EP0001103B1 - Révélateur liquide et agent de contrôle de charge approprié - Google Patents

Révélateur liquide et agent de contrôle de charge approprié Download PDF

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Publication number
EP0001103B1
EP0001103B1 EP78100815A EP78100815A EP0001103B1 EP 0001103 B1 EP0001103 B1 EP 0001103B1 EP 78100815 A EP78100815 A EP 78100815A EP 78100815 A EP78100815 A EP 78100815A EP 0001103 B1 EP0001103 B1 EP 0001103B1
Authority
EP
European Patent Office
Prior art keywords
liquid developer
copolymer
weight
percent
control agent
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
EP78100815A
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German (de)
English (en)
Other versions
EP0001103A1 (fr
Inventor
Heinz Dr. Herrmann
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
Publication of EP0001103A1 publication Critical patent/EP0001103A1/fr
Application granted granted Critical
Publication of EP0001103B1 publication Critical patent/EP0001103B1/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 a liquid developer for the development of positively charged electrostatic charge images consisting of an electrically insulating carrier liquid in which pigment, resinous binder, charge control agent from a copolymer with a methacrylic ester component and additives are dispersed or dissolved and to a charge control agent.
  • Liquid developers are used in electrophotographic or electrographic copying processes to make latent electrostatic charge images visible. They basically consist of colored particles which are dispersed in a solution of resinous binders and charge control agent in a carrier liquid. In the electric field of the charge image, the colored particles with charge control agent and binder are deposited electrophoretically.
  • the resins which can also be polymers, are combined with the pigment particles physically or also chemically, for example by graft polymerization (US Pat. No. 3,968,044, DE-OS 25 38 581). This results in particularly stable dispersions.
  • the charge control substance which is soluble in the aliphatic solvent, is generally absorbed by the pigment particles out of the solution and determines the amount and sign of their charge.
  • the charge control agent also acts as a dispersant. If this is not the case, the liquid developer also contains dispersing agents.
  • Most known charge control agents impart a positive charge to the pigment particles. They can be used for the deposition on negatively charged electrostatic charge images; these include in particular metal soaps.
  • Negative charging of the pigment particles is caused by charge control agents, such as lecithin, alkylated polyvinylpyrrolidones, metal salts of long-chain alkylbenzenesulfonic acids or like metal salts of long-chain dialkylsulfosuccinic acid (DE-OS 19 30 784, DE-OS 24 02 953).
  • charge control agents such as lecithin, alkylated polyvinylpyrrolidones, metal salts of long-chain alkylbenzenesulfonic acids or like metal salts of long-chain dialkylsulfosuccinic acid
  • an electrophotographic liquid developer which contains in a carrier liquid as a negative charge control agent a soluble copolymer which has a methacrylic acid ester as the solubility-controlling component and sulfonic acid salts as the charge-controlling component and optionally compounds containing amino groups.
  • graft copolymers As charge control agents, the use of graft copolymers as charge control agents is also known (US Pat. No. 3,876,610), the core component of which consists of N-vinyl-2-pyrrolidone building blocks and the charge-controlling effect of which is achieved by the grafted-on monomer.
  • the object was achieved by a liquid developer of the type mentioned at the outset, which is characterized in that the charge control agent is a copolymer which is soluble in the carrier liquid and consists of 1-50% by weight of N-vinyl-2-pyrrolidone and 50-99% by weight of methacrylic acid ester.
  • the copolymer contains 15-40 percent by weight of N-vinyl-2-pyrrolidone and 60-80 percent by weight of methacrylic acid ester.
  • the liquid developers mixed with the charge control agents according to the invention develop positively charged, latent electrostatic charge images in a clean and fog-free manner.
  • Such copolymers with methacrylic acid esters with alcohol components which carry at least 6 carbon atoms in a straight or branched chain are particularly suitable.
  • 2-ethylhexyl methacrylate, dodecyl methacrylate and octadecyl methacrylate are used as methacrylic acid esters.
  • control substance according to the invention is readily soluble in the carrier liquid and, at the same time, is an excellent dispersant, by means of which the liquid developer is given good stability.
  • Control materials according to the invention advantageously have a low electrical conductivity. They can therefore be added to the liquid developer in high concentration without reaching disturbing conductivity values. On the other hand, they do not attack photoconductor layers which consist of or contain selenium.
