EP0102025A2 - Dry electrostatographic toner and process for its preparation - Google Patents
Dry electrostatographic toner and process for its preparation Download PDFInfo
- Publication number
- EP0102025A2 EP0102025A2 EP83108097A EP83108097A EP0102025A2 EP 0102025 A2 EP0102025 A2 EP 0102025A2 EP 83108097 A EP83108097 A EP 83108097A EP 83108097 A EP83108097 A EP 83108097A EP 0102025 A2 EP0102025 A2 EP 0102025A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- weight
- parts
- toner
- dispersion
- pigment
- 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.)
- Granted
Links
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- 238000002360 preparation method Methods 0.000 title description 4
- 239000000725 suspension Substances 0.000 claims abstract description 31
- 239000002245 particle Substances 0.000 claims abstract description 29
- 239000000178 monomer Substances 0.000 claims abstract description 22
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- 238000012673 precipitation polymerization Methods 0.000 claims abstract description 6
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 claims abstract description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 4
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 4
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 3
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- 239000000126 substance Substances 0.000 claims description 13
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- 125000004432 carbon atom Chemical group C* 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 11
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- 229910052698 phosphorus Inorganic materials 0.000 claims description 7
- 239000011574 phosphorus Substances 0.000 claims description 7
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- SBPHGSQJPXQMGY-UHFFFAOYSA-M P(=O)(OC(C)CC)(OCCCCCCCC)[O-].[Zn+] Chemical group P(=O)(OC(C)CC)(OCCCCCCCC)[O-].[Zn+] SBPHGSQJPXQMGY-UHFFFAOYSA-M 0.000 claims description 5
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- 238000004519 manufacturing process Methods 0.000 claims description 5
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- RUMACXVDVNRZJZ-UHFFFAOYSA-N 2-methylpropyl 2-methylprop-2-enoate Chemical compound CC(C)COC(=O)C(C)=C RUMACXVDVNRZJZ-UHFFFAOYSA-N 0.000 claims description 3
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
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- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 2
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- 150000002432 hydroperoxides Chemical class 0.000 description 1
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 235000010187 litholrubine BK Nutrition 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- YLGYACDQVQQZSW-UHFFFAOYSA-N n,n-dimethylprop-2-enamide Chemical compound CN(C)C(=O)C=C YLGYACDQVQQZSW-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- HMZGPNHSPWNGEP-UHFFFAOYSA-N octadecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C(C)=C HMZGPNHSPWNGEP-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 229940055577 oleyl alcohol Drugs 0.000 description 1
- XMLQWXUVTXCDDL-UHFFFAOYSA-N oleyl alcohol Natural products CCCCCCC=CCCCCCCCCCCO XMLQWXUVTXCDDL-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical class OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000001007 phthalocyanine dye Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000196 poly(lauryl methacrylate) Polymers 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- FBCQUCJYYPMKRO-UHFFFAOYSA-N prop-2-enyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC=C FBCQUCJYYPMKRO-UHFFFAOYSA-N 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- RGBXDEHYFWDBKD-UHFFFAOYSA-N propan-2-yl propan-2-yloxy carbonate Chemical compound CC(C)OOC(=O)OC(C)C RGBXDEHYFWDBKD-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical class [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 239000001016 thiazine dye Substances 0.000 description 1
- ANRHNWWPFJCPAZ-UHFFFAOYSA-M thionine Chemical compound [Cl-].C1=CC(N)=CC2=[S+]C3=CC(N)=CC=C3N=C21 ANRHNWWPFJCPAZ-UHFFFAOYSA-M 0.000 description 1
- AAAQKTZKLRYKHR-UHFFFAOYSA-N triphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 AAAQKTZKLRYKHR-UHFFFAOYSA-N 0.000 description 1
- 230000007306 turnover Effects 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 0.000 description 1
- 239000001018 xanthene dye Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 150000003738 xylenes Chemical class 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
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
Definitions
- the invention relates to an electrostatographic suspension developer, based on pigment particles coated with crosslinked precipitation polymer, and to a method for producing the developer.
- Dry and wet development methods are known for developing electrostatic images on electrostatographic recording materials.
- the wet development processes are superior to the dry development processes with regard to edge sharpness and resolving power, especially in color copying processes.
