EP0102039B1 - Révélateur liquide électrophotographique - Google Patents

Révélateur liquide électrophotographique Download PDF

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Publication number
EP0102039B1
EP0102039B1 EP83108200A EP83108200A EP0102039B1 EP 0102039 B1 EP0102039 B1 EP 0102039B1 EP 83108200 A EP83108200 A EP 83108200A EP 83108200 A EP83108200 A EP 83108200A EP 0102039 B1 EP0102039 B1 EP 0102039B1
Authority
EP
European Patent Office
Prior art keywords
vinyl
pyrrolidone
liquid developer
poly
alkylated
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
Application number
EP83108200A
Other languages
German (de)
English (en)
Other versions
EP0102039A1 (fr
Inventor
Heinz Dr. Herrmann
Hans-Joachim Dr. Schlosser
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Hoechst AG
Original Assignee
Hoechst AG
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Hoechst AG filed Critical Hoechst AG
Priority to AT83108200T priority Critical patent/ATE19698T1/de
Publication of EP0102039A1 publication Critical patent/EP0102039A1/fr
Application granted granted Critical
Publication of EP0102039B1 publication Critical patent/EP0102039B1/fr
Expired legal-status Critical Current

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Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00—Developers
    • G03G9/08—Developers with toner particles
    • G03G9/12—Developers with toner particles in liquid developer mixtures
    • G03G9/13—Developers with toner particles in liquid developer mixtures characterised by polymer components
    • G03G9/131—Developers with toner particles in liquid developer mixtures characterised by polymer components obtained by reactions only involving carbon-to-carbon unsaturated bonds