  • Monomers are suitable here which represent acrylic monomers with a polar side group, such as methacrylic acid, acrylic acid amide or hydroxyalkyl methacrylate. They are polymerized in amounts of up to 5 percent by weight. isized.
  • methacrylic acid esters with an alcohol component having at most 6 carbon atoms are also suitable as a further monomer component, the copolymer containing up to 30 percent by weight of the short-chain methacrylic acid ester.
  • the copolymers can be prepared by heating a solution of N-vinyl-2-pyrrolidone and the methacrylic acid ester component in a nitrogen atmosphere with stirring in the presence of a polymerization initiator.
  • a starter z. B. azoisobutyronitrile (AIBN) can be used as a starter z. B. azoisobutyronitrile (AIBN) can be used.
  • the polymerization temperature depends on the type of starter. AIBN is preferably used in the range from about 70 to 90 ° C.
  • the polymerization takes place in a solvent, which is preferably the same aliphatic hydrocarbon that is later the main component of the carrier liquid. If a polymerization component does not dissolve here, the polymerization can of course also be carried out in another solvent, e.g. B. toluene, drain. The solvent used is then stripped off and the remaining polymer is dissolved in the aliphatic hydrocarbon.
  • a solvent which is preferably the same aliphatic hydrocarbon that is later the main component of the carrier liquid. If a polymerization component does not dissolve here, the polymerization can of course also be carried out in another solvent, e.g. B. toluene, drain. The solvent used is then stripped off and the remaining polymer is dissolved in the aliphatic hydrocarbon.
  • the charge control agent according to the invention is suitable for the production of all types of liquid developers. So you can z. B. disperse bare carbon blacks in the polymer solution, then add fixing agents - such as soluble resins or polymer organosols - and possibly add a further amount of charge control agent. Instead of the carbon black, you can also use resinated, flushed or polymer grafted carbon blacks or other pigments. In any case, the control agents according to the invention bring about clear negative charging of the pigment particles.
  • the liquid developers can contain, for example, waxes as additives which have a favorable influence on the sedimentation behavior of the liquid developer or the smudge resistance of the developed images. These additives are generally used in amounts corresponding to the pigment content.
  • Highly chlorinated or fluorinated paraffins are particularly suitable as halogen-containing waxes, the latter being obtained by thermal degradation of polytetrafluoroethylene and being soluble in aliphatic hydrocarbons.
  • Examples 1-8 describe the preparation of the charge control substance according to the invention.
  • Examples 9 to 12 relate to liquid developers produced with it.
  • a 2 I 4-necked flask equipped according to Example 1 is charged with 600 g of an aliphatic hydrocarbon, boiling range about 160-180 ° C, 390 g of 2-ethylhexyl methacrylate, 90 g of N-vinyl-2-pyrrolidone and 1.8 g of AIBN. After flushing with nitrogen for ten minutes, the mixture is polymerized at 80 ° C. for 5 hours. The resulting viscous polymer solution is cloudy.
  • Example 1 is repeated with the following mixture: 100 g of the aliphatic hydrocarbon, 62.5 g of 2-ethylhexyl methacrylate, 17.5 g of N-vinyl-2-pyrrolidone and 0.3 g of AIBN.
  • the polymerization time is 5 hours. The result is a cloudy polymer solution.
  • Example 1 100 g of an aliphatic hydrocarbon, boiling range about 160-180 ° C, 65 g of 2-ethylhexyl methacrylate, 15 g of N-vinyl-2-pyrrolidone and 0.3 AIBN are stirred under a nitrogen atmosphere at an increasing temperature. The heating bath is kept at 65, 70, 75, 80, 85 and 90 ° C for 1 hour each. The resulting polymer solution has almost the same properties as the solution according to Example 2.
  • the following mixture is polymerized in the apparatus according to Example 1 for 5 hours at 80 ° C. under nitrogen.
  • a slightly cloudy polymer solution is formed.
  • the polymerization is stopped by slowly cooling the container to about 30 ° C.
  • the suspension of the grafted carbon black is finally diluted with a further 450 g of an aliphatic hydrocarbon, boiling range 175-190 ° C.
  • Example 2 60 g of the graft black suspension produced are mentioned with 20 g of that in Example 1 organic polymer dispersion and stirred with a further 10 g of polymer solution according to Example 2. Dilution with 2.5 liters of an aliphatic hydrocarbon, boiling range 160-180 ° C, yields a good negative liquid developer.
  • 1350 g of the soot dispersion obtained are stirred with 60 g of the above-mentioned commercial terpolymer solution, 1350 g of an aliphatic hydrocarbon with a boiling range of 160-180 ° C. and 12 g of saturated solution of a chlorinated paraffin with 70% chlorine in the same hydrocarbon.