- the known electrostatographic suspension developers are generally prepared by pigment particles together with soluble polymer and in a highly insulating carrier liquid a charge-determining substance, also called a control substance.
- the polymer is absorbed by the pigment particles, producing what is known as a toner, and gives the pigment dispersion formed (usually referred to as a toner dispersion) a certain stability.
- Such liquid developers have been widely used in electrostatographic processes. However, they have a number of disadvantages.
- the presence of non-adsorbed polymer in the carrier liquid is particularly disadvantageous, the proportion of which is increased when the used toner is replaced by the addition of developer concentrate when the toner dispersion is used for image development.
- the enrichment of the dissolved polymer then leads to changes in the electrostatographic properties of the developer and thus to a deterioration in quality.
- This disadvantage is linked to the existing adsorption-desorption equilibrium and is therefore unavoidable when using soluble polymer.
- DE-A 2 157 143 describes a process for the preparation of an electrostatographic suspension developer by graft polymerization of acrylic ester monomers Pigment known.
- graft polymerization reactions have the disadvantage that, in addition to the graft polymerization, there is also an "ordinary" homopolymerization or copolymerization and in this way, in addition to the desired grafting product, homopolymer or copolymer which is not anchored to the pigment is formed.
- Elaborate separation processes are necessary to display the graft product.
- a further difficulty is that the grafting yield depends to a large extent on the type of the grafting substrate, which makes it difficult to provide similar, differently colored suspension developers for color copying processes.
- DE-B 1 933 362 describes the shell-like coating of pigments with polymers.
- An inner insoluble polymer shell and an outer shell swellable in the carrier liquid are applied to the pigment.
- the polymers used are uncrosslinked. They are produced in the absence of the pigment by bulk polymerization and applied to the pigment as a solution (e.g. in toluene) or as a melt.
- the particle size is adjusted by grinding in a ball mill.
- a disadvantage of this process is that relatively coarse toner particles (approx. 0.09 mm) which limit the resolving power are obtained.
- DE-A 2 026 390 describes the production of toner particles by polymerizing synthetic resin monomers and coloring materials by the process known as suspension polymerization.
- the polymer particles obtained in this way are primarily suitable for use as dry developers due to their particle size and other properties.
- GB-A 868 974 describes a liquid electrostatographic developer containing toner particles which are precoated with a polymer of an acrylic or methacrylic acid ester of hydrogenated abietyl alcohol.
- the polymer is prepared separately or synthesized in the presence of the pigment by a bulk polymerization process.
- the T eilchen Anlagennspektrum Developer is relatively wide, which becomes disturbing when playing the tonal values.
- the invention is based on the object includes an electrostatographic suspension developer which finely divided polymer-coated pigment particles having an improved storage stability and can be used with advantage for arbkopierphal F to provide.
- Another object of the invention is a method for producing an electrostatographic suspension developer by precipitation polymerization in a carrier liquid as defined above in the presence of the pigment.
- the precipitation polymer formed according to the invention is firmly anchored on the pigment surface and has the fine structure typical of precipitation polymers, which can be made visible, for example, by scanning electron microscope images.
- the suspension developers according to the invention have excellent dispersion stability, which does not change during use and storage.
- the method for preparing the suspension developer according to the invention has the advantage over the previously used method has the advantage that the operations to be carried out separately: Polymerisather too, P igmentumhüllung, milling and dispersion are reduced in number and are combined into a single operation.
- a pigment dispersion in an electrically insulating liquid suitable as a carrier liquid is assumed.
- the pigments used in the customary electrostatographic suspension developers are suitable as pigment particles. These include e.g. Azo dyes, xanthene dye, phthalocyanine dyes, such as DE-A 2 944 021 describes triphenylmethane dyes, acridine dyes, quinoline dyes, quinonimine dyes, thiazine dyes or azine dyes.
- Spirit black C.I. No. 50415), aniline black (C.I. No. 50440), cyanine blue (C.I. No. 74250), brilliant carmine 6 B (C.I. 15850), real red (C.I. No.
