられている（例えば
特公昭45−5394号、特公昭46−3005号、特公昭49
−14271号公報参照）。これらの感光体における表
面層は電子写真複写装置内での繰り返し使用にお
いて機械的、電気的及び化学的ストレスを絶えず
受ける事になる。このためこれら感光体表面の損
傷を防ぎ、寿命を高めるため感光体表面に表面保
護層を設ける事が種々提案されている。これら表
面保護層の１つとしてフエノール樹脂、エポキシ
樹脂、アルキド樹脂などの熱硬化性樹脂を含む層
を用い、これに適当な導電性を付与し、カールソ
ンプロセスに用いた電子写真感光体では表面硬度
及び耐摩耗性の面で優れた改善効果が見い出され
ている。しかしながら上記熱硬化性樹脂を表面保
護層として例えばシート状の感光体上に被膜形成
した場合、被膜としての可撓性が不足し、十分満
足できる特性が得られないと言う問題がある。
Many photoreceptors have been put into practical use as photoreceptors used in electrophotography including processes such as charging, exposure, development, transfer, and cleaning, as disclosed in, for example, US Pat. No. 2,297,619. For example, an organic photoconductive material is provided directly on a suitable conductive substrate by coating or vapor deposition, or the above material is provided together with a suitable organic binder, or in a binder.
Products in which inorganic photoconductive materials such as ZnO, CdS, and TiO 2 are dispersed, or materials in which amorphous selenium or its alloys are vapor-deposited are used (for example, Japanese Patent Publication No. 45-5394, Japanese Patent Publication No. 46-3005 No., Special Publication 1977
-Refer to Publication No. 14271). The surface layer of these photoreceptors is constantly subjected to mechanical, electrical and chemical stress during repeated use within an electrophotographic copying apparatus. For this reason, various proposals have been made to provide a surface protective layer on the surface of the photoreceptor in order to prevent damage to the surface of the photoreceptor and extend its life. A layer containing a thermosetting resin such as phenol resin, epoxy resin, or alkyd resin is used as one of these surface protective layers, and is given appropriate conductivity. Excellent improvement effects have been found in terms of wear resistance and abrasion resistance. However, when the above-mentioned thermosetting resin is used as a surface protective layer to form a film on, for example, a sheet-like photoreceptor, there is a problem that the film lacks flexibility and sufficiently satisfactory characteristics cannot be obtained.
本発明の目的はこのような問題を確実に除去す
る事のできる電子写真用感光体を提供する事にあ
る。
An object of the present invention is to provide an electrophotographic photoreceptor that can reliably eliminate such problems.
本発明は種々検討の結果、熱硬化性樹脂、更に
詳しくはポリオール硬化型ポリウレタン樹脂中
に、分子量が150〜600の範囲で１分子中に１〜３
個のエステル結合を有するフタル酸、脂肪酸、及
び脂肪酸２塩基酸系エステル化合物の中から選ば
れる少なくとも１種類の化合物を適当量含有させ
る事により、上記熱硬化性樹脂本来の優れた表面
硬度及び耐摩耗性を何ら損なう事なく極めて優れ
た可撓性を有し、且つ電子写真特性に関しても極
めて良好な性能を有する表面保護層を電子写真用
感光体上に被膜形成し得る事を見い出した。
As a result of various studies, the present invention found that thermosetting resins, more specifically polyol-curing polyurethane resins, have molecular weights in the range of 150 to 600, and have a molecular weight of 1 to 3 per molecule.
By containing an appropriate amount of at least one type of compound selected from phthalic acid, fatty acid, and fatty acid dibasic acid ester compounds having ester bonds, the thermosetting resin has excellent surface hardness and resistance. It has been found that it is possible to form a surface protective layer on an electrophotographic photoreceptor, which has extremely excellent flexibility without any loss in abrasion resistance, and also has extremely good electrophotographic properties.
