KR100424633B1 - Bipolar monolayer-type electrophotographic photoconductor composition - Google Patents

Bipolar monolayer-type electrophotographic photoconductor composition Download PDF

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KR100424633B1
KR100424633B1 KR1019960078686A KR19960078686A KR100424633B1 KR 100424633 B1 KR100424633 B1 KR 100424633B1 KR 1019960078686 A KR1019960078686 A KR 1019960078686A KR 19960078686 A KR19960078686 A KR 19960078686A KR 100424633 B1 KR100424633 B1 KR 100424633B1
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group
formula
fluorescent film
photoconductor composition
panel
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KR19980059348A (en
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김민호
심재호
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삼성에스디아이 주식회사
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    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03GELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G5/00Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
    • G03G5/02Charge-receiving layers
    • G03G5/04Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
    • G03G5/06Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor characterised by the photoconductive material being organic
    • G03G5/0601Acyclic or carbocyclic compounds
    • G03G5/0612Acyclic or carbocyclic compounds containing nitrogen
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03GELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G5/00Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
    • G03G5/02Charge-receiving layers
    • G03G5/04Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
    • G03G5/06Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor characterised by the photoconductive material being organic
    • G03G5/0622Heterocyclic compounds
    • G03G5/0624Heterocyclic compounds containing one hetero ring
    • G03G5/0635Heterocyclic compounds containing one hetero ring being six-membered
    • G03G5/0637Heterocyclic compounds containing one hetero ring being six-membered containing one hetero atom
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01JELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J9/00Apparatus or processes specially adapted for the manufacture, installation, removal, maintenance of electric discharge tubes, discharge lamps, or parts thereof; Recovery of material from discharge tubes or lamps
    • H01J9/20Manufacture of screens on or from which an image or pattern is formed, picked up, converted or stored; Applying coatings to the vessel
    • H01J9/22Applying luminescent coatings
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01JELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J29/00Details of cathode-ray tubes or of electron-beam tubes of the types covered by group H01J31/00
    • H01J29/02Electrodes; Screens; Mounting, supporting, spacing or insulating thereof
    • H01J29/06Screens for shielding; Masks interposed in the electron stream
    • H01J29/07Shadow masks for colour television tubes

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Photoreceptors In Electrophotography (AREA)

Abstract

PURPOSE: Provided is a simple and functional monolayer-type electrophotographic photoconductor composition, which has bipolar charge transportability for transporting both holes and electrons and charge generation capability through complexation. CONSTITUTION: The electrophotographic photoconductor composition comprises N,N'-diphenyl-N,N'-bis(4-methylphenyl)-£1,1'-biphenyl|-4,4'-diamine represented by formula 1 as an electron donor compound; a thioxanthene derivative represented by formula 2 as an electron acceptor compound; and a binder polymer, wherein R is a functional group selected from the group consisting of ethoxycarbonyl, butoxycarbonyl, phenoxycarbonyl, oxycarbonyl, ethyl, propyl and t-butyl.

Description

양극성 단층형 전자사진용 광도전체 조성물Bipolar Single-layer Electrophotographic Photoconductor Composition

[산업상 이용 분야][Industrial use]

본 발명은 양극성 단층형 전자사진용 광도전체 조성물에 관한 것으로서, 더욱 상세하게는 바인더 폴리머에 충분한 상용성을 갖고있으며, 전하수송능과 전하유지능이 우수한 전자공여체 화합물인 하기한 화학식 1의 하기한 화학식 2의 전자수용체 화합물인 티옥산센 유도체를 바인더 폴리머에 분자 분산시킨 (+)와 (-) 전하 모두를 수송할 수 있는 양극성(bipolar) 단층형 전자사진용 광도전체 조성물에 관한 것이다.The present invention relates to a bipolar single-layer electrophotographic photoconductor composition, and more particularly, to an electron donor compound having sufficient compatibility with a binder polymer and having excellent charge transport ability and charge retention ability. The present invention relates to a bipolar single layer electrophotographic photoconductor composition capable of transporting both (+) and (−) charges in which a thioxanthene derivative, which is an electron acceptor compound of 2, is molecularly dispersed in a binder polymer.