Definitions

  • the invention relates to an electrophotographic liquid developer for the reverse development of negatively charged charge images consisting of an insulating carrier liquid of high electrical resistance and low dielectric constant, in which pigment, resinous binder, charge control agent from a copolymer of N-vinyl-2-pyrrolidone and methacrylic acid ester and conventional additives are dispersed or are solved, as well as a process for its preparation.
  • a negative working electrostatic toner composition for producing positive images and reverse images is also known (US-A-3542681), which disperses pigment and an alkylated polymer of heterocyclic N-vinyl monomer, such as N-vinyl-2-pyrrolidone, in an electrically insulating carrier liquid contains.
  • an alkylated polymer of heterocyclic N-vinyl monomer such as N-vinyl-2-pyrrolidone
  • a liquid developer for the reverse development of negatively charged charge images is also known (DE-B-2125 668), consisting of a mixture of pigment, polycyclopentadiene resin and a phospholipid as control agent dispersed in an aliphatic carrier liquid. Control with lecithin, for example, does not always prove to be reproducible.
  • an electrophotographic liquid developer of the type mentioned at the outset which is characterized in that it additionally contains a poly-N-vinyl-2-pyrrolidone alkylated with an a-olefin.
  • the liquid developer preferably contains 0.005 to 1.0 percent by weight of alkylated poly-N-vinyl-2-pyrrolidone. It is hereby achieved that a liquid developer for reverse development can be made available which is built on the basis of a liquid developer for the development of positive charge images and which is dissolved by diluting the toner concentrate with an alkylated poly-N-vinyl-2-pyrrolidone containing carrier liquid can be used for use as a reverse developer.
  • the poly-N-vinyl-2-pyrrolidone alkylated with an a-olefin is known per se (US Pat. No. 3,417,054). It is produced by reaction at an elevated temperature of the poly-N-vinyl-2-pyrrolidone with the corresponding ⁇ -olefins in the presence of organic peroxide catalysts.
  • Those poly-N-vinyl-2-pyrrolidones which are substituted with ⁇ -olefins and have 12 to 20 carbon atoms have proven particularly suitable according to the invention. These include e.g. B.
  • a mixture of the different olefins can also be present.
  • Such alkylated poly-N-vinyl-2-pyrrolidones, which contain about 20 percent by weight of vinyl-2-pyrrolidone, can be advantageous according to the invention because the high degree of alkylation gives particularly good solubility properties.
  • alkylated poly-N-vinyl-2-pyrrolidone used according to the invention is limited, on the one hand, by the fading of images produced if too much of the additive should be present, and, on the other hand, by a decrease in the effectiveness of the liquid developer.
  • Suitable insulating carrier liquids are, for example, petroleum-like aliphatic hydrocarbons such as n-hexane, ligroin, n-heptane, n-pentane, isododecane and isooctane and also their halogen derivatives such as perchlorethylene, all of which have a high insulating capacity (the specific resistance is greater than 10 9 ⁇ cm) and a low dielectric constant (less than 3).
  • the commercially available aliphatic hydrocarbons such as “Isopar (R) E, G, L, H or K” from Esso-Chemie, Hamburg, are particularly suitable. These can be used alone or in combination.
  • Carbon blacks such as gas black, furnace black or flame black (CI no. Of all types of carbon black 77 266) are generally used to produce black developers. Acidic carbon blacks having an average particle size of 20-30 nm and a surface area of 80-200 m 2 / g (BET) are preferably suitable.
  • organic pigments such as phthalocyanine blue (CI No. 74160), phthalocyanine green (CI No. 74 260 or 42 040), sky blue (CI No. 42 780), rhodamine (CI No. 45 170), malachite green (CI No. 42 000), methyl violet (CI No. 42 535), peacock blue (CI No. 42090), naphthol green B (CI No.
  • Inorganic pigments can also be used, for example Berlin blue (CI No. Pigmentblue 27).
  • a pigment or pigment mixture is preferably used in the preparation of the toner.
  • Pigments are generally superior to dyes in terms of bleaching ability.
  • it can usually be used to produce high-contrast image copies compared to toners containing dye.
  • the resinous binders that can be used are known per se and are selected from the group of natural or synthetic resins. They serve to fix the pigment particles on the charge image or, after transfer, to fix them on the appropriate medium, such as paper, plastic or metal foil.
  • Suitable resins are, for example, resins which are practically insoluble in the aliphatic hydrocarbons used as carrier liquid, for example maleic acid resins modified with natural resins, Dammar, Kopal, shellac, rosin, hardened rosin, ester gum, glycerol ester-modified maleic resins, styrene / butadiene mixed polymers, vinyl toluene / butadiene Copolymers and the like.
  • Common additives are understood to mean those which influence the most diverse toner properties and which may be present in some cases. They influence the amount of charge, the sedimentation behavior, the service life, the redispersibility of agglomerates, the transferability and the smudge resistance of the liquid developer or the toner particles on the copy carrier.
  • Possible additives are conventional substances such as waxes, especially polyethylene, paraffin and chloroparaffin waxes. According to the invention, such a wax or polyethylene with a softening point in the range from 60 to 130 ° C. can be used.
  • the waxes or polyethylenes mentioned have properties which - in terms of specific weight - resemble those of the carrier liquid used.
  • Polymers which are soluble in aliphatics such as polyvinyl alkyl ethers, polyisobutylene, polyvinyl stearate and polyacrylates or polymethacrylates with a higher alcohol residue or plasticizers such as, for example, dialkyl phthalates, are also suitable.
  • the invention also relates to a method for producing the electrophotographic liquid developer for the reverse development of negatively charged charge images, in which a mixture of electrically insulating carrier liquid of high electrical resistance and low dielectric constant, pigment, resinous binder, charge control agent from a copolymer of N-vinyl-2-pyrrolidone and methacrylic acid esters and conventional additives to a homogeneous paste, diluted with carrier liquid, which may contain charge control substance, to a toner concentrate and mixed with further carrier liquid to form the finished liquid developer, which is characterized in that the toner concentrate is mixed with a carrier liquid in which a-olefin alkylated poly-N-vinyl-2-pyrrolidone is contained dissolved.
  • a liquid developer is preferably prepared which contains 0.005 to 1.0 percent by weight of alkylated poly-N-vinyl-2-pyrrolidone. This ensures that a liquid developer suitable for reverse development is produced in a simple manner from a finished toner concentrate that can be used for normal development, with not even a new dispersing step or additional operation being necessary because the toner concentrate must be diluted anyway.
  • Homogenization to a paste can be carried out with a three-roll mill, a ball or colloid mill or an agitator ball mill, which is generally preferred, at temperatures in the range from room temperature to approximately the boiling range of the carrier liquid. The duration of exposure depends on the grinding result.
  • the finished particles have sizes in the range between about 0.05 and 10 microns.
  • the toner concentrates are adjusted to a solids content of about 5 to 10 percent by weight by diluting the paste with high-speed stirrers.
  • the further mixing with carrier liquid to the finished, usable liquid developer can take place, for example, before the liquid developer is used in the developing device.
  • mixing is done at concentrations ranging between 0.05 and about 5 percent by weight.
  • the invention is illustrated by the following comparative examples and examples.
  • the finished liquid developer was prepared by mixing 7 ml of the toner concentrate with 1 of the aliphatic hydrocarbon mentioned. With this liquid developer, reverse development was carried out using a microfilm enlarger on ZnO paper. The pictures were very solid and unsuitable for practical use.
  • 60 g of carbon black, described as in Comparative Example 1 were prepared with 600 of an aliphatic hydrocarbon (boiling range 160-180 ° C.) and with 160 a 20 percent by weight solution of a grafted terpolymer made from 76% dodecyl methacrylate, 20% methyl methacrylate and 4% N-vinyl 2-pyrrolidone mixed in the hydrocarbon (boiling range 160-180 ° C), 30 g of a polyethylene wax (dropping point 103-107 ° C) and 16 of a chlorinated paraffin wax (softening point 105 ° C) and in a stirred ball mill under the same conditions as in Comparative Example 1 grind.
  • a polyethylene wax dropping point 103-107 ° C
  • 16 of a chlorinated paraffin wax softening point 105 ° C
  • the dispersion was diluted with 900 g of the aliphatic hydrocarbon.
  • the toner concentrate thus obtained was diluted 1:10 with the aliphatic hydrocarbon.
  • a copier with a photosensitive layer of selenium i. H. if the development was positive, qualitatively perfect copies were obtained. However, if you used this liquid developer for reverse development on ZnO paper, you obtained very basic copies that were unusable for practical use. Even with a 1:20 dilution, no better result was achieved.
  • a toner concentrate prepared according to Comparative Example 2 was treated with a solution containing 0.075% by weight alkylated poly-N-vinyl-2-pyrrolidone (Antaron V 220) with an average chain length of 20 carbon atoms and 20% by weight vinyl-2-pyrrolidone in an aliphatic hydrocarbon (boiling range 160 -180 ° C) diluted 1:20.
  • a liquid developer thus produced when reversing development on ZnO paper, produced with a commercially available microfilm re-enlarger, gave copies of good quality in terms of basic freedom, blackening and sharpness. The liquid developer proved to be well storable for several weeks.
  • a liquid developer produced according to Example 1 gave images of good quality on reverse development using a commercially available microfilm re-enlarger on a polyvinyl carbazole photoconductor.
  • a toner concentrate prepared according to Comparative Example 2 was mixed with a 0.3% by weight alkylated poly-N-vinyl-2-pyrrolidone solution (average alkyl chain length 16 carbon atoms) in an aliphatic hydrocarbon (boiling range 175-190 ° C.) in a ratio of 1:30 diluted.
  • the liquid developer produced gave good quality copies when reversed on ZnO paper.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Liquid Developers In Electrophotography (AREA)