Landscapes

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

Claims (16)

1. Révélateur liquide pour le développement d'images de charge électrostatique à charge positive comprenant un liquide porteur électriquement isolant, dans lequel sont dispersés ou dissous du pigment, du liant résineux, un agent de contrôle de charge qui est un produit de copolymérisation renfermant un ester d'acide méthacrylique et des additifs, caractérisé en ce que la substance de contrôle de charge est un produit de copolymérisation soluble dans le liquide porteur, formé de 1 à 50% en poids de N - vinyl - 2 - pyrrolidone et de 50 à 99% en poids d'ester d'acide méthacrylique.
2. Révélateur liquide selon la revendication 1, caractérise en ce que l'agent de contrôle de charge est un produit de copolymérisation formé de 15 à 40% en poids de N - vinyl - 2 - pyrrolidone et de 60 à 85% en poids d'ester d'acide méthacrylique.
3. Révélateur liquide selon les revendications 1 et 2 caractérisé en ce que l'ester d'acide méthacrylique comprend une partie alcool possédant au moins 6 atomes de carbone.
4. Révélateur liquide selon l'une quelconque des revendications 1 à 3, caractérisé en ce que le produit de copolymérisation contient du méthacrylate de 2 - éthyle - hexyle.
5. Révélateur liquide selon l'une quelconque des revendications 1 à 3, caractérisé en ce que le produit de copolymérisation contient du méthacrylate de dodécyle.
6. Révélateur liquide selon l'une quelconque des revendications 1 à 3, caractérisé en ce que le produit de copolymérisation contient du méthacrylate d'octadécyle.
7. Révélateur liquide selon l'une quelconque des revendications 1 à 6, caractérisé en ce que l'agent de contrôle de charge est un produit de copolymérisation contenant additionnelle ment un monomère acrylique.
8. Révélateur liquide selon la revendication 7, caractérisé en ce que l'agent de contrôle de charge est un produit de copolymérisation contenant additionnellement un monomère acrylique ayant une chaîne latérale polaire.
9. Révélateur liquide, selon la revendication 8, caractérisé en ce que le produit de copolymérisation contient une fraction allant jusqu'à environ 5% en poids d'un monomère acrylique ayant une chaîne latérale polaire.
10. Révélateur liquide selon les revendications 8 et 9, caractérisé en ce que le monomère acrylique ayant une chaîne latérale polaire est choisi parmi l'acide méthacrylique, l'amide de l'acide acrylique et le méthacrylate d'hydroxyalkyle.
11. Révélateur selon la revendication 7, caractérisé en ce que l'agent de contrôle de charge est un produit de copolymérisation, contenant additionnellement un ester d'acide méthacrylique renfermant une partie alcool ayant au maximum 6 atomes de carbone.
12. Révélateur liquide selon la revendication 11, caractérisé en ce que le produit de copolymérisation contient jusqu'à environ 30% en poids d'ester d'acide méthacrylique à chaîne courte.
13. Révélateur liquide selon l'une quelconque des revendications 1 à 12, caractérisé en ce qu'il contient de 0,1 à 5% en poids par rapport au pigment ou au colorant, d'une cire halogènée.
14. Révélateur liquide selon la revendication 13 caractérisé en ce que la cire halogénée est une paraffine ayant une teneur élevée en chlore.
15. Révélateur selon la revendication 13, caractérisé en ce que la cire halogénée est une paraffine fluorée.
16. Agent de contrôle de charge formé d'un produit de copolymérisation comprenant de 1 à 50% en poids de N - vinyl - 2 - pyrrolidone et de 50 à 99% en poids d'ester d'acide méthacrylique utilisé pour donner une charge négative à des particules de pigment dans des révélateurs liquides pour le développement d'images de charge électrostatiques à charge positive.
EP78100815A 1977-09-10 1978-09-04 Révélateur liquide et agent de contrôle de charge approprié Expired EP0001103B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19772740870 DE2740870A1 (de) 1977-09-10 1977-09-10 Fluessigentwickler und hierzu geeignetnr ladungssteuerstoff
DE2740870 1977-09-10

Publications (2)

Publication Number Publication Date
EP0001103A1 EP0001103A1 (fr) 1979-03-21
EP0001103B1 true EP0001103B1 (fr) 1981-09-16

Family

ID=6018644

Family Applications (1)

