EP0403178B1 - Agent de contraste comprenant un liant polymérisé en suspension - Google Patents

Agent de contraste comprenant un liant polymérisé en suspension Download PDF

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Publication number
EP0403178B1
EP0403178B1 EP19900306269 EP90306269A EP0403178B1 EP 0403178 B1 EP0403178 B1 EP 0403178B1 EP 19900306269 EP19900306269 EP 19900306269 EP 90306269 A EP90306269 A EP 90306269A EP 0403178 B1 EP0403178 B1 EP 0403178B1
Authority
EP
European Patent Office
Prior art keywords
toner
polymerisation
acid
dispersing agent
vinyl
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 - Lifetime
Application number
EP19900306269
Other languages
German (de)
English (en)
Other versions
EP0403178A3 (fr
EP0403178A2 (fr
Inventor
Keiji C/O Products Development Lab. Yoshida
Ryo C/O Products Development Lab. Funato
Syuji C/O Products Development Lab. Takahiro
Shinji C/O Toyohashi Plants Kubo
Motoshi C/O Products Development Lab. Inagaki
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.)
Mitsubishi Rayon Co Ltd
Original Assignee
Mitsubishi Rayon Co Ltd
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Filing date
Publication date
Application filed by Mitsubishi Rayon Co Ltd filed Critical Mitsubishi Rayon Co Ltd
Publication of EP0403178A2 publication Critical patent/EP0403178A2/fr
Publication of EP0403178A3 publication Critical patent/EP0403178A3/fr
Application granted granted Critical
Publication of EP0403178B1 publication Critical patent/EP0403178B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime 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
    • G03G9/087—Binders for toner particles
    • G03G9/08702—Binders for toner particles comprising macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds

