JPS6335977B2 - - Google Patents
Info
- Publication number
- JPS6335977B2 JPS6335977B2 JP17344480A JP17344480A JPS6335977B2 JP S6335977 B2 JPS6335977 B2 JP S6335977B2 JP 17344480 A JP17344480 A JP 17344480A JP 17344480 A JP17344480 A JP 17344480A JP S6335977 B2 JPS6335977 B2 JP S6335977B2
- Authority
- JP
- Japan
- Prior art keywords
- titanium dioxide
- fluorine
- photosensitive
- photosensitivity
- electrophotographic
- 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
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical group O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 64
- 239000004408 titanium dioxide Substances 0.000 claims description 28
- 239000000463 material Substances 0.000 claims description 23
- 229910052731 fluorine Inorganic materials 0.000 claims description 15
- 239000011737 fluorine Substances 0.000 claims description 15
- 239000000843 powder Substances 0.000 claims description 8
- 239000011230 binding agent Substances 0.000 claims description 7
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 23
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 12
- 206010034972 Photosensitivity reaction Diseases 0.000 description 12
- 230000036211 photosensitivity Effects 0.000 description 12
- 230000014759 maintenance of location Effects 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 229910010413 TiO 2 Inorganic materials 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 239000007789 gas Substances 0.000 description 6
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 6
- 238000010306 acid treatment Methods 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 239000000975 dye Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000011701 zinc Substances 0.000 description 5
- -1 H 2 SO 4 Chemical class 0.000 description 4
- 150000001450 anions Chemical class 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 4
- 150000002222 fluorine compounds Chemical class 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 3
- 230000003301 hydrolyzing effect Effects 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 230000001235 sensitizing effect Effects 0.000 description 3
- WSFQLUVWDKCYSW-UHFFFAOYSA-M sodium;2-hydroxy-3-morpholin-4-ylpropane-1-sulfonate Chemical compound [Na+].[O-]S(=O)(=O)CC(O)CN1CCOCC1 WSFQLUVWDKCYSW-UHFFFAOYSA-M 0.000 description 3
- ZDTNHRWWURISAA-UHFFFAOYSA-N 4',5'-dibromo-3',6'-dihydroxyspiro[2-benzofuran-3,9'-xanthene]-1-one Chemical compound O1C(=O)C2=CC=CC=C2C21C1=CC=C(O)C(Br)=C1OC1=C(Br)C(O)=CC=C21 ZDTNHRWWURISAA-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- BHHYHSUAOQUXJK-UHFFFAOYSA-L zinc fluoride Chemical compound F[Zn]F BHHYHSUAOQUXJK-UHFFFAOYSA-L 0.000 description 2
- PYMRLXLRQJTTDA-UHFFFAOYSA-N 3-[4-[5-(3-ethyl-1,3-benzothiazol-2-ylidene)penta-1,3-dienyl]quinolin-1-ium-1-yl]propanoic acid;iodide Chemical compound [I-].C1=CC=C2C(/C=C/C=C/C=C3/N(C4=CC=CC=C4S3)CC)=CC=[N+](CCC(O)=O)C2=C1 PYMRLXLRQJTTDA-UHFFFAOYSA-N 0.000 description 1
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 241001561902 Chaetodon citrinellus Species 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 206010034960 Photophobia Diseases 0.000 description 1