Application Number Title Priority Date Filing Date
EP78100815A Expired EP0001103B1 (fr) 1977-09-10 1978-09-04 Révélateur liquide et agent de contrôle de charge approprié

Country Status (5)

Country Link
US (1) US4243736A (fr)
EP (1) EP0001103B1 (fr)
JP (1) JPS5451531A (fr)
AU (1) AU518690B2 (fr)
DE (2) DE2740870A1 (fr)

Families Citing this family (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3011193A1 (de) * 1980-03-22 1981-10-01 Hoechst Ag, 6000 Frankfurt Fluessigentwickler zur entwicklung elektrostatischer ladungsbilder
US4374918A (en) * 1981-09-16 1983-02-22 Nashua Corporation Thermally stable liquid negative developer
JPS58203455A (ja) * 1982-05-21 1983-11-26 Canon Inc 静電荷現像用シアントナー及び電子写真法
DE3231505A1 (de) * 1982-08-25 1984-03-01 Hoechst Ag, 6230 Frankfurt Elektrophotographischer fluessigentwickler
JPS59102253A (ja) * 1982-12-06 1984-06-13 Ricoh Co Ltd 電子写真用液体現像剤
DE3247925A1 (de) * 1982-12-24 1984-06-28 Hoechst Ag, 6230 Frankfurt Fluessigentwickler fuer die entwicklung elektrostatischer ladungsbilder und verfahren zu seiner herstellung
EP0176629B1 (fr) * 1984-10-02 1988-08-03 Agfa-Gevaert N.V. Révélateur liquide pour le développement d'images électrostatiques
US5264313A (en) * 1984-12-10 1993-11-23 Spectrum Sciences B.V. Charge director composition
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
USH509H (en) 1987-12-22 1988-08-02 Preparation of adhesives
JP3076921B2 (ja) * 1989-02-06 2000-08-14 スペクトラム、サイエンセズ、ベーヴェー チャージディレクタ組成物
US5047306A (en) * 1989-05-19 1991-09-10 Spectrum Sciences B. V. Humidity tolerant charge director compositions
JP2818914B2 (ja) * 1991-04-05 1998-10-30 シャープ株式会社 多目的スチーム発生器
CN104105714B (zh) * 2011-12-21 2017-04-05 路博润高级材料公司 制备丙烯酸聚合物的方法以及由此制得的产物
JP6484938B2 (ja) * 2014-07-03 2019-03-20 コニカミノルタ株式会社 液体現像剤およびその製造方法

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2497705A (en) * 1946-10-16 1950-02-14 Du Pont Copolymerization product of n-vinyl lactams and polymerizable esters, and process for making same
US3044873A (en) * 1958-12-17 1962-07-17 Polaroid Corp Photographic products and processes
GB1016072A (en) * 1960-11-14 1966-01-05 Gen Aniline & Film Corp Electrophotographic recording process
US3542681A (en) * 1968-07-10 1970-11-24 Gaf Corp Negative working electrostatic toners
US3876610A (en) * 1969-07-25 1975-04-08 Agfa Gevaert Nv Manufacture of an electrostatic toner material
US3969238A (en) * 1972-08-15 1976-07-13 Canon Kabushiki Kaisha Liquid developer for electrophotography and process for developing latent images
US3954640A (en) * 1973-06-27 1976-05-04 Xerox Corporation Electrostatic printing inks
JPS5080136A (fr) * 1973-11-13 1975-06-30
US3993483A (en) * 1974-01-22 1976-11-23 Canon Kabushiki Kaisha Liquid developer for electrostatic image
JPS51126152A (en) * 1974-09-03 1976-11-04 Ricoh Co Ltd Liquid developer for electrophotography
JPS5140465A (ja) * 1974-10-02 1976-04-05 Enshu Seisaku Kk Shokukinonunomakitorisochiniokeruteichoryokuijisochi
JPS5540865B2 (fr) * 1975-01-07 1980-10-21
JPS6015063B2 (ja) * 1976-10-26 1985-04-17 オーリン ハント スペシャルティ プロダクツ インコーポレイテッド 電子写真用混合液体ト−ナ−

Also Published As

Publication number Publication date
US4243736A (en) 1981-01-06
JPS649630B2 (fr) 1989-02-17
DE2740870A1 (de) 1979-03-22
JPS5451531A (en) 1979-04-23
AU3967978A (en) 1980-03-13
DE2861086D1 (en) 1981-12-03
AU518690B2 (en) 1981-10-15
EP0001103A1 (fr) 1979-03-21

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