EP0913735B1 - Particules de toner contenant un mélange d'un polymère linéaire modifié, un polymère réticulé et une cire - Google Patents

Particules de toner contenant un mélange d'un polymère linéaire modifié, un polymère réticulé et une cire Download PDF

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Publication number
EP0913735B1
EP0913735B1 EP19980203500 EP98203500A EP0913735B1 EP 0913735 B1 EP0913735 B1 EP 0913735B1 EP 19980203500 EP19980203500 EP 19980203500 EP 98203500 A EP98203500 A EP 98203500A EP 0913735 B1 EP0913735 B1 EP 0913735B1
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EP
European Patent Office
Prior art keywords
toner particles
polymer
compound
lpc
dry toner
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EP19980203500
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German (de)
English (en)
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EP0913735A3 (fr
EP0913735A2 (fr
Inventor
Serge Tavernier
Werner Op De Beeck
Stefaan De Meutter
Geert Tersago
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Xeikon Manufacturing NV
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Xeikon International NV
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Publication of EP0913735A3 publication Critical patent/EP0913735A3/fr
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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
    • G03G9/08784—Macromolecular material not specially provided for in a single one of groups G03G9/08702 - G03G9/08775
    • G03G9/08797—Macromolecular material not specially provided for in a single one of groups G03G9/08702 - G03G9/08775 characterised by their physical properties, e.g. viscosity, solubility, melting temperature, softening temperature, glass transition temperature
    • 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
    • G03G9/08742—Binders for toner particles comprising macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • G03G9/08755—Polyesters
    • 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
    • G03G9/08775—Natural macromolecular compounds or derivatives thereof
    • G03G9/08782—Waxes
    • 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
    • G03G9/08784—Macromolecular material not specially provided for in a single one of groups G03G9/08702 - G03G9/08775
    • G03G9/08791—Macromolecular material not specially provided for in a single one of groups G03G9/08702 - G03G9/08775 characterised by the presence of specified groups or side chains
    • 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
    • G03G9/08784—Macromolecular material not specially provided for in a single one of groups G03G9/08702 - G03G9/08775
    • G03G9/08793—Crosslinked polymers
    • 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
    • G03G9/08784—Macromolecular material not specially provided for in a single one of groups G03G9/08702 - G03G9/08775
    • G03G9/08795—Macromolecular material not specially provided for in a single one of groups G03G9/08702 - G03G9/08775 characterised by their chemical properties, e.g. acidity, molecular weight, sensitivity to reactants

Definitions

  • the present invention relates to dry toner particles, especially to dry toner particles useful in eletrostatographic or magnetographic imaging methods wherein the toner particles are fixed to the final image receiving member by simultaneous application of heat and pressure.
  • Toner particles are basically polymeric particles comprising a polymeric resin as main component and various ingredients mixed with said toner resin.
  • the toner particles comprise at least one black and/or colouring substances, e.g., coloured pigment.
  • the toner particles can be present in a liquid or in a dry developer composition.
  • the latent image After development of the latent image (in e.g. electro(photo)graphy, magnetography, ionography, etc.) the developed image is transferred to a substrate.
  • DEP direct electrostatic printing
  • the toner image is directly deposited on the substrate.
  • the visible image, on this substrate, of electrostatically or magnetically attracted toner particles is not permanent and has to be fixed by causing the toner particles to adhere to each other and the substrate by softening or fusing them followed by cooling. Normally fixing proceeds on more or less porous paper by causing or forcing the softened or fused toner mass to penetrate into the surface irregularities of the paper.
  • fusing processes used for fusing a toner powder image to its support. Some are based upon fixation primarily on fusing by heat, others are based on softening by solvent vapours, or by the application of cold flow at high pressure in ambient conditions of temperature. In the fusing processes based on heat, two major types should be considered, the "non-contact" fusing process and the “contact” fusing process. In the non-contact fusing process there is no direct contact of the toner image with a solid heating body.
  • a heating roller also called fuser roller and another roller backing the support and functioning as pressure exerting roller, called pressure roller.
  • This roller may be heated to some extent so as to avoid strong loss of heat within the copying cycle.
  • the last mentioned fusing process has been employed widely in low-speed as well as high-speed fusing systems, since a remarkably high thermal efficiency is obtained because the surface of the heating roller is pressed against the toner image surface of the sheet to be fixed.
  • toner particles designed to be fixed in a "contact” process, special resins and/or special additives for minimising the need of external release agent or for totally avoiding the use of such an agent.
  • polyesters as toner resin that comprise moieties derived from a long chain aliphatic dicarboxylic acid (e.g. eicosanedicarboxylic acid) or that contain long chain mono-carboxylic acid.
  • a long chain aliphatic dicarboxylic acid e.g. eicosanedicarboxylic acid
  • polyester toner resins modified by long chain aliphatic acids or alcohols are described.
  • EP-A-712 881 the modification of an amorphous polymer by two different long chain aliphatic acids or alcohols has been described.
  • EP-A-298 279 it is disclosed to blend multiphase polyorganosiloxane block or graft condensation copolymers in the toner resin.