- Carbon black C.I. No. 77266
- Helio real blue HG C.I. No. 74160
- Fanalrosa B C.I. No. 45160
- Helio real yellow GRN C.I. No. 21100
- Electrically insulating liquids with a volume resistance of at least 10 9 ohm'cm and a dielectric constant below 3, preferably based on hydrocarbons, are used as the liquid component or carrier liquid for the pigment dispersion, for example aromatic hydrocarbons such as benzene, toluene or xylenes or aliphatic C 6 -C 15 hydrocarbons such as n-hexane, cyclohexane, n-heptane, n-octane or decalin. Mixtures of different hydrocarbons can also be used. Branched aliphatic hydrocarbons such as isodecane and isododecane are particularly suitable.
- the proportion by weight of the pigment should be 0.5 to 50%, preferably 5-30%, based on the pigment dispersion.
- the pigment dispersion can be used without stabilizing additives. In many cases, however, it is advantageous to pre-stabilize the dispersion by adding small amounts (0.05-15% by weight, based on the pigment content) of a soluble polymer.
- Homopolymers or copolymers of (meth) acrylic acid esters are suitable for this purpose, for example a 1: 1 copolymer of isobutyl methacrylate and lauryl methacrylate.
- Copolymers with a proportion of 0.1-10% by weight of copolymerized monomers with -OH, -COOH, -NH 2 , -NHR, -NR 2 groups, such as 2-hydroxyethyl methacrylate, (meth) are also very suitable.
- acrylic acid (meth) acrylamide, NN-dimethylacrylamide, N, N-dimethylaminoethyl methacrylate and N-vinylpyrrolidone.
- the preferred molecular weight is in the range of 50,000 to 250,000.
- (Meth) acrylic acid esters (A) with 8-24 carbon atoms in the alcohol part are understood to mean the esters of acrylic acid or methacrylic acid and straight-chain and branched C 8 -C 24 alkanes, examples being: 2-ethylhexyl methacrylate, decyl methacrylate, dodecyl methacrylate, Lauryl methacrylate and stearyl methacrylate.
- Crosslinkers (B) are e.g. polyfunctional (meth) acrylates, such as ethylene di (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, glycerol trimethacrylate and trimethylolpropane trimethacrylate, but also divinylbenzene and allyl methacrylate are suitable.
- polyfunctional (meth) acrylates such as ethylene di (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, glycerol trimethacrylate and trimethylolpropane trimethacrylate, but also divinylbenzene and allyl methacrylate are suitable.
- (meth) acrylic acid esters with 1-7 C atoms in the alcohol part are suitable as component (C).
- Compounds suitable as component (D) are, for example, hydroxy and (optionally N-alkyl-substituted) aminoalkyl methacrylates such as 2-hydroxyethyl methacrylate or N, N-dimethylaminoethyl methacrylate, further styrene, vinyl toluene, ⁇ -methylstyrene, maleic anhydride, vinyl acetate, allyl alcohol and vinyl pyrrolidone.
- the ratio of pigment to the total amount of monomers should be 3: 1 to 1:10, preferably 2: 1 to 1: 5.
- R adikal horrinsky, particularly peroxides and Azoverbinschreibgen are suitable.
- examples include: aliphatic azodicarboxylic acid derivatives such as azobisisobutyronitrile or azodicarboxylic acid esters, peroxides such as lauroyl peroxide, succinyl peroxide, dibenzoyl peroxide, p-chlorobenzoyl peroxide, ketone peroxides such as methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, tert-butyl peroxide, cyclohexanone peroxide, cyclohexanone peroxides, Mono-tert-butyl permaleinate, percarbonates such as dicyclohexyl and diisopropyl percarbonate, dialkyl peroxides such as di-tert-butyl peroxide,
- a combination of different starting components for example starting components with different decay temperatures, can also be used with advantage in many cases.
- polymerizable radical starters is advantageous if the release of decomposition products of the starter into the liquid phase is to be prevented.
- Suitable starting components of this type are, for example, dimethacryloyl peroxide and p, p'-divinylbenzoyl peroxide (US Pat. No. 2,593,399).
- the reaction temperature depends on the type of starting component used, it is generally in the range of 50-150 ° C.
- the polymerization reaction can be carried out either under normal pressure or under positive pressure. The use of negative pressure can be indicated as a degassing stage after the reaction has ended.
- the precipitation polymerization reaction can be carried out by a "batch process".