- OAJHWYJGCSAOTQ-UHFFFAOYSA-N [Zr].CCCCCCCCO.CCCCCCCCO.CCCCCCCCO.CCCCCCCCO Chemical compound [Zr].CCCCCCCCO.CCCCCCCCO.CCCCCCCCO.CCCCCCCCO OAJHWYJGCSAOTQ-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 208000013469 light sensitivity Diseases 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000006864 oxidative decomposition reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 239000011698 potassium fluoride Substances 0.000 description 1
- 235000003270 potassium fluoride Nutrition 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- UCFSULAKAYDAAE-UHFFFAOYSA-N quinolin-1-ium;iodide Chemical compound I.N1=CC=CC2=CC=CC=C21 UCFSULAKAYDAAE-UHFFFAOYSA-N 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 229910000349 titanium oxysulfate Inorganic materials 0.000 description 1
- 229910000348 titanium sulfate Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 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
- G03G5/087—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor characterised by the photoconductive material being inorganic and being incorporated in an organic bonding material
Description
本発明は、二酸化チタンを感光層成分として含
有する電子写真感光材料に関し、更に詳しくは、
光感度、耐湿性の改良された二酸化チタンを含有
する電子写真感光材料に関する。
二酸化チタンを感光性粉末として感光層に含有
する電子写真感光材料についてはよく知られてい
る。しかしながら、二酸化チタンが電子写真感光
材料として広く実用されるに到つていないのは、
他の無機感光性粉末であるZnOやCdSなどに比べ
て光感度が劣ることによる。
二酸化チタンの光感度を向上させる方法につい
ては、種々の提案がなされているが、その中には
特開昭51−118434のように鉱酸で処理する方法に
ついても提案されている。しかしながら、HCl、
H2SO4などの鉱酸で処理した場合、処理後充分
水洗することは通常行なわれているにも拘らず、
Cl-、SO2- 4などの陰イオンがわずかに残存し、こ
れが、湿分によつて導電性を増し、暗保持性を低
下させ、いわゆる耐湿性に欠点を生じ、必ずしも
よい方法とは言えない。
ところが、発明者らは、弗酸や弗素化合物で二
酸化チタンを処理したところ、意外にも光感度特
に前露光後の光感度について良好な改良が行われ
るばかりでなく、耐湿性をも改良される知見を得
た。そして、その場合処理された二酸化チタンに
は、弗素が結合して含有されていることを見出
し、更に広汎な検討を進めて本発明を完成するに
到つた。
すなわち、本発明は無機感光性粉末と結合剤と
を主成分として含有する感光層を導電性基材上に
積層してなる電子写真感光材料において、前記無
機感光性粉末が弗素を0.01〜0.2％含む二酸化チ
タンを主成分とすることを特徴とする電子写真感
光材料である。
本発明に用いられる二酸化チタンは、種々の方
法で製造されたもの、例えば四塩化チタン又は硫
酸チタンを加水分解して得られる水和酸化チタン
を〓焼したり、四塩化チタンを酸素含有ガスで気
相酸化したり、アンモニウムチタニルサルフエー
トを熱分解したりして製造されたものでよく、光
感度を低下させるようなAl、Fe、Ni、Mn、Ｖ、
Ｐなどの不純物を多く含まないものであることが
好ましい。一方、特開昭51−118434に記載されて
いるような、二酸化チタンの電子写真特性を改良
するZn、Li、Mg、Ca、Sr、或いはBaなどの添
加剤をドープしたものであつても差支えない。
本発明の感光材料に用いられる無機感光性粉末
は、前記の弗素含有二酸化チタンを主成分とする
が、それ以外に例えばZnOやCdSなどの他の無機
感光性粉末を混用したものであつてもよく、弗素
含有二酸化チタンを50％以上含有するのが好まし
い。また、増感色素や、その他の添加剤を必要に
応じて併用することも差支えないし、本発明の二
酸化チタンに金属石鹸を表面処理するなどの方法
を適用するのも差支えない。
本発明に用いられる弗素を0.01〜0.2％含む二
酸化チタンは、通常水溶性であつて弗素イオンを
放出する弗素化合物を水に溶解させて、0.001〜
35％の濃度でかつPHが３以下である水溶液とし
て、この中に上記の二酸化チタンを加えて撹拌し
て処理し、処理後過、水洗した後、乾燥、粉砕
して得ることができる。
水溶性であつて弗素イオンを放出する弗素化合
物としては、例えば弗化アンモニウム、弗化カリ
ウム、弗化リチウム、弗化亜鉛、弗化水素などが
挙げられる。また、弗化水素のように容易に気相
状態で存在しうる化合物の場合は、これを気相で
二酸化チタンに作用させて処理することもでき
る。例えばKHF2を約250℃に加熱して弗化水素
ガスを発生させ、これを二酸化チタンの充填層に
導いて処理する方法なども適用される。二酸化チ
タンに含有される弗素の量は、二酸化チタンの比
表面積、OH基密度、処理条件などによつて一概
にいえないが、望ましくは0.01〜0.2％である。
弗素処理時の水溶液の濃度が0.001％より低いと
所望量の弗素処理が望めず、また35％を越えると
二酸化チタン自体が水溶液に溶解したり、不経済
であるため好ましくない。処理時間は通常数分〜
５時間である。
本発明に用いられる導電性基材は、紙、プラス
チツクス、シートなどに導電性塗料を塗布したも
の、金属を蒸着したもの、金属箔をラミネートし
たもの或いは金属板など通常電子写真に用いられ
る導電性基材を用いることができ、また感光層を
形成する結着剤としては、アクリル樹脂、アルキ
ツド樹脂、ポリエステル樹脂、ビニル樹脂など通
常電子写真感光材料に用いられるものが使用でき
るが、電子写真特性には結着剤として適当なもの
を適宜選択して用いることが好ましい。どのよう
な結着剤が好ましいかは、使用目的によつて重視
される性能が異なるので、試行によつて好ましい
結着剤をよく評価して選定して用いるようにする
のが好ましい。
本発明は改良された光感度及び耐湿性を有する
電子写真感光材料を得ることにあり、そのために
は、二酸化チタンが弗素を含む必要がある。この
原因について理論的に解明されるに至つていない
が、二酸化チタンの表面に塩素や硫酸根のような
陰イオンが存在すると、湿分によつて遊離の陰イ
オンとなり易く、そのため導電性を増して暗保持
性を低下させると考えられるのに対し、弗素の場