  • EP-A-740 217 the modification of a polymer for use in toner particles by a reacting a polymer containing free hydroxyl or acid groups with specified polysiloxanes has been disclosed.
  • toner particles comprising a high softening point polyester, a low softening point polyester and a long-chain alkyl compound selected from the group consisting of long chain alcohols with 23 to 252 carbon atoms and long chain acid with 22 to 251 carbon atoms.
  • toner particles comprising as toner resin a mixture of high softening point polyester, a low softening point polyester and a polyester modified by reacting it with a long-chain alkyl compound selected from the group consisting of long chain alcohols with 23 to 252 carbon atoms and long chain acid with 22 to 251 carbon atoms. Toner particles with such toner resin are very resistant to hot-offset.
  • EP-A-0 606 873 also discloses such a mixture with the presence of a wax in the toner composition.
  • toner particles with acceptable to good hot-offset properties (i.e. do show very low hot-offset).
  • Toner particles need to have other properties together with the hot-offset properties.
  • toner particles are also exposed to severe mechanical stresses, e.g. during mixing, transport trough the devices, by doctor blades regulating the thickness of a toner layer, etc.
  • toner particles When toner particles are used in full-colour development the particles must have a very good fluidity during fixing for good interflow of the four colours (Y,M,C,K) and still show good hot-offset properties.
  • a similar good melt fluidity is essential when the grey scale (tonal range) in a black and white electrostatographic image fixed to a final substrate, is extended by realising the necessary different shades of grey with the superposition of toner particles comprising different amounts of black pigment as disclosed in EP-A-768 577 .
  • an undesirably high surface relief making the image very sensitive to scratches can be present, unless there is a very good interflow of the toner particles when fused.
  • dry toner particles comprising a resinous matrix and a wax, characterised in that said resinous matrix contains a mixture of a polymer (LPC) with weight average molecular weight (M w ) between 2,000 and 20,000, a tg ⁇ > 3 at 120 °C and 100 rad/sec and a low softening point T sLPC such that 90 °C ⁇ T sLPC ⁇ 120 °C, modified by a modifier (D) selected from the group consisting of long chain aliphatic compounds with a reactive end group and having between 20 and 250 carbon atoms and a polysiloxane, said modifier and said polymer being present in a molar ratio LPC/D between 0.8 and 1.25 and a non-linear polymer with a softening point T sB such that 110 °C ⁇ T sB ⁇ 135 °C making up at least 25 % by weight of said resinous matrix, and said wax has a melting point M
  • LPC polymer
  • the Hildebrand solubility factor of two compounds e.g. of compounds C and D
  • the Hildebrand solubility factors of two compounds are different (i.e. ⁇ B ⁇ ⁇ A ) it is meant that the factors differ more than 2 J 1/2 /cm 3/2 .
  • non-linear polymers is used to indicate both heavily branched polymers and totally or partially cross-linked polymers.
  • electrostatographic electrostatographic
  • ionography direct electrostatic printing
  • magnetographic imaging apparatus wherein dry toner particles are used to form an image on a final substrate and wherein the toner particles are fixed on the substrate in a contact fusing station comprising heated rollers
  • contact fusing means very simple contact fusing means.
  • hot-offset adheresion of toner particles on the fusing rollers instead of on the final substrate
  • complicated fusing station incorporating means for applying an external release agent on the image and means for metering the amount of release agent that is applied.
  • toner particles with good anti-hot-offset properties When in the imaging systems toner particles with good anti-hot-offset properties are used it is possible to simplify the fusing station. Ways and means for making toner particles with good anti-offset properties were already described in the background art section of this document and are described in, e.g., EP-A-276 147, JP-A-5967554, US-A-5 344 737, DE-A-195 20 580, EP-A-712 881, EP-A-298 279, EP-A-740 217, etc.. When toner particles are used in full-colour development the particles must have a very good fluidity during fixing for good interflow of the four colours (Y,M,C,K) and still show good anti-hot-offset properties.
  • toner particles comprising a resinous matrix and a wax, wherein in said resinous matrix a polymeric chain (polymer LPC) with a weight average molecular weight (M w ) between 2,000 and 20,000, a tg ⁇ > 3 at 120 °C and 100 rad/sec and with a fairly low softening point, T sLPC such that 90 °C ⁇ T sLPC ⁇ 120 °C and being modified with a long chain compound (compound D) to form polymer A, is present together with a heavily branched or (partially) cross-linked polymer (polymer B) with a softening point, T sB such that 110 °C ⁇ T sB ⁇ 135 °C and wherein said wax (compound C) has a melting point M p related to the softening point of the polymers such that 85°C ⁇ M p ⁇ 135 °C and M p ⁇ T sB + 10, did
  • said resinous matrix contains at least 50 % by weight with respect to the total weight of the resinous matrix of said polymer LPC modified by said compound D and said non-linear polymer B.
  • said resinous matrix of the toner particles consistsof said mixture of said polymer LPC modified by said compound D and said non-linear polymer B.
  • said polymer, LPC, with a tg ⁇ > 3 at 120 °C and 100 rad/sec is a linear polymer.