- the monomers and the starting component are added to the pigment dispersion all at once and the reaction is initiated by increasing the temperature. In this way, pigment particles with a largely uniform polymer shell are obtained.
- the monomers and the starting components are metered in during the polymerization.
- This embodiment opens up a number of technically very interesting possibilities. So you can ignore change and build in this way a cup-shaped Polymerisathülle as the monomer composition over the D osierzeitraum. It is possible, and in certain cases sensible, to first set the crosslinker content high and then to lower it during the metering period. With this procedure, a slightly crosslinked outer shell is obtained which is more swellable than the inner shell. Pigment particles constructed in this way are notable for high dispersion stability.
- (D) contains polar groups such as -OH, -NH 2 , -COOH, preferably at the start of the polymerization, and thus to polymerize these monomers in the vicinity of the pigment surface .
- the starting component is also advantageously metered in over the reaction period.
- Solid starting components are expediently dissolved in solvents or monomers.
- the pigment dispersion is mixed by shaking or stirring, including that
- the turnover should therefore be at least 80%. It can be influenced in a known manner by the reaction time, the reaction temperature and the concentration of the starting component.
- the coated pigment particles have an average particle size of 0.2 to 2 ⁇ m.
- the dispersion obtained by precipitation polymerization according to the present process can be diluted to the desired working concentration, for example to 0.01% to 1%, by adding further carrier liquid. On this occasion, if desired, the present carrier liquid can be exchanged for another.
- the organic group preferably contains a chain of at least 4 carbon atoms, in particular 10 to 18 carbon atoms, and it can also be substituted and / or interrupted by one or more heteroatoms, e.g. through oxygen, sulfur or nitrogen.
- the solubility of the metal salts described in the electrically insulating carrier liquid can be determined by one or more organic groups of branched structure, e.g. are promoted by branched aliphatic groups such as a 2-butyloctyl group.
- Suitable positive charge control agents contain a metal alkyl sulfonate in which the metal ion is one of the divalent metal ions zinc (II), lead (II), cadmium (II) or copper (II) or a trivalent metal ion from group VIII of the periodic table, for example iron (III), or from the group VIB, for example chromium (III), and in which the sulfonate group is present directly on a straight-chain alkyl chain with at least 6 carbon atoms.
- the metal ion is one of the divalent metal ions zinc (II), lead (II), cadmium (II) or copper (II) or a trivalent metal ion from group VIII of the periodic table, for example iron (III), or from the group VIB, for example chromium (III), and in which the sulfonate group is present directly on a straight-chain alkyl chain with at least 6 carbon atoms.
- control substance is either added to the concentrate of the suspension developer or when the developer is diluted to the desired working concentration.
- the cheapest amount can easily be determined by simple experiments.
- Zinc mono (2-butyl) octyl phosphate is preferred as the control substance.
- fixatives are incorporated into the finished developer.
- Suitable fixing substances are resins which are said to be compatible with the binding material of the photoconductive recording material, e.g. with the binder of a photoconductive zinc oxide layer, so that good adhesion of the generated image to the base is obtained after development.
- Suitable resins are esters of hydrogenated rosin and fatty oil varnish ("long-oil"), rosin-modified phenol-formaldehyde resin, pentaerythritol esters of rosin, glycerol esters of hydrogenated rosin, ethyl cellulose, various alkyd resins, polyacrylic and polymethacrylic resin, polystyrene, poly (vinyl acetate), poly (vinyl acetate). Specific examples of such resins can be found in the literature on electrostatographic suspension developers, e.g. in BE-A 699 157 and in GB-A 1 151 141.
- a pigment dispersion prepared with the aid of a ball mill made of 30 g helio-real yellow GRN (CI 21100), 270 g isododecane and 0.3 g polylauryl methacrylate (MW 150000), was introduced and heated to 80 ° C.
- the dispersion was gassed with N 2 , stirred at 500 rpm, and 0.5 g of azoisobutyronitrile (AIBN) was added.
- AIBN azoisobutyronitrile
- the dispersion was diluted with isododecane to a solids content of 4% by weight and 12 mg of zinc mono- (2-butyl) octyl phosphate per gram of solid were added.
- the charge of the toner particles was stabilized after 24 hours of storage.
- the particle size was 0.8-1.2 pm.