合は弗素が二酸化チタンの表面に存在するOH基
と置換して強固に結合するため、弗素が陰イオン
となつて遊離することが少なく、また二酸化チタ
ンの表面のOH基の数が減少することによつて二
酸化チタン表面への水分の吸着性が低減されるた
めであろうと推定される。
以下の実施例によつて更に詳細に説明する。
実施例 １〜５
四塩化チタンを気相法で酸化分解して得た高純
度のTiO2（酸化チタンNo.１）を、表−１に示す所
定の濃度の弗酸液（PH３以下）中にて１時間浸
漬、撹拌し、これを過、水洗し、300℃で乾燥
した後、粉砕して弗酸処理したTiO2を得た。次
いでこのTiO2に増感色素として、ジブロムフル
オレツセイン及び、１−（２−カルボキシエチル）
−４−〔３−（３−エチルベンゾチアゾリン−２−
イリデン）−１−プロペン−１−イル〕キノリニ
ウムヨージドをTiO2に対してそれぞれ0.03％を
被着処理した。
前記色素被着TiO216ｇ、ナフテン酸亜鉛（Zn
として８％のもの）0.6ｇ、アロセツト5804×
C12.7ｇ、パラーtert−ブチルカテコール3.3mg、
キシレン14.4ml、ガラスビーズ50ｇを140mlのガ
ラス容器に入れ、レツドデビルペイントコンデイ
シヨナーで20分間振盪した後、ガラスビーズを分
離除去して、ペーストを得た。上記ペーストを、
アルミ蒸着した合成紙上に30μドクターブレード
で塗布した後、100℃で10分間乾燥して感光材料
を得た。これを暗所にて48時間デシケータ中に保
存した後測定に供した。また比較のため、弗酸処
理を行わない以外は前記と同様にして比較例１の
サンプルを作成した。それぞれのサンプルについ
て暗保持率及び光感度を測定した結果を表−１に
示す。
The present invention relates to an electrophotographic photosensitive material containing titanium dioxide as a photosensitive layer component, and more specifically,
The present invention relates to an electrophotographic material containing titanium dioxide with improved photosensitivity and moisture resistance. Electrophotographic materials containing titanium dioxide as a photosensitive powder in a photosensitive layer are well known. However, the reason why titanium dioxide has not been widely used as an electrophotographic light-sensitive material is that
This is because the photosensitivity is inferior to other inorganic photosensitive powders such as ZnO and CdS. Various proposals have been made regarding methods of improving the photosensitivity of titanium dioxide, including a method of treating it with a mineral acid, as in JP-A-51-118434. However, HCl,
When treated with mineral acids such as H 2 SO 4 , although it is common practice to wash thoroughly with water after treatment,
A small amount of anions such as Cl - and SO 2- 4 remain, which increases conductivity with moisture and reduces dark retention, resulting in a drawback in so-called moisture resistance, and is not necessarily a good method. do not have. However, when the inventors treated titanium dioxide with hydrofluoric acid or a fluorine compound, they surprisingly not only improved the photosensitivity, especially the photosensitivity after pre-exposure, but also improved the moisture resistance. I gained knowledge. They discovered that the treated titanium dioxide contained bound fluorine, and after conducting further extensive studies, they completed the present invention. That is, the present invention provides an electrophotographic photosensitive material in which a photosensitive layer containing an inorganic photosensitive powder and a binder as main components is laminated on a conductive substrate, wherein the inorganic photosensitive powder contains 0.01 to 0.2% of fluorine. This electrophotographic material is characterized by containing titanium dioxide as a main component. The titanium dioxide used in the present invention can be produced by various methods, such as by calcining hydrated titanium oxide obtained by hydrolyzing titanium tetrachloride or titanium sulfate, or by heating titanium tetrachloride with an oxygen-containing gas. It may be produced by gas phase oxidation or thermal decomposition of ammonium titanyl sulfate, and it may contain Al, Fe, Ni, Mn, V, etc. that reduce photosensitivity.