  • toner particles with a wax and a resinous matrix containing a polymer with a tg ⁇ > 3 at 120 °C and 100 rad/sec and being modified by compound D and a non-linear polyester did not show the same good quality with respect to interflow during fusing and anti-offset properties as toner particles having a wax and a resinous matrix according to this invention.
  • toner particles could be enhanced and the gloss of the resulting toner images could easily be controlled to give a satin look, when polymer LPC, compound D, polymer B and compound C have Hildebrand solubility factors in a specific range and in relation to each other.
  • Such toner particles combined good anti-hot-offset properties, good fluidity in molten state and good physical strength.
  • HILDEBRAND solubility parameter is described in the book "The Solubility of Non-electrolytes” by J.H. Hildebrand and R.L. Scott, Dover Publications, Inc., New York, 3th. ed. (1964) and in the book “Properties of Polymers” by D.W. Van Krevelen, 2nd. ed., Elseviers Scientific Publishing Company, New York, 1976, Chapter 7.
  • the resinous matrix of toner particles according to this invention contains a polymer LPC modified with compound D, a polymer B and a compound C, characterised in that :
  • ⁇ C is between 15 and 19 J 1/2 /cm 3/2 and ⁇ D between 15 and 18 J 1/2 /cm 3/2 , ⁇ LPC between 19 and 22 J 1/2 /cm 3/2 , and ⁇ B between 19 and 22 J 1/2 /cm 3/2 .
  • ⁇ C and ⁇ D are equal, in this document this means that they do not differ more than 2 J 1/2 /cm 3/2 .
  • the difference between the ⁇ 's is not larger than 6 units (6 J 1/2 /cm 3/2 ).
  • 6 units 6 J 1/2 /cm 3/2 .
  • a slight incompatibility (expressed by the difference in Hildebrand solubility factor being between 2 and 6 units) had a beneficial effect on the look of the image since a very pleasing satin look was obtained. This effect has been described in EP-A-656 129.
  • Said polymer chain LPC with a tg ⁇ > 3 at 120 °C and 100 rad/sec can be any polymer known in the art as long as it comprises at least one reactive end group.
  • Preferably said polymeric chain LPC is a linear polymeric chain. It can, e.g., be an addition polymer comprising a carboxyl group at the end, such as Co(Styrene/n-butylmethacrylate), diCOOH terminated (65/35), a polyester, an epoxy resin or a mixed polycondensate (block or random polymer) comprising polyester and polyamide moieties.
  • Linear mixed polycondensates comprising polyester and polyamide moieties, can be prepared by copolycondensation of at least one di-carboxylic acid, at least one diol, and at least one aliphatic diamine or aminocarboxylic acid or a lactam.
  • Said diamine, aminocarboxylic acid or lactam is present in the polycondensation mixture for at most 30 % mol for mol.
  • useful diamines, aminocarboxylic acids or lactam are e.g. hexamethylene diamine, pentamethylene diamine, tetramethylene diamine, 11-amino-undecanoic acid, ⁇ -caprolactam, etc.
  • Expoxy resins useful as polycondensation backbone in a complex macromolecule according to the present invention, are linear adduct of bis-phenol A and epichlorhydrin having a Tg of about 54 °C.
  • epoxy resins are linear adducts of bisphenol compounds and epichlorhydrin as described e.g. by D. H. Solomon in the book “The Chemistry of Organic Film Formers” - John Wiley & Sons, Inc., New York (1967) p. 180-181, e.g. EPIKOTE 1004 (EPIKOTE is a registered trade mark of the Shell Chemical Co).
  • the polymer chain LPC used to form polymer A after reaction with long chain aliphatic compound D, is a homo- or copolyester.
  • Said homo- or copolyesters (hereinafter termed polyester) can be produced by any known polycondensation reaction between at least one dicarboxylic acid and one diol.
  • the polyester, used according to this invention can comprise aromatic dicarboxylic acid moieties.
  • the polyester, used according to this invention can comprise aromatic dicarboxylic acid moieties.
  • aromatic dicarboxylic acid moieties are moieties of terephthalic acid, isophthalic acid, naphthalene dicarboxylic acids, 4,4' diphenylene dicarboxylic acid, 4,4'diphenylether dicarboxylic acid, 4,4' diphenylmethane dicarboxylic acid, 4,4' diphenylsulphodicarboxylic acid, 5-sulphoisophthalic acid, etc. and mixtures of these acid moieties.
  • Polyesters to be used as polymer chain LPC, according to the present invention, can also comprise aliphatic dicarboxylic acid moieties. It may comprise saturated aliphatic dicarboxylic acid moieties derived from, e.g., malonic acid, succinic acid, glutaric acid, adipic acid, etc. and/or unsaturated aliphatic carboxylic acid moieties derived from, e.g., maleic acid, fumaric acid, etc.
  • Polyesters useful as polymer chain LPC, according to the present invention, have a minimum Tg (glass transition temperature) of 45 °C. Any polyester resin having a Tg higher than 45 °C can be used.
