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WO1993019101A1 - Procede de production de resines pour toner - Google Patents

Procede de production de resines pour toner Download PDF

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Publication number
WO1993019101A1
WO1993019101A1 PCT/EP1993/000515 EP9300515W WO9319101A1 WO 1993019101 A1 WO1993019101 A1 WO 1993019101A1 EP 9300515 W EP9300515 W EP 9300515W WO 9319101 A1 WO9319101 A1 WO 9319101A1
Authority
WO
WIPO (PCT)
Prior art keywords
molecular weight
carbon atoms
toner
alkylene group
peroxide
Prior art date
Application number
PCT/EP1993/000515
Other languages
English (en)
Inventor
Wilfridus Maria Brouwer
Petrus Johannes Theodorus Alferink
Original Assignee
Akzo Nobel N.V.
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 Akzo Nobel N.V. filed Critical Akzo Nobel N.V.
Priority to JP5516206A priority Critical patent/JPH07506199A/ja
Publication of WO1993019101A1 publication Critical patent/WO1993019101A1/fr

Links

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
    • G03G9/08706—Polymers of alkenyl-aromatic compounds
    • G03G9/08708—Copolymers of styrene
    • G03G9/08711—Copolymers of styrene with esters of acrylic or methacrylic acid
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/28—Oxygen or compounds releasing free oxygen
    • C08F4/32—Organic compounds
    • 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 process for manufacturing toner resins in the presence of peroxides.
  • Electrographic methods comprise the use of a heated roller for fixing electrostatic latent images, which are visualized with the use of a dry development toner.
  • a low fixing temperature can be obtained by using polymeric material of low molecular weight.
  • the use of a low molecular weight polymer alone as the dry development toner material has the disadvantage that it causes blocking.
  • high molecular weight polymer is essential to imparting high temperature offset properties to a dry development toner.
  • a dry toner must consist of polymers (hereinafter described as toner resins) having both a low molecular weight and a high molecular weight in order to provide fixability at low temperatures, offset properties and anti-blocking properties.
  • the present invention relates to a process for manufacturing high molecular weight toner resins by polymerizing at least one polymerizable vinyl monomer in the presence of at least one polyfunctional polymerization initiator having at least one peroxide functionality and at least one unsaturated functionality.
  • the polyfunctional polymerization initiator is an organic peroxide represented by the general formula:
  • Ri is an alkylene group having from 1 to 22 carbon atoms, a sec-alkylene group having from 2 to 22 carbon atoms, or a tert-a kylene group having from 3 to 22 carbon atoms and n is an integer from 0 to 5, the organic peroxide being present in the process in an amount of 0.001 to 2 wt%.
  • the organic peroxides of the present invention have the advantage of not needing to be phlegmatized. Therefore, dry development toners comprising high molecular weight toner resins of the present invention have a good offset resistance. Furthermore, the use of the organic peroxides of the present invention results in nearly complete conversion to polymer.
  • Z in the general formula I represents a hydrogen atom.
  • the organic peroxide is 4-isopropenylcumyl tert-butyl peroxide.
  • the organic peroxides of the present invention may be prepared in a manner as described in M.A. Dikii, V.A. Puchin, S.A. Voronov, V.S. Tokarev, 0.1. Gevus (Lvov. Politekh. Inst., Lvov, USSR), Zh. Org. Khim., 1981, 17 (2), 337-9.
  • Suitable polymerizable monomers include aromatic vinyl monomers, such as styrene and styrene homologues or substituted styrenes, including C ⁇ _8 alkylstyrenes, al oxy-substituted styrenes, halogen-substituted styrenes; acrylic or methacrylic monomers, such as C ⁇ _8 alkyl (meth)acrylates, aryl (meth)acrylates, hydroxyl-containing (meth)acrylates, amino-containing ( eth)acrylates, epoxy-containing (meth)acrylates, and ( eth)acrylic acids and derivatives thereof; vinyl esters, such as vinyl acetate and vinyl propionate; aliphatic hydrocarbon monomers, such as butadiene; vinyl ethers, such as vinylmethyl ether, vinylethyl ether, and vinyl-iso-butyl ether; vinyl ketones, such as vinylmethyl ketone, vinylhexyl ketone
  • Preferred polymerizable monomers are styrene, alkyl (meth)acrylates (more particularly, methyl, ethyl, butyl, and 2-ethylhexyl (meth)acrylates), (meth)acrylic acids, vinyl esters, aliphatic hydrocarbon monomers, and mixtures thereof.
  • copolymers of styrene and alkyl (meth)aerylates are prepared by the process of the present invention.
  • the polymerization process It is preferred to carry out the polymerization process at a temperature not lower than 60°C and not higher than 160°C. More preferably, the process is carried out at a temperature of 110 o -140°C.
  • the process of the invention may be carried out using any known polymerization technique, such as solution polymerization, bulk polymerization, suspension polymerization, emulsion polymerization, and combinations thereof.
  • Suitable solvents used in solution polymerization include cycloalkanes, such as cyclohexane; aromatic hydrocarbons, such as benzene, toluene, xylene, ethylbenzene, and cu ene; esters, such as ethyl acetate and butyl acetate; ethers, such as methyleellosolve, ethylcellosolve and butylcellosolve; and the like. Preferred among these to obtain high molecular weight polymer are cycloalkanes and aromatic hydrocarbons.