It is preferable that the material does not contain a large amount of impurities such as P. On the other hand, titanium dioxide may be doped with additives such as Zn, Li, Mg, Ca, Sr, or Ba, which improve the electrophotographic properties, as described in JP-A No. 51-118434. do not have. The inorganic photosensitive powder used in the photosensitive material of the present invention has the above-mentioned fluorine-containing titanium dioxide as its main component, but may also contain other inorganic photosensitive powders such as ZnO or CdS. It is preferable to contain 50% or more of fluorine-containing titanium dioxide. Further, a sensitizing dye and other additives may be used in combination as necessary, and a method such as surface treatment with metal soap may be applied to the titanium dioxide of the present invention. Titanium dioxide containing 0.01 to 0.2% fluorine used in the present invention is obtained by dissolving in water a fluorine compound that is usually water-soluble and releases fluorine ions.
An aqueous solution having a concentration of 35% and a pH of 3 or less can be obtained by adding the above-mentioned titanium dioxide into the solution, stirring and treating it, filtering it after treatment, washing it with water, drying it, and pulverizing it. Examples of fluorine compounds that are water-soluble and release fluorine ions include ammonium fluoride, potassium fluoride, lithium fluoride, zinc fluoride, and hydrogen fluoride. Further, in the case of a compound such as hydrogen fluoride that can easily exist in a gas phase, it can be treated by allowing it to act on titanium dioxide in the gas phase. For example, a method of heating KHF 2 to about 250°C to generate hydrogen fluoride gas and introducing it into a packed bed of titanium dioxide for treatment is also applicable. Although the amount of fluorine contained in titanium dioxide cannot be determined unconditionally depending on the specific surface area of titanium dioxide, OH group density, processing conditions, etc., it is preferably 0.01 to 0.2%.
If the concentration of the aqueous solution during fluorine treatment is lower than 0.001%, the desired amount of fluorine treatment cannot be achieved, and if it exceeds 35%, titanium dioxide itself may dissolve in the aqueous solution, which is undesirable. Processing time usually takes a few minutes
It is 5 hours. The conductive substrate used in the present invention is paper, plastic, sheet, etc. coated with conductive paint, metal deposited, laminated with metal foil, metal plate, etc., which are usually used in electrophotography. As the binder for forming the photosensitive layer, those commonly used in electrophotographic photosensitive materials such as acrylic resin, alkyd resin, polyester resin, and vinyl resin can be used. It is preferable to select and use an appropriate binder as the binder. What kind of binder is preferable depends on the performance that is important depending on the purpose of use, so it is preferable to carefully evaluate and select a preferable binder through trials. The object of the present invention is to obtain an electrophotographic material having improved photosensitivity and moisture resistance, and for this purpose, titanium dioxide must contain fluorine. Although the cause of this has not yet been theoretically elucidated, when anions such as chlorine and sulfate radicals exist on the surface of titanium dioxide, they tend to become free anions due to moisture, which reduces conductivity. However, in the case of fluorine, fluorine replaces the OH groups present on the surface of titanium dioxide and bonds strongly, so fluorine becomes an anion and is liberated. It is presumed that this is because the adsorption of water to the titanium dioxide surface is reduced due to a decrease in the number of OH groups on the surface of titanium dioxide. This will be explained in more detail with reference to the following examples. Examples 1 to 5 High-purity TiO 2 (titanium oxide No. 1) obtained by oxidative decomposition of titanium tetrachloride by a gas phase method was added to a hydrofluoric acid solution (PH 3 or less) at a predetermined concentration shown in Table 1. The mixture was immersed and stirred for 1 hour, filtered, washed with water, dried at 300°C, and pulverized to obtain hydrofluoric acid-treated TiO 2 . Next, dibromofluorescein and 1-(2-carboxyethyl) were added to this TiO 2 as sensitizing dyes.