  • Preferred polyester resins are linear polycondensation products of (i) difunctional organic acids, e.g. maleic acid, fumaric acid, terephthalic acid and isophthalic acid and (ii) difunctional alcohols such as ethylene glycol, triethylene glycol, an aromatic dihydroxy compound, preferably a bisphenol such as 2,2-bis(4-hydroxyphenyl)-propane called "bisphenol A" or an alkoxylated bisphenol, e.g. propoxylated bisphenol examples of which are given in US-P 4,331,755.
  • difunctional organic acids e.g. maleic acid, fumaric acid, terephthalic acid and isophthalic acid
  • difunctional alcohols such as ethylene glycol, triethylene glycol, an aromatic dihydroxy compound, preferably a bisphenol
  • ATLAC T500 which is a trade name of Atlas Chemical Industries Inc. Wilmington, Del. U.S.A.
  • ATLAC T500 is a linear polyester of fumaric acid and propoxylated bisphenol A, having a Tg of about 55°C, a T sp of 100 °C, an average numerical molecular weight (M n ) of 4,000 and a weight average molecular weight (M w ) of 12,000. This polymer is described in e.g. NL 71/16891.
  • DIACRON FC150 a trade name of Mitsubishi Rayon, Japan for a linear polyester resin produced by the polycondensation of terephthalic acid, propoxylated bisphenol A and ethylene glycol, having a T sp of 110 °C, an average numerical molecular weight (M n ) of 3,700 and a weight average molecular weight (M w ) of 12,000.
  • a further interesting linear polyester for use as linear polymer chain in this invention is a linear bisphenol A based saturated polyester sold under trade name ALMACRYL P-501 by Image Polymers Europe, having a Tg between 52 and 56 °C, a T sp of 95 °C, an average numerical molecular weight (M n ) of 3,500 and a weight average molecular weight (M w ) of 8,000.
  • linear polyesters are polycondensation products of terephthalic acid, isophthalic acid, di-ethoxylated Bisphenol A and ethylene glycol.
  • Said compound D for reacting with the reactive end group on the chain LPC in order to produce polymer A can be a long chain aliphatic compound or a polysiloxane.
  • an aliphatic long chain compound as compound D, it is preferred to use a compound corresponding to the general formula : wherein 0 ⁇ x ⁇ 12, 10 ⁇ y ⁇ 90 and R 1 is a member selected from the group consisting of -OH, -COOH, -COCl, -NH 2 , -NCO, -O-CH 2 -CHOH-CH 2 Cl, -COO-CH 2 -CHOH-CH 2 Cl and COOM (with M is alkali metal ion), R 2 is CH 3 or H, preferably H, and R 3 is either C 2 H 5 or CH 3 .
  • Examples of monofunctional, hydroxyl terminated polyolefinic polymers are polyolefinic monoalcohols, commercially available as UNILIN 425, UNILIN 550, UNILIN 700, (trade names of PETROLITE, 6910 East 14th street, TULSA, Oklahoma 74112, USA for polyolefinic alcohols with average molecular weight of 425, 700), or UNITHOX 720, a trade name for a hydroxyterminated, polyolefinicpolyoxyethylenic macromolecule, with average molecular weight of 875 of the same PETROLITE company.
  • a typical example of a monofunctional carboxyl terminated polyolefine is UNICID 700 a trade name of PETROLITE for a polyolefinic monocarboxylic acid with average molecular weight of 700.
  • Further experimental polyolefinic compounds, of PETROLITE, terminated by an hydroxyl group or a carboxyl group and having molecular weight between 1000 and 2500 can also be used.
  • a polymer A for use in toner particles according to this invention could very beneficially be made by reacting a polymeric chain LPC with two different compounds D, one compound having a molecular weight between 400 and 1000 and one compound having a molecular weight between 1500 and 2500.
  • a preferred combination of compounds D in this invention is the combination of a polyolefinic alcohol or polyolefinic carboxylic acid with molecular weight 700 or 1000 and a polyolefinic alcohol or polyolefinic carboxylic acid with molecular weight 2000.
  • Such polymers have been disclosed in, e.g., EP-A-712 881.
  • said compound D is a polysiloxane
  • it is preferably a polysiloxane it is preferred to use a polysiloxane corresponding to formula : wherein X' is Y' has the same meaning as X', or represents a lower (C1 to C4) alkyl group, Z' and Z", which may be the same or different, represent a lower (C1 to C4) alkyl group or an aryl group, 2 ⁇ m ⁇ 35, and 1 ⁇ n ⁇ 6.
  • Epoxy terminated polysiloxane derivatives are commercially available from Th. Goldschmid AG, Essen, Germany under trade names TEGOMER E-Si 2130 AND TEGOMER E-Si 2330.
  • the first method which is preferred for modifying the polymer LPC for use in toner particles according to this invention, is a method wherein a finished chain polymer with a reactive end group is mixed with an amount of at least one compound D and then reacted together.
  • at least one compound D is mixed with the reagents for forming the polymeric chain (LPC) so that in a single pot synthesis the polymer A, useful in toner particles of this invention is directly obtained.