R은 에톡시카르보닐기, 부톡시카르보닐기, 페녹시카르보닐기, 옥시카르보닐기, 에틸기, 프로필기 및 t-부틸기를 나타낸다.R represents an ethoxycarbonyl group, butoxycarbonyl group, phenoxycarbonyl group, oxycarbonyl group, ethyl group, propyl group and t-butyl group.

[종래 기술][Prior art]

일반적으로 칼라표시패널용 형광막은 스핀법을 이용한 슬러리 도포방식에 의하여 제조되는데, 우선 세정된 유리 벌브의 패널을 회전하여 폴리비닐 알코올과 암모늄 디크로메이트와 같은 포토레지스트(photoresist)가 고르게 도포되게 한 후에 가열 건조시킨다. 마스크 어셈블리를 조립시킨 패널을 노광대 위에 올려놓고 섀도우 마스크 슬롯을 통하여 자외선을 주사하여 패널 내면의 포토레지스트를 도트(dot)나 스트립(stripe)상으로 노광시킨다. 이렇게 포토레지스트를 패널의 내부에 고착시킨 후에 이온을 제거한 증류수로 세척하여 자외선에 노광되지 않은 포토레지스트를 제거하고 건조한다. 도트 또는 스트립 사이의 빈 공간에는 흑연 용액과 같은 비발광성 광흡수제를 도포하고 열에 의해 건조한 후에 과산화수소로 세척한다. 그리고 나서 고 압 증류수 스프레이로 패널을 세정하여 포토레지스트와 그 위를 덮은 흑연 용액을 제거한다. 패널을 급속히 회전하여 습기를 건조시키면 남아 있는 흑연 용액이 블랙매트릭스를 형성한다. 형성된 블랙매트릭스 사이에 적색, 녹색 및 청색 형광체를 각각 적용시켜 형광막을 완성한다. 상기한 적, 녹 청색 형광체를 블랙매트릭스에 적용시키는 공정에는 슬러리 방식과 전자 사진 방식의 두 가지 방식이 있다. 슬러리 방식은 우선 적색 형광체 슬러리를 도포하고 패널을 일정한 속도로 회전하여 형광체 슬러리가 고르게 도포되도록 한다. 그 후에 패널을 가열하여 형광체를 건조시키고 마스크와 패널을 재조립하여 노광한다. 노광 후에 마스크를 분리하고 노광되지 않은 형광체를 이온을 제거한 증류수 스프레이를 사용하여 제거하면 패널 내면에 적색 형광체 도트나 스트립이 형성된다. 녹색과 청색 형광체에 대해서도 동일한 과정으로 진행되며 완성된 패널은 수천개의 도트 또는 스트립으로 되어있다. 이 과정에서 정해진 포인트에서만 형광체가 노광되어 3가지의 형광체가 중첩되지 않게 하기 위하여 광원의 특정각을 설정한 후에 노광하는 것을 제외하고는 상기한 노광의 방법과 동일하다. 마지막으로 건조대에서 건조 증기로 형광막을 건조시키면 형광면이 완성되는 것이다. 이 방법에 의하여 형성되는 형광막은 패널의 중앙부와 주변부의 건조되는 속도의 차이가 발생하여 노광시 패널 중앙부 도트의 폭과 주변부 도트의 폭에 있어서 그 폭의 차이가 심하게 나며 도트의 형상 또한 나빠져서 칼라표시패널의 색순도(color purity)를 저하시키는 문제점이 있다.In general, the fluorescent film for color display panels is manufactured by a slurry coating method using a spin method. First, a panel of the cleaned glass bulb is rotated to evenly apply photoresist such as polyvinyl alcohol and ammonium dichromate. Heat drying. The panel on which the mask assembly is assembled is placed on an exposure table, and ultraviolet rays are scanned through a shadow mask slot to expose the photoresist on the inner surface of the panel onto a dot or strip. After the photoresist is fixed to the inside of the panel, the photoresist is washed with distilled water from which ions are removed to remove the photoresist that is not exposed to ultraviolet rays and dried. The empty space between the dots or strips is coated with a non-luminescent light absorber such as a graphite solution, dried by heat and then washed with hydrogen peroxide. The panel is then cleaned with a high pressure distilled water spray to remove the photoresist and the graphite solution covering it. The panel is rapidly rotated to dry the moisture and the remaining graphite solution forms a black matrix. Red, green, and blue phosphors are respectively applied between the formed black matrices to complete the fluorescent film. There are two methods of applying the red and green blue phosphors to the black matrix, a slurry method and an electrophotographic method. The slurry method first applies a red phosphor slurry and rotates the panel at a constant speed so that the phosphor slurry is evenly applied. The panel is then heated to dry the phosphor and the mask and panel are reassembled and exposed. After exposure, the mask is removed and the unexposed phosphor is removed using a deionized water spray to form red phosphor dots or strips on the inner surface of the panel. The same goes for green and blue phosphors, and the finished panel consists of thousands of dots or strips. In this process, the phosphor is exposed only at a predetermined point, and thus the exposure is performed after setting a specific angle of the light source so that the three phosphors do not overlap. Finally, when the fluorescent film is dried with dry steam in the drying zone, the fluorescent surface is completed. In the fluorescent film formed by this method, the difference in the drying speed of the center portion and the peripheral portion of the panel is generated. There is a problem of lowering the color purity of the panel.