すなわち本発明は、導電性基板上に光導電層及
び表面保護層を順次積層してなる電子写真用感光
体において、上記表面保護層がポリオール硬化型
ポリウレタン樹脂及び分子量が150〜600の範囲で
１分子中に１〜３個のエステル結合を有するフタ
ル酸あるいは脂肪酸、あるいは脂肪族２塩基酸系
エステル化合物の中から選ばれる少なくとも１種
類の化合物を含む事を特徴とする電子写真用感光
体である。 That is, the present invention provides an electrophotographic photoreceptor in which a photoconductive layer and a surface protective layer are sequentially laminated on a conductive substrate, in which the surface protective layer is made of a polyol-curable polyurethane resin and a molecular weight in the range of 150 to 600. An electrophotographic photoreceptor characterized by containing at least one compound selected from phthalic acid or fatty acid having 1 to 3 ester bonds in the molecule, or an aliphatic dibasic acid ester compound. .
本発明において用いられる光導電体には例えば
適当な導電性基板上に無定形セレン又はその合金
などを蒸着したもの、あるいはバインダー中に
ZnO，CdS，TiO2などの無機光導電材料を分散
させたもの、あるいは有機光導電体として例えば
ポリ−Ｎ−ビニルカルバゾール（PVK）、PVK
と２，４，７−トリニトロフルオレノンとの電荷
移動型錯体、フタロシアニンなどの顔料をバイン
ダー中に分散させた光導電体、電荷発生層と電荷
移動層を移層させた機能分離型光導電体などが含
まれる。 The photoconductor used in the present invention is, for example, one in which amorphous selenium or its alloy is deposited on a suitable conductive substrate, or in a binder.
Dispersed inorganic photoconductive materials such as ZnO, CdS, TiO2, etc., or organic photoconductors such as poly-N-vinylcarbazole (PVK), PVK
and 2,4,7-trinitrofluorenone, a photoconductor in which a pigment such as phthalocyanine is dispersed in a binder, and a functionally separated photoconductor in which a charge generation layer and a charge transfer layer are transferred. etc. are included.
本発明において用いられる表面保護層としては
特開昭57−30846号公報に開示されているような
金属酸化物を種々の熱硬化性樹脂中に分散させた
ものがあるが、熱硬化性樹脂としてはポリエーテ
ルポリオール硬化型、ポリエステルポリオール硬
化型、アクリルポリオール硬化型のポリウレタン
樹脂を用いる。 As the surface protective layer used in the present invention, there is one in which a metal oxide is dispersed in various thermosetting resins as disclosed in JP-A No. 57-30846. A polyurethane resin of a polyether polyol-curing type, a polyester polyol-curing type, or an acrylic polyol-curing type is used.
上記熱硬化性樹脂中に含有させる事のできるエ
ステル系化合物としては、フタル酸エステル類と
してフタル酸ジメチル、フタル酸ジエチル、フタ
ル酸ジイソブチル、フタル酸ジブチル、フタル酸
ジヘプチル、フタル酸ジ２−エチルヘキシル、フ
タル酸ジイメオクチル、フタル酸ジｎ−オクチ
ル、フタル酸ジノニル、フタル酸ジイソデシル、
フタル酸ジトリデシル、フタル酸ジシクロヘキシ
ル、フタル酸ブチルベンジル、フタル酸ブチルラ
ウリル等、脂肪酸エステル類としてはオレイン酸
ブチル、アセチルリシノール酸メチル等、脂肪族
２塩基酸エステル類としてはコハク酸ジイソデシ
ル、アジピン酸ジオクチル、アジピン酸ジイソデ
シル、アゼライン酸ジオクチル、セバシン酸ジブ
チル、セバシン酸ジオクチル、テトラヒドロフタ
ル酸ジオクチル等がある。 Examples of ester compounds that can be contained in the thermosetting resin include phthalate esters such as dimethyl phthalate, diethyl phthalate, diisobutyl phthalate, dibutyl phthalate, diheptyl phthalate, di2-ethylhexyl phthalate, Diimeoctyl phthalate, di-n-octyl phthalate, dinonyl phthalate, diisodecyl phthalate,
Ditridecyl phthalate, dicyclohexyl phthalate, butylbenzyl phthalate, butyl lauryl phthalate, etc. Fatty acid esters include butyl oleate, methyl acetyl ricinolate, etc. Aliphatic dibasic acid esters include diisodecyl succinate, dioctyl adipate, etc. , diisodecyl adipate, dioctyl azelaate, dibutyl sebacate, dioctyl sebacate, dioctyl tetrahydrophthalate, and the like.