  • the polymer B in the resinous matrix is branched or partially cross-linked polymer, it can e.g. be an addition polymer carrying free hydroxyl of carboxyl groups that has been partially cross-linked by reaction with a polyisocyanate. It can be a styrene, acrylate or methacrylate co-polymer comprising between 1 and 10 mol % of moieties derived from divinylbenzene, or ethyleneglycoldiacrylate or ethyleleneglycoldimethacrylate.
  • polymer B a branched polyester.
  • polycarboxylic acids as, e.g. trimellitic acid, etc. or polyhydroxy compounds, as, e.g., trimethylolpropane, glycerol, pentaerythritol, etc.
  • interesting branched polyesters are polyester produced by the polycondensation of DIANOL 22 (di-ethoxylated Bisphenol A), DIANOL 33 (di-propoxylated Bisphenol A), terephthalic acid and trimellitic acid .
  • DIANOL 22 and DIANOL 33 are trade names of AKZO CHEMIE of the Netherlands.
  • the polymer B is a branched polyester it comprises preferably between 1 and 10 mol percent of moieties derived from a polyfunctional monomer
  • the polymer B has preferably a tg ⁇ between 1 and 2.5, when measured at 120 °C and 100 rad/sec.
  • the polymer B, for use in toner particles of this invention has preferably a Tg larger than 45 °C, preferentially larger than 50 °C and a Hildebrand solubility parameter between 19 and 22 J 1/2 /cm 3/2 .
  • the compound C for use in this invention may include the following. It may include aliphatic hydrocarbon waxes such as low-molecular weight polyethylene, low molecular weight polypropylene, microcrystalline wax and paraffin wax, oxides of aliphatic hydrocarbon waxes such as polyethylene wax oxide, and block copolymers thereof; waxes mainly composed as a fatty acid ester, such as carnauba wax and montanic acid ester wax; and those obtained by deoxidising part or the whole of a fatty acid ester, such as deoxidised carnauba wax.
  • aliphatic hydrocarbon waxes such as low-molecular weight polyethylene, low molecular weight polypropylene, microcrystalline wax and paraffin wax, oxides of aliphatic hydrocarbon waxes such as polyethylene wax oxide, and block copolymers thereof
  • waxes mainly composed as a fatty acid ester such as carnauba wax and montanic acid ester wax
  • saturated straight-chain fatty acids such as palmitic acid, stearic acid and montanic acid
  • unsaturated fatty acids such as brassidic acid, oleostearic acid and patinatic acid
  • saturated alcohols such as stearyl alcohol, aralkyl alcohol, behenyl alcohol, carnaubyl alcohol, ceryl alcohol and melissyl alcohol
  • polyhydric alcohol such as sorbitol
  • fatty acid amides such as linoleic acid amide, oleic acid amide and lauric acid amide
  • saturated fatty acid bisamides such as methylenebisstearic acid amide, ethylenebiscapric acid amide, ethylenebislauric acid amide and hexamethylenebisstearic acid amide
  • unsaturated fatty acid amides such as ethylenebisoleic acid amide, hexamethylenebisoleic acid amide, N,N'-dioleyladipic acid amide and N,N'-d
  • Examples of compounds C, useful in the resinous matrix of toner particles according to this invention, are waxes commercially available under trade name MITSUI HI-WAX 100P, MITSUI HI-WAX 110P, MITSUI HI-WAX 1105A, MITSUI HI-WAX 1120H, etc., from Mitsui Petrochemical Industries, Ltd Japan or under trade name HOECHST-WACHS U, HOECHST-WACHS PE520, HOECHST-WACHS PE130, HOECHST-WACHS PED 121, etc., from Hoechts, Germany.
  • Compound C has preferably a molecular weight between 400 and 2,500, more preferably a molecular weight between 500 and 1,600.
  • polymer A, B and compound C i.e. several resinous matrices
  • polymer A and compound(s) C are present in a weight ratio between 1 and 10, more preferably between 2 and 5.
  • the compounds C are preferably present in the resinous matrix of this invention in an amount between 2 and 8 % weight for weight (wt/wt), more preferably in a amount between 4 and 6 % wt/wt.
  • Toner particles according to this invention can be prepared by any method known in the art, but it is preferred to produced the toner particles according to this invention by a melt kneading process at a temperature that is higher than the melting point M p compound C that is used. When more than one compound C is used the melt kneading proceeds preferably at a temperature higher than the highest melting point of the compounds C.
  • the present invention also encompasses a method for producing dry toner particles comprising the steps of :
  • the present invention comprises also a method for producing dry toner particles comprising the steps of :
  • Toner particles comprising a resinous matrix, according to the present invention, can comprise any normal toner ingredient e.g. charge control agents, pigments both coloured and black, inorganic fillers, fine magnetic material, etc..
  • charge control agents e.g. charge control agents, pigments both coloured and black, inorganic fillers, fine magnetic material, etc.
  • a description a charge control agents, pigments and other additives useful in toner particles, can be found in e.g. EP A 601 235.
  • Toner particles comprising a resinous matrix, according to the present invention, when used in a multicomponent dry developer can be mixed with any known carrier material.
  • Suitable carrier particles are carrier particles as disclosed in, e.g., EP-A-289 663; EP-A-559 250; EP-A-656 130 and European Application 97202551 filed on August 20, 1997.