Definitions

  • the present invention relates to a toner which includes a vinyl polymer binder that has been prepared by a particular polymerisation method.
  • the vinyl polymer binder used in the toner of the present invention is prepared by suspension polymerisation using a particular dispersing agent and initiator.
  • Vinyl polymers for use as binder resins in toners are produced by many different types of polymerisation such as suspension polymerisation, bulk polymerisation, solution polymerisation, emulsion polymerisation, etc. Suspension polymerisation is preferred because the manufacturing costs are minimised.
  • EP-A-297839 describes a method for making a toner by polymerisation of vinyl monomers in the presence of carbon black.
  • GB-A-2197656 relates to preparation of toners having uniform particle size distribution.
  • suspension polymerisation is disadvantageous in that the binder resin produced will contain residue of the suspension polymerisation process, including residues of the dispersing agent and initiator used in the polymerisation.
  • binder resins are undesirable because toners prepared using them are problematic in terms of chargeability and stability (life) of the image quality.
  • the present inventors have studied these problems and found that if the toner is prepared using a vinyl polymer binder obtained by suspension polymerisation of a polymerised vinyl monomer with a non-ionic dispersing agent and an azo initiator, the resultant toner will have superior stability of image quality.
  • a toner comprising a polymeric binder obtained by suspension polymerisation of a mixture of vinyl monomers including both styrene or a styrene derivative and a (meth)acrylic acid ester and an acid vinyl monomer in an amount of 0.5 to 10 wt% based on the total weight of the vinyl monomers, the suspension polymerisation being carried out using a non-ionic dispersing agent and an azo initiator.
  • the polymerisable vinyl monomer includes an acid monomer in an amount 1 to 10 wt%.
  • vinyl monomers which may be included are vinyl esters such as vinyl acetate, vinyl propionate, etc.; and acrylic acid derivatives or methacrylic acid derivatives such as acrylonitrile, methacrylonitrile, etc. These polymerisable vinyl monomers are used alone or in admixture of two or more of them.
  • the preferred monomer mixtures include those having styrene and/or its derivatives and alkyl (meth) acrylates as the main constituents of the mixture.
  • the amount of the acid monomer is 0.5 to 10 wt.% based on the total weight of the polymerisable vinyl monomers.
  • the amount of the acid monomer is 0.5 to 10 wt.% based on the total weight of the polymerisable vinyl monomers.
  • Suitable acid monomers for use in the present invention are monomers having one or more acid substituents in addition to the polymerisable vinyl group.
  • suitable monomers are acrylic acid, methacrylic acid, itaconic acid, citraconic acid, maleic acid, fumaric acid, crotonic acid, monobutyl itaconate, monomethyl maleate, monobutyl maleate, monooctyl maleate, monooctyl itaconate, 2-sulfoethyl methacrylate, 2-sulfoethyl acrylate, 2-acrylamide-2-methylpropanesulfonic acid, vinylbenzenesulfonic acid, etc.
  • These acid monomers are used alone or in admixture of two or more of them.
  • the vinyl polymer used in the present invention is produced by suspension polymerisation.
  • the azo initiator used in this method is not critical, it being possible to use the well-known ones. Suitable examples are azobisisobutyronitrile, 2,2′-azobis-(2,4-dimethylvaleronitrile), dimethyl-2,2′-azobisisobutyronitrile, 2,2′-azobis-(2-methylbutyronitrile), 1,1′-azobis-(cyclohexane-1-carbonitrile), 2,2′-azobis-(2-cyclopropylpropionitrile), 2,2′-azobis-(4-methoxy-2,4-dimethylvaleronitrile), etc.
  • azobisisobutyronitrile 2,2′-azobis- (2,4-dimethylvaleronitrile), dimethyl-2,2′-azobisisobutyronitrile or 2,2′-azobis-(2-methylbutyronitrile) because these initiators have properties to keep a polymerisation activity upon the monomer and complete the polymerisation in a relatively short time, and because they do not have a high tendency to leave their decomposition by-products in the resulting polymer.
  • azo initiators are used alone or in admixture of two or more of them.
  • the toner of the present invention has a remarkably improved life as compared with toners containing binder polymers obtained by the conventional methods, because it uses a vinyl polymer binder obtained by suspension polymerisation with a non-ionic dispersing agent.
  • the non-ionic dispersing agents for use in the present invention are preferably polymeric. Suitable examples include polyvinyl alcohol, methyl cellulose, ethyl cellulose, hydroxypropyl cellulose, gelatin, polyethylene oxide, etc. of these nonionic dispersing agents, polyvinyl alcohol having a saponification degree of 70 to 90% and a polymerisation degree of 500 to 3000 is preferred because resins obtained with it have good binder characteristics for toners.
  • the nonionic dispersing agent is used in such an amount that the polymerisation operation can be completed without causing aggregation of the produced resin particles in the course of the polymerisation.