이러한 슬러리 방식의 단점을 개선하기 위한 다른 하나의 방법인 전자 사진 방식은 다음과 같다.Another method for improving the shortcomings of the slurry method is as follows.

칼라표시패널 내면에 도전성 물질을 코팅하여 형성한 도전층과 그 위에 광도전성 물질을 코팅하여 이루어진 광도전층을 형성한다. 그 후에 대전공정을 통하여 패널 내면에 일정한 표면 전위를 갖도록 대전한 다음 가시광선을 이용하여 선택적으로 노광을 실시하면 노광된 부분은 전하를 잃게 되고 그 전하가 제거된 부분에 형광체 분말을 분사하여 형광면을 형성한다.A conductive layer formed by coating a conductive material on the inner surface of the color display panel and a photoconductive layer formed by coating a photoconductive material thereon are formed thereon. Then, after charging to have a constant surface potential on the inner surface of the panel through a charging process, and then selectively exposed using visible light, the exposed portion loses charge, and the phosphor powder is sprayed on the portion where the charge is removed to form a fluorescent surface. Form.

여기에서 광도전성 물질로 이루어진 광도전층은 어두운 곳에서는 일반적으로 절연층 역할을 하지만 자외선이나 가시광선과 같은 일정 영역의 파장을 갖는 광원하에서는 전자 또는 정공을 방출하여 전기적인 특성을 띠고 있다.Here, the photoconductive layer made of a photoconductive material generally serves as an insulating layer in the dark but emits electrons or holes under a light source having a wavelength of a certain region such as ultraviolet rays or visible light, thereby exhibiting electrical characteristics.

광도전층을 사용하여 칼라표시패널용 형광막을 형성한 구조를 도 2에 나타내었다.The structure in which the fluorescent film for color display panels was formed using the photoconductive layer is shown in FIG.

도 2에 나타낸 광도전층은 칼라표시패널(11)위에 유기 도전층(13)과 전하발생 및 전하수송물질을 분산시킨 폴리머로 이루어진 전하발생 및 수송층(15)으로 이루어진 단층형의 광도전층이며 이 경우에 히드라존 화합물, 스티릴 화합물, 피라조린 화합물, 트리페닐아민 화합물 등의 정공수송성 또는 전자수송성의 전하수송물질을 첨가해도 무방하다.The photoconductive layer shown in FIG. 2 is a single-layer photoconductive layer composed of an organic conductive layer 13 and a charge generation and transport layer 15 composed of a polymer in which charge generation and charge transport materials are dispersed on the color display panel 11. A hole transporting or electron transporting charge transporting material such as a hydrazone compound, a styryl compound, a pyrazoline compound, or a triphenylamine compound may be added to the compound.