上記エステル系化合物の上記ポリオール硬化型
ポリウレタン樹脂への含有量は0.1〜50重量部で
あり、２〜30重量部の含有量において表面保護層
として電子写真用感光体上に被膜形成した場合に
特にその効果が著しい。 The content of the ester compound in the polyol-curable polyurethane resin is from 0.1 to 50 parts by weight, and when the content is from 2 to 30 parts by weight, it is particularly useful when forming a film on an electrophotographic photoreceptor as a surface protective layer. The effect is remarkable.
以下、本発明を実施例により説明する。 The present invention will be explained below using examples.
実施例 １
ポリエステルフイルム上にアルミニウムを蒸着
させた支持体にダイアンブルー（CI21180）をテ
トラヒドロフラン中に分散させた分散液を塗布
し、厚さ0.5μの電荷発生層を形成した。この上に
構造式(1)で示されるヒドラゾン２部、ポリカーボ
ネート樹脂３部をテトラヒドロフランに溶解させ
た溶液を塗布して厚さ15μの電荷輸送層を得た。Example 1 A dispersion of Diane Blue (CI21180) in tetrahydrofuran was applied to a support made of polyester film on which aluminum was vapor-deposited to form a charge generation layer with a thickness of 0.5 μm. A solution prepared by dissolving 2 parts of hydrazone represented by structural formula (1) and 3 parts of polycarbonate resin in tetrahydrofuran was applied onto this to obtain a charge transport layer with a thickness of 15 μm.
構造式(1)
さらにこの上に、粒径0.1μ以下の酸化スズ35重
量部をポリエステルポリオール硬化型樹脂（関西
ペイント社製、レタン2000）65重量部、フタル酸
ジｎ−オクチル（花王石鹸社製、＃85）10重量部
中に分散させた後、デイツピングにより、乾燥後
の膜厚が2μとなるように表面保護層を塗布した。
このようにして得られた表面保護層を有する電子
写真用感光体を富士ゼロツクス株式会社製FX−
1075に装着し、画像出しを150000回繰り返した。 Structural formula (1) Furthermore, on top of this, 35 parts by weight of tin oxide with a particle size of 0.1μ or less, 65 parts by weight of polyester polyol curable resin (manufactured by Kansai Paint Co., Ltd., Rethane 2000), and di-n-octyl phthalate (manufactured by Kao Soap Co., Ltd., #85). After dispersing in 10 parts by weight, a surface protective layer was applied by dipping so that the film thickness after drying was 2 μm.
The electrophotographic photoreceptor having the surface protective layer thus obtained was manufactured by Fuji Xerox Co., Ltd.
1075, and image output was repeated 150,000 times.
その結果、画像出し150000回後においても表面
保護層の摩耗劣化はまつたく観察されなかつた。
同時に表面保護層の可撓性が不足している場合に
引き起こされる表面保護層中の亀裂の発生に関し
ても画像出し150000回を経てまつたく発生せず、
初期の画質と比較しても何んら遜色のない極めて
鮮明な画像が得られた。 As a result, no wear and tear deterioration of the surface protective layer was observed even after 150,000 images were printed.
At the same time, even after 150,000 images, cracks did not occur in the surface protective layer, which is caused by insufficient flexibility of the surface protective layer.
We were able to obtain extremely clear images that were comparable in quality to the initial image quality.
尚、この時同時に作製された、表面保護層中に
フタル酸ジｎ−オクチルを含まない感光体におい
ては、画像出しを20000回繰り返した後に、表面
保護層中に多数の微細な亀裂が生じ画像の著しい
劣化が観察された。 In addition, in a photoreceptor that did not contain di-n-octyl phthalate in its surface protective layer, which was manufactured at the same time, many fine cracks were formed in the surface protective layer after image formation was repeated 20,000 times. Significant deterioration was observed.