  • Suspension polymerization can be carried out in an aqueous medium, as known in the art.
  • This invention relates also to dry development toners comprising the high molecular weight toner resin produced by the process of the present invention. Dry development toners of the present invention have a good offset resistance.
  • the dry development toner comprising said high molecular weight toner resin may further contain one or more other components. It preferably contains one or more lower molecular weight toner resins.
  • toner resins of a molecular weight of 3000 to 50000 are present, such as styrene/acrylic copolymers, polyester resins, ' polyepoxide resins, polyurethane resins, and the like. Among these, styrene/acrylic copolymers and polyester resins are preferred.
  • said low molecular weight toner resin can be prepared beforehand, either separately or simultaneously with the preparation of said high molecular weight toner resin.
  • dry development toner may be produced by blending, in a solution or in the melted state, the high and low molecular weight toner resins being prepared separately beforehand; or by polymerizing said monomer to a high molecular weight toner resin in the presence of a low molecular weight toner resin and the organic peroxide of the present invention.
  • said low molecular weight toner resin may be produced by polymerizing in bulk or in solution at least one precursor monomer for a low molecular weight toner resin in the presence of a high molecular weight polymer.
  • a high molecular weight polymer is dissolved in said precursor monomer, which precursor monomer is then polymerized to obtain a low molecular weight polymer.
  • the polymerizing of said precursor monomer is by bulk polymerization or solution polymerization rather than suspension polymerization, because when using the former two techniques, one can remarkably reduce the amount of the polymerization initiator to provide the same molecular weight and, therefore, can remedy or reduce objectionable influences (such as excessive charging of toner, environmental instability, and so on) caused by the presence of initiator residues.
  • the low and high molecular weight toner resins may be blended or used in bonded form, such as through covalent bonding.
  • the content of the high molecular weight toner resin is usually 10-50 wt%, preferably 15-45 wt%, and that of the low molecular weight toner resin 50-90 wt%, preferably 55-85 wt%, based on the total weight of these toner resins.
  • the dry development toner may contain one or more known colorants in an amount of 5 to 10 wt%, magnetic powders in an amount of 0 to 50 wt%, and other additives, -such as charge controllers and lubricants in an amount of 0 to 5 wt%.
  • Colorants may be inorganic or organic pigments, such as carbon black, iron black, benzidine yellow, quinacridone pigments, rhodamine B, phthalocyanine pigments, and the like.
  • Preferred magnetic powders are powders of ferromagnetic metals and compounds such as iron, cobalt, nickel, magnetite, hematite, ferrite, and the like.
  • the dry development toner may be prepared by dry blending these components and then melting them under kneading, followed by crushing, finely pulverizing with a grinder, and finally classifying to obtain particles of 5-20 microns diameter.
  • the dry development toner may be optionally mixed with one or more carrier particles, such as iron powder, glass beads, nickel powder, ferrite, and the like, and used as a developer for electrical latent images.
  • carrier particles such as iron powder, glass beads, nickel powder, ferrite, and the like
  • hydrophobic colloidal silica powder may be used to improve flowability of the powders.
  • ampoules - 2.5 cm 3 in volume, were 80% filled with a monomer mixture of 80 wt% styrene and 20 wt% butyl acrylate, in which mixture different peroxides in an amount of 0.75 meq active oxygen groups/lOOg were dissolved.
  • the ampoules were sealed under nitrogen and immersed in a pre-heated oil bath. Each two hours an ampoule was taken from the oil bath and analysed for monomer conversion and polymer molecular weight. The results obtained after 10 hours of polymerization have been reported in Table I.
  • Examples 1-3 are carried out with an organic peroxide according to the invention.
  • Examples A-E are comparative examples using organic peroxides disclosed in GB-A-2 232 160. Table I
  • Tx 171 4-isopropenylcumyl tert-butyl peroxide
  • Px 12 2,2-bis(4,4-di-tert-butylperoxycyclohexyl )propane
  • Mw weight-average molecular weight
  • Mn number-average molecular weight
  • the peroxide of the present invention (Ex. 1-3) is able to convert a styrene/butylacrylate monomer mixture more completely at a higher molecular weight than the other two peroxides (Ex. A-E), under the same reaction conditions. Further, the peroxides of the present invention are able to be applied at higher temperatures than the other mentioned peroxides thus enabling reactor output to be increased.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • General Physics & Mathematics (AREA)
  • Materials Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Developing Agents For Electrophotography (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