상기한 광도전층을 형성하는 광도전층 조성물에는 유기 바인더, 전자수용체 화합물 및 전자공여체 화합물로 이루어진 전하수송 재료 그리고 잔여의 용매가 혼합되어 구성되어 있다.The photoconductive layer composition forming the photoconductive layer is composed of an organic binder, an electron acceptor compound, a charge transport material composed of an electron donor compound, and a residual solvent.

유기전하 수송 재료의 경우 전자공여체 화합물, 전자수용체 화합물 각각에 의해 정공 및 전자의 수송이 가능하나, 유기광도전 재료가 보다 기능적이고, 공정 단순화의 필요성에 부응하기 위해서는 하나의 재료에서 정공 및 전자의 수송이 가능한 양극성 전하 수송재료의 개발이 필요하며, 이러한 정공 및 전자의 수송이 가능한 양극성 전하 수송 재료의 연구로서 J. Appl. Phys., 70(2), 855(1991)가 보고되어 있으나, 전하의 발생능력이 없기 때문에 별도의 전하 발생물질을 사용해야 하는 단점이 있다.In the case of the organic charge transport material, holes and electrons can be transported by the electron donor compound and the electron acceptor compound, respectively.However, in order to meet the necessity of the process simplification, the organic photoconductive material is more effective in the process of hole and electron The development of a bipolar charge transport material capable of transport is required. As a study of the bipolar charge transport material capable of transporting holes and electrons, J. Appl. Phys., 70 (2) and 855 (1991) have been reported, but there is a disadvantage that a separate charge generating material must be used since there is no charge generating ability.

본 발명은 상기 문제점을 해결하기 위하여 안출된 것으로서, 본 발명은 정공(hole) 및 전자(electron)의 수송이 가능한 양극성 전하수송능을 가지며, 동시에 착체 형성에 의한 전하 발생능을 갖는 단순하며, 기능적인 단층형 전자사진용 광도전체 조성물를 제공하는데 있다.The present invention has been made to solve the above problems, the present invention has a bipolar charge transport ability capable of transporting holes and electrons, and at the same time has a simple, function of generating charges by complex formation To provide a single layer electrophotographic photoconductor composition.

도 1은 양극성(bipolar)전하 이동도에 대한 그래프.1 is a graph of bipolar charge mobility.

도 2는 칼라 브라운관 패널용 형광막 형성을 위한 단층형 광도전층의 구조를 나타낸 단면도.2 is a cross-sectional view showing the structure of a single-layer photoconductive layer for forming a fluorescent film for a color CRT panel.

* 도면의 주요부분에 대한 부호의 설명* Explanation of symbols for main parts of the drawings

도1에서의 " : "는 전자공여체인 화학식 1 : 전자수용체인 화학식 2(R이 부톡시카르보닐기인 경우)의 혼합비율을 나타낸다.In FIG. 1, ":" represents the mixing ratio of the chemical formula 1: electron acceptor: chemical formula 2 (when R is a butoxycarbonyl group).

11 : 패널11: panel

13 : 유기도전층13: organic conductive layer

15 : 전하발생 및 수송층15: charge generation and transport layer

상기와 같은 본 발명의 목적을 달성하기 위하여, 본 발명은 하기한 화학식 1의 전자공여체 화합물인 N, N'-디페닐-N, N'-비스(4-메틸페닐)-[1, 1'-바이페닐]-4, 4'-디아민과 하기한 화학식 2의 전자수용체 화합물인 티옥산센 유도체와 바인더 폴리머를 포함하는 전자사진용 광도전체 조성물을 제공한다.In order to achieve the object of the present invention as described above, the present invention is the electron donor compound of formula 1, N, N'- diphenyl-N, N'-bis (4-methylphenyl)-[1, 1'- Provided is an electrophotographic photoconductor composition comprising biphenyl] -4, 4'-diamine, a thioxanthene derivative which is an electron acceptor compound of formula (2), and a binder polymer.