-4-[3-(3-ethylbenzothiazoline-2-
Ylidene)-1-propen-1-yl]quinolinium iodide was applied at a concentration of 0.03% based on TiO 2 . 16g of the dye-coated TiO2 , zinc naphthenate (Zn
8%) 0.6g, Aroset 5804×
C12.7g, para-tert-butylcatechol 3.3mg,
14.4 ml of xylene and 50 g of glass beads were placed in a 140 ml glass container, and after shaking for 20 minutes with red devil paint conditioner, the glass beads were separated and removed to obtain a paste. Paste the above,
After coating with a 30μ doctor blade on aluminum-deposited synthetic paper, it was dried at 100°C for 10 minutes to obtain a photosensitive material. This was stored in a desiccator in the dark for 48 hours and then subjected to measurement. For comparison, a sample of Comparative Example 1 was prepared in the same manner as above except that the hydrofluoric acid treatment was not performed. Table 1 shows the results of measuring the dark retention rate and photosensitivity of each sample.
【表】【table】
【表】
上記表−１の結果より明らかなように、本発明
の感光材料は比較例１に比べて、暗保持率、及び
青色、緑色、及び赤色の各色分光共光感度、特に
前露光後の光感度が改良されている。
実施例６及び７
使用するTiO2として、酸化チタンNo.１を下記
の酸化チタンNo.２及びNo.３に代えること、弗酸処
理時の弗酸濃度を18％に代えること、増感色素を
ジブロモフルオレツセインと１−（２−カルボキ
シエチル）−４−〔５−（３−エチルベンゾチアゾ
リン−２−イリデン）−１，３−ペンタジエン−
１−イル〕キノリニウムヨージドに代えること及
び色素被着処理前に弗酸処理したTiO2にナフテ
ン酸亜鉛をZnとして0.3％相当量を被覆すること
以外は実施例１〜５の場合と同様にして感光材料
を作成した。またそれぞれのTiO2について、弗
酸処理をしない以外は前記と同様にして比較例
２、及び３のサンプルを作成した。それぞれのサ
ンプルについて暗保持率及び光感度を測定した結
果を表−２に示す。
酸化チタンNo.２……チタニル硫酸水溶液を熱加
水分解して得られる水和二酸化チタンを
焼成する工程に、Znを１モル％存在さ
せて作成した。
酸化チタンNo.３……四塩化チタンの水溶液を熱
加水分解して得られる水和二酸化チタン
を焼成する工程に、Znを１モル％存在
させて作成した。[Table] As is clear from the results in Table 1 above, compared to Comparative Example 1, the photosensitive material of the present invention has a higher dark retention rate and spectral sensitivity for each color of blue, green, and red, especially after pre-exposure. has improved light sensitivity. Examples 6 and 7 As TiO 2 used, titanium oxide No. 1 was replaced with titanium oxide No. 2 and No. 3 below, the hydrofluoric acid concentration during hydrofluoric acid treatment was changed to 18%, and sensitizing dye dibromofluorescein and 1-(2-carboxyethyl)-4-[5-(3-ethylbenzothiazolin-2-ylidene)-1,3-pentadiene-
1-yl]quinolinium iodide and coating TiO 2 treated with hydrofluoric acid with zinc naphthenate in an amount equivalent to 0.3% of Zn before the dye deposition treatment. A photosensitive material was prepared in the same manner. Further, for each TiO 2 , samples of Comparative Examples 2 and 3 were prepared in the same manner as described above except that the hydrofluoric acid treatment was not performed. Table 2 shows the results of measuring the dark retention rate and photosensitivity of each sample. Titanium oxide No. 2...Produced by adding 1 mol% of Zn to the firing process of hydrated titanium dioxide obtained by thermally hydrolyzing a titanyl sulfuric acid aqueous solution. Titanium oxide No. 3...Produced by adding 1 mol% of Zn to the firing process of hydrated titanium dioxide obtained by thermally hydrolyzing an aqueous solution of titanium tetrachloride.