  • Known fluidity enhancers as e.g. hydrophobized silica, can be mixed with said toner particles.
  • the toner particles can be used as a monocomponent dry developer (both magnetic and nonmagnetic) or mixed with carrier particles to form a multi component developer.
  • Toner particles comprising a resinous matrix, according to the present invention, can have an average volume diameter between 1 and 50 ⁇ m, preferably between 3 and 20 ⁇ m and more preferably between 3 and 10 ⁇ m.
  • the particle size distribution of said toner particles can be of any type. It is however preferred to have a Gaussian or normal particle size distribution, either by number or volume, with a coefficient of variability (standard deviation divided by the average) (v) smaller than 0.5, more preferably of 0.3.
  • the toner particles can have any shape, the particles can irregular, rounded, etc.
  • Toner particles according to this invention are especially useful for use in electrostatographic or magnetographic imaging methods wherein the fixing proceeds in a "contact fusing" station and wherein a very low amount of external release agent is applied to the heated rollers of the fusing station to prevent hot-offset.
  • the toner particles of this invention are used in an imaging method using dry toner particles comprising the steps of :
  • the amount of release agent is preferably applied to the heated rollers by a supply roller with a surface in NOMEX-felt (NOMEX is a trade name of Du Pont de Nemours, Wilmington, US) as described in article titled "Innovative Release Agent Delivery Systems" by R. Bucher et al. in The proceedings of IS&T's Eleventh International Congress on Advances in Non-Impact Printing Technologies, page 219 - 222. This congress was held in Hilton Head, from 29.10.95 to 03.11.95. The proceedings are published by IS&T, Springfield, US 1995.
  • NOMEX-felt NOMEX is a trade name of Du Pont de Nemours, Wilmington, US
  • NO external release agent means for the purposes of this document less than 1 mg/m 2
  • the heated rollers can be made from any material known in the art, but can preferably be heated rollers with a surface comprising compounds selected from the group consisting of compounds containing Si-atoms and compounds containing F-atoms. Rollers having a surface with both compounds containing Si-atoms and compounds containing F-atoms at the surface and rollers comprising compounds with F-atoms at the surface but not compounds with Si-atoms are very well suited for fixing toner particles according to this invention.
  • wt/wt polymer chain
  • LPC polymer chain
  • UNILIN700 a monofunctional polyolefinic molecule, consisting of -CH 2 -CH 2 - groups terminated at one side with a -CH 3 group and at the other by a HO-group, having an average molecular weight of 700 and a Hildebrand value of 17 J 1/2 /cm 3/2
  • LPC polymer chain
  • A bis-propoxylated 2,2-bis(4-hydroxyphenyl)propane
  • B bis-ethoxylated 2,2-bis(4-hydroxyphenyl)propane
  • C terephthalic acid
  • D trimellitic acid
  • A/B 70 mol %/30 mol %
  • C/D 60 mol %/40 mol %
  • A+B/C+D 100 mol %/70 mol %.
  • UNILIN700 a monofunctional polyolefinic molecule, consisting of -CH 2 -CH 2 - groups terminated at one side with
  • the mixture was melt homogenised at 130 °C, cooled and pulverised, classified to give cyan toner particles volume average diameter d v50 8.5 ⁇ m, as determined by COULTER COUNTER (trade name), and numerical average diameter d n50 of 6.3 ⁇ m.
  • the mixture was melt homogenised at 130 °C, cooled and pulverised, classified to give cyan toner particles volume average diameter d v50 8.5 ⁇ m, as determined by COULTER COUNTER (trade name), and numerical average diameter d n50 of 6.3 ⁇ m.
  • a developer was prepared by adding 0.5 % (wt/wt) of AEROSIL R972 5 (trade name of Degussa, Germany) for hydrophobic silica and mixing 5 % wt/wt of this toner particles and silica mixture with silicone-coated ferrite carrier particles with average volume particle diameter dv50 of 50 ⁇ m
  • the developers were used to produce images on a paper substrate in the XC305 colour copier (trade name of Agfa-Gevaert N.V, Mortsel, Belgium).
  • the images contained 1 mg of toner per cm2.
  • the images were fixed in four different "contact fusing" stations A to D, comprising heated rollers.
  • the fusing device of said XC305 colour copier was used with certain modifications.
  • the fusing station of this apparatus comprises a dual silicone coated roller pair, showing a typical 5-6 mm contact zone.
  • the temperature setting was made changeable in the range of 160-175 °C, so as to make it a variable parameter in the examples. In all examples the fusing proceeded under the conditions of speed and pressure of the standard design of the apparatus.
  • the standard oiling device supplying normally between 40-80 mg silicone oil per copy on a DIN A4 page, (i.e. 640 to 1,280 mg/m 2 , all scraping devices and the cleaning web were taken out of the fusing station.
  • the heated rollers were rollers with a silicone surface and with lifetime of 5,000 copies. In this fusing station, contact fusing proceeded without having an external release agent on the heated rollers.