Claims (7)

1. Développateur électrophotographique liquide pour le développement par inversion d'images de charge négativement chargées constitué d'un liquide porteur isolant ayant une résistance électrique élevée et une faible constante diélectrique, dans lequel sont dispersés ou dissous un pigment, un liant résineux, une substance régulatrice de charge constituée d'un copolymère de la N-vinyl-2-pyrrolidone et d'un ester de l'acide méthacrylique et des additifs habituels, caractérisé en ce que le développateur liquide contient en plus une poly-N-vinyl-2-pyrro- lidone alkylée avec une a-oléfine.
2. Développateur liquide selon la revendication 1, caractérisé en ce qu'il contient de 0,005 à 1,0 pour cent en poids d'une poly-N-vinyl-2-pyrroli- done alkylée.
3. Développateur liquide selon la revendication 1 ou 2, caractérisé en ce qu'il contient de 0,02 à 0,5 pour cent en poids d'une poly-N-vinyl-2-pyrro- lidone alkylée.
4. Développateur liquide selon l'une des revendications 1 à 3, caractérisé en ce que la poly-N-vinyl-2-pyrrolidone alkylée avec une a-oléfine contient environ 20 % en poids de N-vinyl-2-pyrro- lidone.
5. Développateur selon l'une des revendications 1 à 4, caractérisé en ce que la poly-N-vinyl-2-pyrrolidone alkylée possède au moins un radical alkyle ayant de 12 à 20 atomes de carbone.
6. Procédé de préparation d'un développateur électrophotographique liquide pour le développement par inversion d'images de charge négativement chargées, dans lequel un mélange d'un liquide porteur électriquement isolant ayant une résistance électrique élevée et une faible constante diélectrique, d'un pigment, d'un liant résineux, d'une substance régulatrice de charge constituée d'un copolymère de la N-vinyi-2-pyrro- lidone et d'un ester de l'acide méthacrylique et d'additifs habituels est mis sous forme d'une pâte homogène, est dilué avec un liquide porteur contenant le cas échéant une substance régulatrice de charge pour donner un concentré de toner et est mélangé à un supplément de liquide porteur pour donner le développateur liquide terminé, caractérisé en ce qu'on mélange le concentré de toner avec un liquide porteur contenant à l'état dissous une poly-N-vinyl-2-pyrroli- done alkylée avec une a-oléfine.
7. Procédé selon la revendication 6, caractérisé en ce qu'on prépare un développateur liquide qui contient de 0,005 à 1,0 % en poids de poly-N-vinyl-2-pyrrolidone alkylée.
EP83108200A 1982-08-25 1983-08-19 Révélateur liquide électrophotographique Expired EP0102039B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT83108200T ATE19698T1 (de) 1982-08-25 1983-08-19 Elektrophotographischer fluessigentwickler.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19823231505 DE3231505A1 (de) 1982-08-25 1982-08-25 Elektrophotographischer fluessigentwickler
DE3231505 1982-08-25