- Example 2 A dispersion of 35 g of Helioechtblau HG (CI 74160) and 315 g of isododecane was placed in the apparatus described in Example 1. The dispersion was stirred at 60 ° C. at 600 rpm added continuously over a period of 60 minutes. The temperature was then kept at 70 ° C. for 1 hour and, after addition of 0.88 g of dibenzoyl peroxide, stirring was continued at 80 ° C. for 2 hours. A stable dispersion resulted.
- Example 1 of DE-A 2 157 143 50 g of the ester of methacrylic acid were reacted with oleyl alcohol, 50 g of finely ground Helio real yellow GRN (C.I. 21100) and 1 g of azobisisobutyronitrile in benzene.
- the reaction product was freed from soluble constituents by repeated pouring into methanol and poured into. dispersed the isoparaffinic solvent specified in said DE-A.
- the dispersion obtained showed insufficient stability for practical use.
- the toner particles tend to agglomerate and sediment.
- the developer delivers unclean images by depositing toner in the non-image areas.
- Example 1 of DE-B 1 933 362 Helioechtblau HG (C.I. 74160) was coated with 2 plastic layers.
- the granules obtained were ground in a ball mill to a particle size of -0.09 mm and dispersed in isododecane.
- the suspension obtained was suitable in principle for developing latent electrostatic images, but the resolution of the images achieved with the developer was inadequate and in particular inadequate for the reproduction of color images.
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Liquid Developers In Electrophotography (AREA)
Abstract
Der Suspensionsentwickler enthält in einer elektrisch isolierenden Trägerflüssigkeit 0,2 bis 2 µm große Tonerteilchen, die einen nach dem Verfahren der Fällungspolymerisation aus unterschiedlichen (Meth)acrylsäureestern, einem Vernetzer und gegebenenfalls einem Vinyl- oder Vinylidenmonomeren hergestellte Hülle aufweist.The suspension developer contains 0.2 to 2 μm large toner particles in an electrically insulating carrier liquid which has a shell produced by the method of precipitation polymerization from different (meth) acrylic acid esters, a crosslinking agent and optionally a vinyl or vinylidene monomer.
Description
Die Erfindung betrifft einen elektrostatographischen Suspensionsentwickler, auf der Basis von mit vernetztem Fällungspolymerisat umhüllten Pigmentteilchen, sowie ein Verfahren zur Herstellung des Entwicklers.The invention relates to an electrostatographic suspension developer, based on pigment particles coated with crosslinked precipitation polymer, and to a method for producing the developer.
Zum Entwickeln von elektrostatischen Bildern auf elektrostatographischen Aufzeichnungsmaterialien sind Trocken und Naßentwicklungsverfahren bekannt. Dabei sind die Naßentwicklungsverfahren den Trockenentwicklungsverfahren hinsichtlich Randschärfe und Auflösungsvermögen, insbesondere bei Farbkopieverfahren, überlegen.Dry and wet development methods are known for developing electrostatic images on electrostatographic recording materials. The wet development processes are superior to the dry development processes with regard to edge sharpness and resolving power, especially in color copying processes.
Die bekannten elektrostatographischen Suspensionsentwickler werden im allgemeinen dadurch hergestellt, daß man in einer hochisolierenden Trägerflüssigkeit Pigmentteilchen zusammen mit löslichem Polymerisat und einer ladungsbestimmenden Substanz, auch Steuerstoff genannt, dispergiert. Das Polymer wird hierbei von den Pigmentteilchen absorbiert, wobei ein sogenannter Toner entsteht, und verleiht der gebildeten Pigmentdispersion (üblicherweise als Tonerdispersion bezeichnet) eine gewisse Stabilität. Derartige Flüssigentwickler haben bei elektrostatographischen Verfahren breite Anwendung gefunden. Sie weisen allerdings eine Reihe von Nachteilen auf.The known electrostatographic suspension developers are generally prepared by pigment particles together with soluble polymer and in a highly insulating carrier liquid a charge-determining substance, also called a control substance. The polymer is absorbed by the pigment particles, producing what is known as a toner, and gives the pigment dispersion formed (usually referred to as a toner dispersion) a certain stability. Such liquid developers have been widely used in electrostatographic processes. However, they have a number of disadvantages.