[화학식 1][Formula 1]

[화학식 2][Formula 2]

상기 식에서, R은 에톡시카르보닐기, 부톡시카르보닐기, 페녹시카르보닐기, 2-에틸헥실카르보닐기,에틸기, 프로필기 및 t-부틸기로 이루어진 군에서 선택되는 작용기를 나타낸다.In the above formula, R represents a functional group selected from the group consisting of an ethoxycarbonyl group, butoxycarbonyl group, phenoxycarbonyl group, 2-ethylhexylcarbonyl group , ethyl group, propyl group and t-butyl group.

또한 본 발명은 상기 화학식 2에 있어서, R이 부톡시카르보닐기 또는 2-에틸헥실카르보닐기인 전자사진용 광도전체 조성물을 제공하며,In another aspect, the present invention provides an electrophotographic photoconductor composition of the formula 2, wherein R is a butoxycarbonyl group or 2-ethylhexylcarbonyl group,

본 발명은 또한 칼라 브라운관의 패널 내면에 도전층을 형성하는 단계, 형성된 도전층 위에 광도전층을 형성하는 단계, 방전을 이용하여 표면전위를 인가하는 단계, 형광체 패턴을 형성하기 위한 형광막의 노광 단계 및 마찰대전을 이용한 형광막의 대전 단계를 포함하는 상기의 광도전체 조성물을 사용하여 칼라브라운관 형광막을 제조하는 방법을 제공한다.The present invention also provides a method of forming a conductive layer on an inner surface of a panel of a color CRT, forming a photoconductive layer on the formed conductive layer, applying a surface potential using discharge, exposing a fluorescent film to form a phosphor pattern, and Provided is a method for producing a color-brown tube fluorescent film using the photoconductor composition comprising the charging step of the fluorescent film using a triboelectric charge.

또한 본 발명은 칼라 브라운관의 패널 내면에 도전층을 형성하는 단계, 형성된 도전층 위에 광도전층을 형성하는 단계, 방전을 이용하여 표면전위를 인가하는 단계, 형광체 패턴을 형성하기 위한 형광막의 노광 단계 및 마찰대전을 이용한 형광막의 대전 단계를 포함하는 상기 광도전체 조성물을 사용하여 칼라 브라운관 감광막을 제조하는 방법을 제공하며, 상기 방법에 따라 제조된 칼라 브라운관 감광막을 제공한다.In another aspect, the present invention is to form a conductive layer on the inner surface of the panel of the color CRT, forming a photoconductive layer on the formed conductive layer, applying a surface potential using a discharge, exposing a fluorescent film to form a phosphor pattern and It provides a method for producing a color CRT photosensitive film using the photoconductor composition comprising the charging step of a fluorescent film using a triboelectric charge, and provides a color CRT photosensitive film prepared according to the method.

[대표적인 실시예]Representative Example

도 2에 표시한 단층형 전자사진용 광도전체 조성물은 PET수지, 유리패널 또는 브라운관용 패널 위에 와이어바(wire bar)코팅, 닥터블레이드(doctor blade)코팅, 또는 스핀(spin)코팅법에 의하여 도전물질을 코팅하여 도전층을 형성시킨 후, 그 위에 화학식 1의 전자공여체 물질과 화학식 2의 전자수용체 물질을 바인더 폴리머에 분산시킨 광도전액을 상기와 같은 코팅법으로 광도전층을 형성시켜 단층형 전자사진용 광도전체 조성물 조성물을 구성하였다. 상기 화학식 2에 있어서, R은 알킬기, 알콕시기 또는 아릴기로 치환된 카르보닐기로서, 카르보닐기로서는 에톡시카르보닐기, 부톡시카르보닐기, 페녹시카르보닐기 및 2-에틸헥실카르보닐기를 들 수 있으며, 알킬기로서는 에틸기, 프로필기, t-부틸기 등을 들 수 있고, 이들 작용기 중 부톡시카르보닐기와 2-에틸헥실카르보닐기가 바람직하다.The single-layer electrophotographic photoconductor composition shown in FIG. 2 is conductive by wire bar coating, doctor blade coating, or spin coating method on PET resin, glass panel or CRT panel. After coating the material to form a conductive layer, a photoconductive layer in which the electron donor material of Formula 1 and the electron acceptor material of Formula 2 are dispersed in a binder polymer is formed thereon to form a photoconductive layer by a coating method as described above. The photoconductor composition composition was constructed. In Formula 2, R is a carbonyl group substituted with an alkyl group, an alkoxy group or an aryl group, and examples of the carbonyl group include ethoxycarbonyl group, butoxycarbonyl group, phenoxycarbonyl group, and 2-ethylhexylcarbonyl group. and a t-butyl group are mentioned, but a butoxycarbonyl group and 2-ethylhexylcarbonyl group are preferable among these functional groups.