  • the amount of the agent is usually 0.01 to 5 parts by weight, preferably 0.05 to 2 parts by weight based on 100 parts by weight of water.
  • a dispersion auxiliary may be used. It includes for example electrolytes such as sodium chloride, potassium chloride, sodium sulfate, potassium sulfate, etc.
  • the necessary conditions for the suspension polymerisation vary with the particular polymerisable vinyl monomer/s, and azo initiator/s used and the amounts thereof.
  • the optimum polymerisation temperature is generally 30° to 130°C, preferably 60° to 100°C, and the polymerisation time is preferably about 1 to about 10 hours.
  • the reaction solution is filtered, and the resulting polymer is thoroughly washed, dehydrated and dried. A coloring agent and other additives are added to this polymer to obtain the toner of the present invention.
  • a toner was obtained in the same manner as in Example 1 except that 82 parts of styrene, 17 parts of 2-ethylhexyl acrylate, 1 part of methacrylic acid and 0.3 part of divinylbenzene were used as the polymerizable vinyl monomer. The performances of this toner were evaluated, and it was found that fog-free high-resolution clear images were obtained even after 20,000 copying operations.
  • a toner was obtained in the same manner as in Example 1 except that 82.5 parts of styrene, 17 parts of 2-ethylhexyl acrylate, 0.5 part of methacrylic acid and 0.3 part of divinylbenzene were used as the polymerizable vinyl monomer.
  • the performances of this toner were evaluated, and it was found that fog-free high-resolution clear images were obtained at the initial stage of copying and after 10,000 copying operations, but after 20,000 copying operations, the images showed a faint touch of fog, which was however of such a degree as to be out of the question in practical use.
  • a toner was obtained in the same manner as in Example 1 except that 73 parts of styrene, 17 parts of 2-ethylhexyl acrylate, 10 parts of methacrylic acid and 0.3 part of divinylbenzene were used as the polymerizable vinyl monomer. The performances of this toner were evaluated, and it was found that fog-free high-resolution clear images were obtained even after 20,000 copying operations, but the fixability and grindability were somewhat lowered.
  • a toner was obtained in the same manner as in Comparative Example 1 except that 3 parts of benzoyl peroxide, which is not an azo initiator, was used as the polymerization initiator, and that the polymerization temperature was 85°C.
  • the performances of this toner were evaluated, and it was found that the images at the initial stage of copying were fog-free high-resolution clear ones, but that after 5,000 copying operations, only images having a touch of fog and a lowered resolution degree were obtained.
  • a toner was obtained in the same manner as in Example 1 except that 3 parts of benzoyl peroxide was used as the initiator and the polymerization temperature was 85°C. The performances of this toner were evaluated, and it was found that the images at the initial stage of copying were fog-free high-resolution clear ones, but that after 10,000 copying operations, only images having a touch of fog and a lowered resolution degree were obtained.
  • a toner was obtained in the same manner as in Comparative Example 1 except that 0.2 part of an anion-modified polyvinyl alcohol (KL-318 produced by KURARAY CO., LTD.), which is not a nonionic dispersing agent, was used as the dispersing agent.
  • KL-318 produced by KURARAY CO., LTD.
  • the performances of this toner were evaluated, and it was found that the images at the initial stage of copying were fog-free high-resolution clear ones, but that after 5,000 copying operations, only images having a touch of fog and a lowered resolution degree were obtained.
  • a toner was obtained in the same manner as in Example 1 except that 0.2 part of an anion-modified polyvinyl alcohol (KL-318 produced by KURARAY CO., LTD.) was used as the dispersing agent. The performances of this toner were evaluated, and it was found that the images at the initial stage of copying were fog-free high-resolution clear ones, but that after 10,000 copying operations, only images having a touch of fog and a lowered resolution degree were obtained.
  • KL-318 produced by KURARAY CO., LTD.
  • a toner was obtained in the same manner as in Comparative Example 1 except that 0.2 part of a cation-modified polyvinyl alcohol (C-318 produced by KURARAY CO., LTD.) was used as the dispersing agent. The performances of this toner were evaluated, and it was found that the images at the initial stage of copying were fog-free high-resolution clear ones, but that after 5,000 copying operations, only images having a touch of fog and a lowered resolution degree were obtained.
  • C-318 produced by KURARAY CO., LTD.
  • a toner was obtained in the same manner as in Example 1 except that 0.2 part of a cation-modified polyvinyl alcohol (C-318 produced by KURARAY CO., LTD.) was used as the dispersing agent. The performances of this toner were evaluated, and it was found that the images at the initial stage of copying were fog-free high-resolution clear ones, but that after 10,000 copying operations, only images having a touch of fog and a lowered resolution degree were obtained.
  • C-318 produced by KURARAY CO., LTD.