Procédé de production de résines pour toner ayant une masse molaire élevée comprenant la polymérisation d'au moins un monomère de vinyle pouvant polymériser, en présence d'au moins un initiateur de polymérisation polyfonctionnel comportant au moins une fonctionnalité peroxyde et au moins une fonctionnalité non saturée. Ce procédé se caractérise par le fait que l'initiateur de polymérisation utilisé est un peroxyde organique, dont le pourcentage en poids est compris entre 0,001 et 2.
PCT/EP1993/000515 1992-03-25 1993-03-05 Procede de production de resines pour toner WO1993019101A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP5516206A JPH07506199A (ja) 1992-03-25 1993-03-05 トナー樹脂の製造方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP92200847 1992-03-25
EP92200847.9 1992-03-25

Publications (1)

Publication Number Publication Date
WO1993019101A1 true WO1993019101A1 (fr) 1993-09-30

Family

ID=8210502

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1993/000515 WO1993019101A1 (fr) 1992-03-25 1993-03-05 Procede de production de resines pour toner

Country Status (2)

Country Link
JP (1) JPH07506199A (fr)
WO (1) WO1993019101A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7582708B2 (en) 2001-06-13 2009-09-01 Beta Technologie Ag Bulk polymerization reactor methods

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0208353A1 (fr) * 1985-06-26 1987-01-14 Akzo N.V. Procédé de réticulation ou de dégradation de polymères et objets obtenus par ce procédé
GB2232160A (en) * 1989-05-24 1990-12-05 Sanyo Chemical Ind Ltd Resin compositions for electrophotographic toner

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0208353A1 (fr) * 1985-06-26 1987-01-14 Akzo N.V. Procédé de réticulation ou de dégradation de polymères et objets obtenus par ce procédé
GB2232160A (en) * 1989-05-24 1990-12-05 Sanyo Chemical Ind Ltd Resin compositions for electrophotographic toner

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, vol. 102, no. 23, 10 June 1985, Columbus, Ohio, US; abstract no. 203721, 'ARYL PEROXIDES HAVING POLYMERIZABLE UNSATURATED GROUPS' page 576 ;column 1 ; *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7582708B2 (en) 2001-06-13 2009-09-01 Beta Technologie Ag Bulk polymerization reactor methods

Also Published As

Publication number Publication date
JPH07506199A (ja) 1995-07-06

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