다음은 본 발명의 이해를 돕기 위하여 바람직한 실시예를 제시한다. 그러나 하기의 실시예들은 본 발명을 보다 쉽게 이해하기 위하여 제공되는 것일 뿐 본 발명이 하기의 실시예에 한정되는 것은 아니다.The following presents a preferred embodiment to aid the understanding of the present invention. However, the following examples are merely provided to more easily understand the present invention, and the present invention is not limited to the following examples.

[실시예]EXAMPLE

실시예 1Example 1

전하이동도의 측정에 의한 양극성 전하 수송능의 확인Confirmation of Bipolar Charge Transport Capacity by Measurement of Charge Mobility

전자공여체 화합물인 N, N'-디페닐-N, N'-비스(4-메틸페닐)-[1, 1'-바이페닐]-4, 4'-디아민과 전자수용체 화합물인 부톡시카르보닐 티옥산센 유도체를 표 1의 조성에 따라 톨루엔 용액에 적당한 비율로 바인더 폴리머인 폴리스티렌 50 중량%에 분산시켜 광도전성 용액을 제조하였다.N, N'-diphenyl-N, N'-bis (4-methylphenyl)-[1,1'-biphenyl] -4,4'-diamine as electron donor compound and butoxycarbonyl thi as electron acceptor compound The oxanthene derivative was dispersed in 50 wt% of polystyrene as a binder polymer in an appropriate ratio in a toluene solution according to the composition of Table 1 to prepare a photoconductive solution.

전자공여체/전자수용체 혼합비에 따른 광도전성 용액의 제조(+) 및 (-)전하를 모두 수송할 수 있는 전자사진용 광도전체 조성물임을 확인하기 위하여 전하 발생물질을 사용하였다. 측정용 시료는 알루미늄 전극 위에 전하 발생물질로서 티타닐 프탈로시아닌(TiOPc)을 스핀코팅법에 의해 전하 발생층을 형성시킨 후, 표 1과 같이 제조한 용액을 각각 스핀 코팅법에 의해 전하수송층을 형성하였다. 그 위에 반투명 전극으로서 금(Au)을 증착하여 샌드위치 형의 시료를 제작하였다. 상기와 같은 시료를 일반적인 전하이동도 측정법(T.O.F)에 의해 전자 및 정공의 이동도를 측정하고 도 1에 이동도의 측정결과를 나타내었다. 도 1에서 알 수 있는 바와 같이 본 연구에서 개발한 광도전체 조성물은 전자 및 정공을 모두 수송하는 양극성 전하 수송능이 있음을 확인하였다. 측정 결과 혼합비(전자공여체/전자수용체, 중량비)가 5:1인 경우에 인가전압 2.35×105V/cm에서 전자이동도가 5.16×10-6/cm2/Vs, 정공 이동도가 4.30×10-6/cm2/Vs으로서, 현재 실용화되고 있는 전하수송물질에 필적하는 이동도의 특성을 나타내었다.Preparation of the photoconductive solution according to the electron donor / electron acceptor mixing ratio The charge generating material was used to confirm that it is an electrophotographic photoconductor composition capable of transporting both (+) and (−) charges. In the sample for measurement, a charge generating layer was formed by spin coating a titanyl phthalocyanine (TiOPc) as a charge generating material on an aluminum electrode, and then a charge transport layer was formed on each of the solutions prepared in Table 1 by spin coating. . Gold (Au) was deposited as a translucent electrode on it, and the sandwich type sample was produced. In the sample as described above, the mobility of electrons and holes was measured by a general charge mobility measurement (TOF) method, and the measurement results of mobility are shown in FIG. 1. As can be seen in Figure 1 it was confirmed that the photoconductor composition developed in this study has a bipolar charge transport ability to transport both electrons and holes. As a result of the measurement, when the mixing ratio (electron donor / electron acceptor, weight ratio) is 5: 1, the electron mobility is 5.16 × 10 -6 / cm 2 / Vs and the hole mobility is 4.30 × at an applied voltage of 2.35 × 10 5 V / cm. As 10 −6 / cm 2 / Vs, the mobility characteristics were comparable to those of charge transport materials that are currently used.