  • fusing station A The same set-up as for fusing station A was used, except that heated rollers with a lifetime of 50,000 copies were used. Also in this fusing station, contact fusing proceeded without having an external release agent on the heated rollers.
  • fusing station B The same set-up as for fusing station B was used, except for the fact that on the heated rollers a small amount of external release agent (silicone oil) was applied to the heated rollers.
  • the amount of silicone oil to be delivered to the heated rollers was adjusted so as to bring 1.6 mg of silicone oil per m 2 on the image. This is 40 to 80 times less than what is usual.
  • the silicone oil was applied to the heated rollers by supply rollers with a surface in NOMEX-felt (NOMEX is a trade name of Du Pont de Nemours, Wilmington, US) as described in article titled "Innovative Release Agent Delivery Systems" by R. Bucher et al.
  • rollers with a pure silicone surface rollers with a silicone, polyflouraacrylate surface were used. These rollers are very resistance to scratching and have a lifetime of about 500,000 copies. The rollers have however a higher surface energy and can more easily than rollers with silicone surface induce hot-offset.
  • the fixing window was determined. First the fixing temperature at which the fixing was adequate was noted as T1. This was done by printing an image with the various toners, fixing the images at differrent temperatures and assesing the fixing quality reached by evaluating them on four topics :
  • the evaluation proceeded for each of the topics on a scale from 4 to 1, with 4 very good, 3 good, 2 marginal and 1 unacceptable.
  • the fixing was taken to be adequate when the image got at least a marking 3 for each of the topics above.
  • the fixing temperature of that image was taken as temperature T1.
  • toner particles TON1 and TON2 toner particles according to this invention give the best results : the widest fixing window and the best image quality.
  • Toner particles TON3 equal to toner particles TON1, except for the fact that the polymeric chain LPC was not modified by a compound D, and thus non-invention toner particles, gave a less wide fixing window.

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  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Developing Agents For Electrophotography (AREA)

Claims (19)

  1. Particules sèches de toner comprenant une matrice résineuse et une cire, caractérisées en ce que
       ladite matrice résineuse contient un mélange de
       un polymère (LPC) ayant un poids moléculaire moyen en poids (Mw) compris entre 2 000 et 20 000, une tgδ > 3 à 120 °C et 100 rad/sec et un point de ramollissement faible TsLPC tel que 90 °C ≤ TsLPC ≤ 120 °C, modifié par un agent modifiant (D) choisi dans le groupe constitué de composés aliphatiques à chaíne longue ayant un groupe terminal réactif et ayant entre 20 et 250 atomes de carbone et un polysiloxane pour former un polymère A, ledit agent modifiant et ledit polymère étant présents dans un rapport molaire LPC/D compris entre 0,8 et 1,25 et
       un polymère non linéaire ayant un point de ramollissement TsB tel que 110 °C ≤ TsB ≤ 135 °C constituant au moins 25% en poids de ladite matrice résineuse, et
       ladite cire a un point de fusion Mp tel que 85 °C ≤ Mp ≤ 135 °C et Mp ≤ TsB + 10.
  2. Particules sèches de toner selon la revendication 1, dans lesquelles ladite matrice résineuse contient au moins 50% en poids dudit mélange dudit polymère LPC modifié par ledit composé D et dudit polymère B non linéaire.
  3. Particules sèches de toner selon la revendication 1, dans lesquelles ladite matrice résineuse consiste en ledit mélange dudit polymère LPC modifié par ledit composé D et dudit polymère B non linéaire.
  4. Particules sèches de toner selon l'une quelconque des revendications 1 à 3, dans lesquelles
       ledit polymère B a en outre une perte viscoélastique tgδ telle que 1,0 ≤ tgδ ≤ 2,5 mesurée à 120 °C et à 100 rad/sec,
       ladite cire a en outre un point de ramollissement TsC tel que TsC ≤ TsB + 20 °C, et un paramètre de solubilité d'Hildebrand δC tel que 15 J1/2/cm3/2 ≤ δC ≤ 19 J1/2/cm3/2
    et dans lesquelles
       ledit polymère B, ledit LPC linéaire à chaíne polymère et lesdits composés C et D ont un paramètre de solubilité d'Hildebrand δC tel que δC = δD ≤ δLPC = δB.
  5. Particules sèches de toner selon l'une quelconque des revendications 1 à 4, dans lesquelles ladite chaíne polymère longue, LPC, représente un polyester linéaire.
  6. Particules de toner sèches selon l'une quelconque des revendications 1 à 5, dans lesquelles ledit composé D à chaíne longue représente un composé aliphatique à chaíne longue ayant la formule :
    Figure 00360001
    dans laquelle 0 ≤ x ≤ 12, 10 ≤ y ≤ 90
    et R1 représente un membre choisi dans le groupe constitué de -OH, -COOH, -COCl, -NH2,
    Figure 00360002
    -NCO,
    -O-CH2-CHOH-CH2Cl, -COO-CH2-CHOH-CH2Cl et COOM, R2 est choisi dans le groupe constitué de CH3 et H, et R3 est choisi dans le groupe constitué de C2H5 et CH3.