Publications (2)

Publication Number Publication Date
EP0102039A1 EP0102039A1 (fr) 1984-03-07
EP0102039B1 true EP0102039B1 (fr) 1986-05-07

Family

ID=6171619

Family Applications (1)

Application Number Title Priority Date Filing Date
EP83108200A Expired EP0102039B1 (fr) 1982-08-25 1983-08-19 Révélateur liquide électrophotographique

Country Status (5)

Country Link
US (1) US4497886A (fr)
EP (1) EP0102039B1 (fr)
JP (1) JPS5949553A (fr)
AT (1) ATE19698T1 (fr)
DE (2) DE3231505A1 (fr)

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6136760A (ja) * 1984-07-30 1986-02-21 Konishiroku Photo Ind Co Ltd 印刷版の製造法
JPS63163373A (ja) * 1986-12-25 1988-07-06 Fuji Photo Film Co Ltd 電子写真用トナ−及び該トナ−を用いた画像形成方法
US4766049A (en) * 1987-01-09 1988-08-23 Xerox Corporation Latex based colored liquid developers
JP2621155B2 (ja) * 1987-01-28 1997-06-18 日本電気株式会社 測角装置
JP2614051B2 (ja) * 1987-09-07 1997-05-28 富士写真フイルム株式会社 電子写真用液体現像剤の製造法
JP2752621B2 (ja) * 1987-09-09 1998-05-18 文化シャッター 株式会社 シャッタの管理制御装置
US5457002A (en) * 1994-08-23 1995-10-10 Lexmark International, Inc. Carrier fluid for liquid electrophotographic toner
US7244540B2 (en) * 2004-10-28 2007-07-17 Samsung Electronics Company Liquid toners comprising amphipathic copolymeric binder having insoluble components in the shell portion thereof
JP5655716B2 (ja) * 2011-06-13 2015-01-21 コニカミノルタ株式会社 液体現像剤
CN110582544A (zh) * 2017-06-07 2019-12-17 惠普印迪戈股份公司 静电墨水

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4014856A (en) * 1972-07-12 1977-03-29 Agfa-Gevaert, N.V. Liquid electrophotographic developers

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US14856A (en) * 1856-05-13 Petess
DE1570646C3 (de) * 1964-01-28 1973-09-20 Gaf Corp., New York, N.Y. (V.St.A.) Verfahren zur Herstellung alkylier ter polymerer N Vinyllactame und ihre Verwendung als Zusätze in Schmierölen
US3542681A (en) * 1968-07-10 1970-11-24 Gaf Corp Negative working electrostatic toners
US3674693A (en) * 1970-05-25 1972-07-04 Dick Co Ab Reversal electrostatic toner composition
DE2740870A1 (de) * 1977-09-10 1979-03-22 Hoechst Ag Fluessigentwickler und hierzu geeignetnr ladungssteuerstoff
DE3011193A1 (de) * 1980-03-22 1981-10-01 Hoechst Ag, 6000 Frankfurt Fluessigentwickler zur entwicklung elektrostatischer ladungsbilder

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4014856A (en) * 1972-07-12 1977-03-29 Agfa-Gevaert, N.V. Liquid electrophotographic developers

Also Published As

Publication number Publication date
US4497886A (en) 1985-02-05
JPS5949553A (ja) 1984-03-22
EP0102039A1 (fr) 1984-03-07
DE3231505A1 (de) 1984-03-01
DE3363403D1 (en) 1986-06-12
ATE19698T1 (de) 1986-05-15

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