【表】【table】
【表】
上記表−２の結果より明らかなように、本発明
の感光材料は、それぞれ比較例２或は３と比較し
て、暗保持率及び光感度が改良されている。
実施例８及び９
弗酸処理時の弗化物及び濃度を下記表−３のよ
うに代えること以外は実施例７の場合と同様にし
て感光材料を作成した。それぞれのサンプルにつ
いて暗保持率及び光感度を測定した結果を表−３
に示す。[Table] As is clear from the results in Table 2 above, the photosensitive material of the present invention has improved dark retention and photosensitivity compared to Comparative Examples 2 and 3, respectively. Examples 8 and 9 Photosensitive materials were prepared in the same manner as in Example 7 except that the fluoride and concentration during hydrofluoric acid treatment were changed as shown in Table 3 below. Table 3 shows the results of measuring the dark retention rate and photosensitivity of each sample.
Shown below.
【表】
上記表−３の結果から明らかなように、本発明
の感光材料は比較例３のサンプルに比べて暗保持
率及び光感度が改良されている。
実施例 10
ナフテン酸亜鉛に代えて、オクチル酸ジルコニ
ウムをZrとして0.3％相当量をTiO2に被覆処理す
ること以外は実施例６の場合と同様にして感光材
料を作成した。また、弗酸処理しないこと以外は
上記の場合と同様にして比較例４の感光材料を作
成した。この感光材料をそれぞれ相対湿度が30℃
で30〜80％の空気中に30分放置した後、暗保持性
を測定した。その結果を表−４に示す。[Table] As is clear from the results in Table 3 above, the light-sensitive material of the present invention has improved dark retention and photosensitivity compared to the sample of Comparative Example 3. Example 10 A photosensitive material was prepared in the same manner as in Example 6, except that zirconium octylate was used as Zr in place of zinc naphthenate and TiO 2 was coated in an amount equivalent to 0.3%. Further, a photosensitive material of Comparative Example 4 was prepared in the same manner as above except that the hydrofluoric acid treatment was not performed. The relative humidity of each photosensitive material is 30℃.
The dark retention property was measured after being left in 30-80% air for 30 minutes. The results are shown in Table-4.
【表】
上記表−４の結果から明らかなように、本発明
の感光材料は、比較例４に比べて、広い相対湿度
の範囲にわたつて、暗保持率が高く、耐湿性がす
ぐれている。[Table] As is clear from the results in Table 4 above, the photosensitive material of the present invention has a higher dark retention rate and better moisture resistance over a wider range of relative humidity than Comparative Example 4. .
Claims (1)
有する感光層を導電性基材上に積層してなる電子
写真感光材料において、前記無機感光性粉末が弗
素を0.01〜0.2％含む二酸化チタンを主成分とす
ることを特徴とする電子写真感光材料。1. An electrophotographic photosensitive material in which a photosensitive layer containing an inorganic photosensitive powder and a binder as main components is laminated on a conductive base material, wherein the inorganic photosensitive powder is titanium dioxide containing 0.01 to 0.2% of fluorine. An electrophotographic material characterized by containing as a main component.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17344480A JPS5796352A (en) | 1980-12-09 | 1980-12-09 | Electrophotography photosensitive material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17344480A JPS5796352A (en) | 1980-12-09 | 1980-12-09 | Electrophotography photosensitive material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5796352A JPS5796352A (en) | 1982-06-15 |
| JPS6335977B2 true JPS6335977B2 (en) | 1988-07-18 |
Family
ID=15960581
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP17344480A Granted JPS5796352A (en) | 1980-12-09 | 1980-12-09 | Electrophotography photosensitive material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5796352A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01113799U (en) * | 1988-01-22 | 1989-07-31 | ||
| JPH0326210U (en) * | 1989-07-15 | 1991-03-18 | ||
| JPH0357685U (en) * | 1989-10-11 | 1991-06-04 |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0376216B1 (en) * | 1988-12-28 | 1994-11-30 | Ishihara Sangyo Kaisha, Ltd. | Titanium dioxide aggregates, process for producing same and electrophotographic photosensitive material containing same |
| JPH0664353B2 (en) * | 1989-02-02 | 1994-08-22 | 石原産業株式会社 | Electrophotographic photoconductor |
-
1980
- 1980-12-09 JP JP17344480A patent/JPS5796352A/en active Granted
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01113799U (en) * | 1988-01-22 | 1989-07-31 | ||
| JPH0326210U (en) * | 1989-07-15 | 1991-03-18 | ||
| JPH0357685U (en) * | 1989-10-11 | 1991-06-04 |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5796352A (en) | 1982-06-15 |
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