실시예 2Example 2

단층형 전자사진용 광도전체 조성물의 대전전위 특성Charge Potential Characteristics of Single Layer Electrophotographic Photoconductor Composition

PET 수지 또는 유리패널 위에 전극으로서 도전성 물질(틴디옥사이드 분산용액)을 스핀코팅하여 건조한 후에 도전층을 형성하고 표 1과 같은 조성으로 광도전 용액을 제조한 다음 이를 닥터 블레이드를 사용하여 도전층을 코팅하여 약 10㎛의 건조 필름을 제조한 다음, 90℃에서 건조시켜 광도전층을 제조하였다. 이렇게 하여 제조된 광도전층을 전자사진 시험장치(모델 EPA-8200, 가와구찌 전기제작소)를 사용하여 전자사진 특성을 측정하였다. 즉, 광도전층에 9kV의 코로나 대전을 시킨다음 표면전위(V0)를 측정하고, 이를 1분 동안 암실에서 정치시킨 후 암감쇠(DD, dark decay)를 측정하고, 200μw/cm2의 광을 크세논 램프로 부터 조사하여 표면전위를 1/2로 감소시키는데 필요한 노출량, 즉 반감노광량(half decay exposure) E1/2(lux.sec.) 및 노광 후 잔류전위(Vr)를 측정하였다. 이 결과는 표 2에 기재하였다.Spin coating a conductive material (tin dioxide dispersion solution) as an electrode on a PET resin or glass panel to form a conductive layer after drying and preparing a photoconductive solution with a composition as shown in Table 1 and coating the conductive layer using a doctor blade. To prepare a dry film of about 10㎛, then dried at 90 ℃ to prepare a photoconductive layer. The electroconductive property of the photoconductive layer thus prepared was measured using an electrophotographic test apparatus (model EPA-8200, Kawaguchi Electric Works). In other words, after applying a 9 kV corona charge to the photoconductive layer, the surface potential (V 0 ) is measured, and after standing in the dark for 1 minute to measure the dark decay (DD, dark decay), and the light of 200μw / cm 2 Irradiation from the xenon lamp was used to determine the exposure required to reduce the surface potential by half, ie half decay exposure E 1/2 (lux.sec.) And residual potential (Vr) after exposure. The results are shown in Table 2.

표2에서 알 수 있는 바와 같이 광도전체 조성물은 모두 1495 또는 1604V의 초기 표면전위, 0.59 또는 0.97 lux.sec.의 반감노광량, 22 또는 48V의 표면전위 등과 같은 전자사진 프로세스 분야에서 크게 요구되는 우수한 특성을 갖고 있으며, 특히 전하발생 물질을 사용하지 않은 실시예 2의 전자사진 광도전체 조성물에 있어서도 전자 공여체 및 전자 수용체 물질이 전하이동 착체를 형성하여 전하를 발생하였기 때문에 광조사 후 표면전위가 급속히 감소하였음을 알 수 있다. 이와같은 전하발생 능력이 있고, 구성이 단순하며, 기능적인 단층형 전자사진 광도전체 조성물은 제조공정이 간단하고, 이에 따른 원가 절감 등의 많은 공업적 잇점을 제공한다.As can be seen from Table 2, the photoconductor compositions all have excellent properties that are highly demanded in the field of electrophotographic processes such as initial surface potential of 1495 or 1604 V, half exposure of 0.59 or 0.97 lux.sec., Surface potential of 22 or 48 V, etc. In particular, even in the electrophotographic photoconductor composition of Example 2, in which the charge generating material was not used, the surface potential decreased rapidly after irradiation because the electron donor and the electron acceptor material formed a charge transfer complex to generate charge. It can be seen. Such charge generating capability, simple configuration, and functional single-layer electrophotographic photoconductor composition provide many industrial advantages such as simple manufacturing process and thus cost reduction.