  7. Particules sèches de toner selon l'une quelconque des revendications 1 à 5, dans lesquelles ledit composé D à chaíne longue représente un polysiloxane ayant la formule :
    Figure 00370001
    dans laquelle
    X' représente
    Figure 00370002
    Y' a la même signification que X', ou représente un groupe alkyle en (C1 à C4) inférieur,
    Z' et Z", qui peuvent être identiques ou différents, représentent un groupe alkyle en (C1 à C4) inférieur ou un groupe aryle, 2 < m < 35, et 1 < n < 6.
  8. Particules sèches de toner selon la revendication 7, dans lesquelles Y' représente un groupe méthyle, n= 3 et m = 10.
  9. Particules sèches de toner selon l'une quelconque des revendications 1 à 8, dans lesquelles ledit polymère B représente un polyester réticulé comprenant entre 1 et 10% en mole de groupes dérivés d'un monomère choisi dans le groupe des acides tricarboxyliques et des composés trihydroxy.
  10. Particules sèches de toner selon l'une quelconque des revendications 1 à 8, dans lesquelles ledit polymère B représente un polymère d'addition ramifié.
  11. Particules sèches de toner selon la revendication 10, dans lesquelles ledit polymère B représente un polymère d'addition ramifié comprenant entre 1 et 10% en mole de groupes dérivés d'un monomère choisi dans le groupe constitué du divynilbenzène, du diacrylate d'éthylène glycol et du diméthacrylate d'éthylène glycol.
  12. Particules de toner sèches selon l'une quelconque des revendications précédentes, dans lesquelles ledit polymère A et ledit composé C sont présents dans un rapport en poids tel que 1 ≤ A/C ≤ 10.
  13. Particules de toner sèches selon l'une quelconque des revendications précédentes, dans lesquelles ledit polymère A et ledit composé C sont présents dans un rapport en poids tel que 2 ≤ A/C ≤ 5.
  14. Procédé d'imagerie utilisant des particules de toner sèches comprenant les étapes :
    d'application aux fins d'image desdites particules de toner à un substrat recevant l'image finale et
    de fixation desdites particules de toner audit substrat dans un site de fusion comprenant des cylindres chauffés ayant une surface,
    caractérisé en ce que
    lesdites particules de toner sont des particules de toner selon l'une quelconque des revendications 1 à 11 et
    sur ladite surface desdits cylindres chauffés un agent de libération externe est ajouté en une quantité telle qu'au plus 160 mg/m2 d'agent de libération est appliqué audit substrat recevant l'image finale.
  15. Procédé selon la revendication 14, dans lequel, sur ladite surface desdits cylindres chauffés, un agent de libération externe est ajouté en une quantité telle qu'au plus 40 mg/m2 d'agent de libération est appliqué audit substrat recevant l'image finale.
  16. Procédé selon la revendication 14, dans lequel, sur ladite surface desdits cylindres chauffés, un agent de libération externe est ajouté en une quantité telle qu'entre 1 et 10 mg/m2 d'agent de libération sont appliqués audit substrat recevant l'image finale.
  17. Procédé selon la revendication 14, dans lequel, sur ladite surface desdits cylindres chauffés, aucun agent de libération externe n'est appliqué.
  18. Procédé selon l'une quelconque des revendications 14 à 17, dans lequel lesdits cylindres chauffés ont une surface comprenant des atomes de F.
  19. Procédé selon la revendication 17, dans lequel ladite surface ne comprend aucun atome de Si.
EP19980203500 1997-10-31 1998-10-16 Particules de toner contenant un mélange d'un polymère linéaire modifié, un polymère réticulé et une cire Expired - Lifetime EP0913735B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP19980203500 EP0913735B1 (fr) 1997-10-31 1998-10-16 Particules de toner contenant un mélange d'un polymère linéaire modifié, un polymère réticulé et une cire

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EP97203377 1997-10-31
EP97203377 1997-10-31
EP19980203500 EP0913735B1 (fr) 1997-10-31 1998-10-16 Particules de toner contenant un mélange d'un polymère linéaire modifié, un polymère réticulé et une cire

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EP0913735A2 EP0913735A2 (fr) 1999-05-06
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EP0913735B1 true EP0913735B1 (fr) 2005-09-14

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Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030134219A1 (en) * 2000-02-18 2003-07-17 Serge Tavernier Toner composition and fixing method
GB0025200D0 (en) * 2000-10-13 2000-11-29 Xeikon Nv Toner composition

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0606873B1 (fr) * 1993-01-11 1998-10-07 Canon Kabushiki Kaisha Révélateur pour le développement d'images électrostatiques, révélateur du type à un composant et révélateur du type à deux composants
DE69426920T2 (de) * 1993-12-29 2001-08-09 Canon Kk Toner für die Entwicklung elektrostatischer Bilder und Hitzefixierungsverfahren
FR2720843B1 (fr) * 1994-06-03 1997-05-23 Tomoegawa Paper Co Ltd Toner pour développer des images de charges statiques, et procédé pour le préparer.
DE69534302T2 (de) * 1994-11-28 2006-04-27 Canon K.K. Toner für die Entwicklung elektrostatischer Bilder

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