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • General Physics & Mathematics (AREA)
  • Developing Agents For Electrophotography (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Claims (8)

  1. Un toner comprenant un liant polymère pouvant être obtenu par polymérisation en suspension d'un mélange de monomères vinyliques comprenant à la fois du styrène ou un dérivé du styrène et un ester d'acide (méth)acrylique, et un monomère vinylique acide en une quantité de 0,5 à 10 % en poids par rapport au poids total des monomères vinyliques, la polymérisation étant effectuée en utilisant un agent dispersant non ionique et un initiateur azoïque.
  2. Un toner selon la revendication 1, comprenant le monomère vinylique acide en une quantité de 1 à 10 % en poids.
  3. Un toner selon l'une quelconque des revendications précédentes, dans lequel l'agent dispersant non ionique est un alcool polyvinylique.
  4. Un toner selon la revendication 3, dans lequel l'alcool polyvinylique a un degré de saponification de 70 à 90 %.
  5. Un toner selon la revendication 3 ou la revendication 4, dans lequel l'alcool polyvinylique a un degré de polymérisation de 500 à 3000.
  6. Un toner selon l'une quelconque des revendications précédentes, dans lequel la quantité d'agent dispersant non ionique est de 0,05 à 2 parties en poids pour 100 parties en poids d'eau.
  7. Un toner selon l'une quelconque des revendications précédentes, dans lequel l'initiateur azoïque est au moins un membre du groupe formé par l'azobisisobutyronitrile, le 2,2′-azobis(2,4-diméthylvaléronitrile), le diméthyl-2,2′-azobisisobutyronitrile.
  8. Utilisation d'un monomère vinylique acide dans un procédé de préparation d'un liant polymère par polymérisation en suspension d'un mélange de monomères vinyliques en présence d'un agent dispersant non ionique et d'un initiateur azoïque, le mélange de monomères vinyliques comprenant à la fois du styrène ou un dérivé du styrène et un ester d'acide (méth)acrylique et comprenant le monomère acide en une quantité de 0,5 à 10 % en poids par rapport au poids total des monomères, pour obtenir une meilleure stabilité de l'image produite en utilisant le polymère dans un toner.
EP19900306269 1989-06-15 1990-06-08 Agent de contraste comprenant un liant polymérisé en suspension Expired - Lifetime EP0403178B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP15053789A JP2855447B2 (ja) 1989-06-15 1989-06-15 トナー
JP150537/89 1989-06-15

Publications (3)

Publication Number Publication Date
EP0403178A2 EP0403178A2 (fr) 1990-12-19
EP0403178A3 EP0403178A3 (fr) 1991-04-10
EP0403178B1 true EP0403178B1 (fr) 1995-11-15

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ID=15499039

Family Applications (1)

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EP19900306269 Expired - Lifetime EP0403178B1 (fr) 1989-06-15 1990-06-08 Agent de contraste comprenant un liant polymérisé en suspension

Country Status (4)

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EP (1) EP0403178B1 (fr)
JP (1) JP2855447B2 (fr)
CA (1) CA2018371C (fr)
DE (1) DE69023553T2 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102004051830B4 (de) 2004-10-25 2007-12-13 Roche Diagnostics Gmbh Multifunktionales Referenzsystem bei Analytbestimmungen durch Fluoreszenz

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4849318A (en) * 1986-10-31 1989-07-18 Mita Industrial Co., Ltd. Processes for producing electrophotographic toner
JP2760499B2 (ja) * 1986-11-05 1998-05-28 三菱レイヨン 株式会社 トナー用樹脂及びその製造法
CA1313968C (fr) * 1987-06-29 1993-03-02 Jiro Yamashiro Methode de fabrication de toners d'electrophotographie

Also Published As

Publication number Publication date
CA2018371A1 (fr) 1990-12-15
JP2855447B2 (ja) 1999-02-10
DE69023553T2 (de) 1996-04-11
EP0403178A3 (fr) 1991-04-10
CA2018371C (fr) 2001-05-01
JPH0317662A (ja) 1991-01-25
DE69023553D1 (de) 1995-12-21
EP0403178A2 (fr) 1990-12-19

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