Claims (5)

하기한 화학식 1의 전자공여체 화합물인 N, N'-디페닐-N, N'-비스(4-메틸페닐)-[1, 1'-바이페닐]-4, 4'-디아민과 하기한 화학식 2의 전자수용체 화합물인 티옥산센 유도체와 바인더 폴리머를 포함하는 전자사진용 광도전체 조성물.N, N'-diphenyl-N, N'-bis (4-methylphenyl)-[1,1'-biphenyl] -4,4'-diamine, which is an electron donor compound of Formula 1, An electrophotographic photoconductor composition comprising a thioxanthene derivative which is an electron acceptor compound and a binder polymer. [화학식 1][Formula 1] [화학식 2][Formula 2] 상기 식에서, R은 에톡시카르보닐기, 부톡시카르보닐기, 페녹시카르보닐기, 옥시카르보닐기, 에틸기, 프로필기 및 t-부틸기로 이루어진 군에서 선택되는 작용기를 나타낸다.In the formula, R represents a functional group selected from the group consisting of an ethoxycarbonyl group, butoxycarbonyl group, phenoxycarbonyl group, oxycarbonyl group, ethyl group, propyl group and t-butyl group. 제 1항에 있어서, R이 부톡시카르보닐기 또는 2-에틸헥실카르보닐기인 전자사진용 광도전체 조성물.The photoconductor composition for electrophotography according to claim 1, wherein R is a butoxycarbonyl group or 2-ethylhexylcarbonyl group. 칼라 브라운관의 패널 내면에 도전층을 형성하는 단계 형성된 도전층 위에 광도전층을 형성하는 단계 방전을 이용하여 표면전위를 인가하는 단계 형광체 패턴을 형성하기 위한 형광막의 노광 단계 및 마찰대전을 이용한 형광막의 대전 단계를 포함하는 상기 1항의 광도전체 조성물을 사용하여 칼라브라운관 형광막을 제조하는 방법.Forming a conductive layer on the inner surface of the panel of the color CRT Forming a photoconductive layer on the formed conductive layer Applying a surface potential by using a discharge Exposure of the fluorescent film to form a phosphor pattern and charging of the fluorescent film using a triboelectric charge A method for producing a color CRT fluorescent film using the photoconductor composition of claim 1 comprising the step. 칼라 브라운관의 패널 내면에 도전층을 형성하는 단계 형성된 도전층 위에 광도전층을 형성하는 단계 방전을 이용하여 표면전위를 인가하는 단계 형광체 패턴을 형성하기 위한 형광막의 노광 단계 및 마찰대전을 이용한 형광막의 대전 단계를 포함하는 상기 1항의 광도전체 조성물을 사용하여 칼라 브라운관 감광막을 제조하는 방법.Forming a conductive layer on the inner surface of the panel of the color CRT Forming a photoconductive layer on the formed conductive layer Applying a surface potential by using a discharge Exposure of the fluorescent film to form a phosphor pattern and charging of the fluorescent film using a triboelectric charge A method for producing a color CRT tube photoresist using the photoconductor composition of claim 1 comprising the step. 제 4항에 따라 제조된 칼라 브라운관 감광막.A color CRT photosensitive film prepared according to claim 4.
KR1019960078686A 1996-12-31 1996-12-31 Bipolar monolayer-type electrophotographic photoconductor composition KR100424633B1 (en)

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US4306008A (en) * 1978-12-04 1981-12-15 Xerox Corporation Imaging system with a diamine charge transport material in a polycarbonate resin
JPH04338761A (en) * 1991-05-15 1992-11-26 Konica Corp Electrophotographic sensitive body
JPH05165232A (en) * 1991-12-13 1993-07-02 Citizen Watch Co Ltd Electrophotographic sensitive body
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