実施例 ２
実施例１のポリエステルポリオール硬化型樹脂
（関西ペイント社製、レタン2000）をアクリルポ
リオール硬化型樹脂（関西ペイント社製、レタン
4000）に変更、フタル酸ジｎ−オクチル（花王石
鹸社製、＃85）をフタル酸ジ２−エチルヘキシル
（花王石鹸社製、＃80）に変更した以外は実施例
１と全く同様にして表面保護層を有する感光体を
作製し富士ゼロツクス株式会社製FX−1075に装
着して画像出しを150000回繰り返した。Example 2 The polyester polyol curable resin (manufactured by Kansai Paint Co., Ltd., Rethan 2000) of Example 1 was mixed with the acrylic polyol curable resin (manufactured by Kansai Paint Co., Ltd., Rethane 2000).
The surface was prepared in the same manner as in Example 1, except that di-n-octyl phthalate (manufactured by Kao Soap Co., Ltd., #85) was changed to di-2-ethylhexyl phthalate (manufactured by Kao Soap Co., Ltd., #80). A photoreceptor with a protective layer was prepared and mounted on FX-1075 manufactured by Fuji Xerox Co., Ltd., and image generation was repeated 150,000 times.
その結果、画像出し150000回後においても表面
保護層の摩耗劣化は全く観察されなかつた。同時
に表面保護層の可撓性が不足している場合に引き
起こされる表面保護層中の亀裂の発生に関しても
画像出し150000回を経て全く観察されず極めて鮮
明な画像が得られた。 As a result, no wear and tear deterioration of the surface protective layer was observed even after 150,000 images were printed. At the same time, regarding the occurrence of cracks in the surface protective layer caused by insufficient flexibility of the surface protective layer, no cracks were observed after 150,000 images, and extremely clear images were obtained.
尚、この時同時に作製された、表面保護層中に
フタル酸ジ２−エチルヘキシルを含まない感光体
においては、画像出しを20000回繰り返した後に、
表面保護層中に多数の微細な亀裂が生じ画像の著
しい劣化が観察された。 In addition, in the photoreceptor that was prepared at the same time and did not contain di-2-ethylhexyl phthalate in the surface protective layer, after image formation was repeated 20,000 times,
Many fine cracks were generated in the surface protective layer and significant deterioration of the image was observed.
本発明によれば、すぐれた可撓性と表面硬度お
よび耐摩耗性を有し、かつすぐれた電子写真特性
を有する表面保護層を備えた電子写真用感光体が
得られる。
According to the present invention, it is possible to obtain an electrophotographic photoreceptor having a surface protective layer having excellent flexibility, surface hardness, and abrasion resistance, and having excellent electrophotographic properties.
Claims (1)
次積層してなる電子写真用感光体において、上記
表面保護層がポリオール硬化型ポリウレタン樹脂
及び分子量が150〜600の範囲で１分子中に１〜３
個のエステル結合を有するフタル酸あるいは脂肪
酸、あるいは脂肪族２塩基酸系エステル化合物の
中から選ばれる少なくとも１種類の化合物を含む
事を特徴とする電子写真用感光体。1. In an electrophotographic photoreceptor in which a photoconductive layer and a surface protective layer are sequentially laminated on a conductive substrate, the surface protective layer comprises a polyol-curable polyurethane resin and a molecular weight of 150 to 600 in one molecule. ~3
1. An electrophotographic photoreceptor comprising at least one compound selected from phthalic acid or fatty acid having ester bonds, or aliphatic dibasic acid ester compounds.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18370584A JPS6162043A (en) | 1984-09-04 | 1984-09-04 | Electrophotografic sensitive body |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18370584A JPS6162043A (en) | 1984-09-04 | 1984-09-04 | Electrophotografic sensitive body |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6162043A JPS6162043A (en) | 1986-03-29 |
| JPH0359431B2 true JPH0359431B2 (en) | 1991-09-10 |
Family
ID=16140509
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP18370584A Granted JPS6162043A (en) | 1984-09-04 | 1984-09-04 | Electrophotografic sensitive body |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6162043A (en) |
-
1984
- 1984-09-04 JP JP18370584A patent/JPS6162043A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6162043A (en) | 1986-03-29 |
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