Besonders nachteilig ist die Anwesenheit von nicht adsorbiertem Polymerisat in der Trägerflüssigkeit, dessen Anteil gesteigert wird, wenn beim Einsatz der Tonerdispersion zur Bildentwicklung der verbrauchte Toner durch Zugabe von Entwicklerkonzentrat ersetzt wird. Die Anreicherung des gelösten Polymerisates führt dann zu Veränderungen der elektrostatographischen Eigenschaften des Entwicklers und damit zur Qualitätsverschlechterung. Dieser Nachteil ist an das bestehende Adsorptions-Desorptions-Gleichgewicht gebunden und daher bei der Verwendung von löslichem Polymerisat nicht vermeidbar.The presence of non-adsorbed polymer in the carrier liquid is particularly disadvantageous, the proportion of which is increased when the used toner is replaced by the addition of developer concentrate when the toner dispersion is used for image development. The enrichment of the dissolved polymer then leads to changes in the electrostatographic properties of the developer and thus to a deterioration in quality. This disadvantage is linked to the existing adsorption-desorption equilibrium and is therefore unavoidable when using soluble polymer.
Es ist versucht worden, durch die Knüpfung chemischer Bindungen eine feste Verankerung des Polymerisates an der Pigmentoberfläche zu erzielen. So ist aus der DE-A 2 157 143 ein Verfahren zur Herstellung eines elektrostatographischen Suspensionsentwicklers durch Pfropfpolymerisation von Acrylestermonomeren auf ein Pigment bekannt. Pfropfpolymerisationsreaktionen haben jedoch den Nachteil, daß neben der Pfropfpolymerisation auch eine "gewöhnliche" Homo- bzw. Copolymerisation stattfindet und auf diese Weise neben dem gewünschten Pfropfprodukt nicht am Pigment verankertes Homo- bzw. Copolymerisat gebildet wird. Zur Reindarstellung des Pfropfproduktes sind aufwendige Trennverfahren notwendig. Eine weitere Schwierigkeit besteht darin, daß die Pfropfausbeute im hohen Maße von der Art des Pfropfsubstrates abhängt, was die Bereitstellung gleichartiger, verschiedenfarbiger Suspensionsentwickler für Farbkopierverfahren erschwert.Attempts have been made to firmly anchor the polymer to the pigment surface by forming chemical bonds. DE-A 2 157 143 describes a process for the preparation of an electrostatographic suspension developer by graft polymerization of acrylic ester monomers Pigment known. However, graft polymerization reactions have the disadvantage that, in addition to the graft polymerization, there is also an "ordinary" homopolymerization or copolymerization and in this way, in addition to the desired grafting product, homopolymer or copolymer which is not anchored to the pigment is formed. Elaborate separation processes are necessary to display the graft product. A further difficulty is that the grafting yield depends to a large extent on the type of the grafting substrate, which makes it difficult to provide similar, differently colored suspension developers for color copying processes.
In der DE-B 1 933 362 wird die schalenartige Beschichtung von Pigmenten mit Polymerisaten beschrieben. Dabei wird eine innere unlösliche Polymerhülle und eine äußere in der Trägerflüssigkeit quellbare Hülle auf das Pigment aufgebracht. Die verwendeten Polymerisate sind unvernetzt. Sie werden in Abwesenheit des Pigmentes durch Massepolymerisation erzeugt und als Lösung (z.B. in Toluol) oder als Schmelze auf das Pigment aufgebracht. Die Einstellung der Teilchengröße erfolgt durch Mahlen in der Kugelmühle. Nachteilig bei diesem Verfahren ist, daß relativ grobe Tonerteilchen (ca. 0,09 mm), die das Auflösungsvermögen begrenzen, erhalten werden.DE-B 1 933 362 describes the shell-like coating of pigments with polymers. An inner insoluble polymer shell and an outer shell swellable in the carrier liquid are applied to the pigment. The polymers used are uncrosslinked. They are produced in the absence of the pigment by bulk polymerization and applied to the pigment as a solution (e.g. in toluene) or as a melt. The particle size is adjusted by grinding in a ball mill. A disadvantage of this process is that relatively coarse toner particles (approx. 0.09 mm) which limit the resolving power are obtained.
Aus der DE-A 2 026 390 ist die Herstellung von Tonerpartikeln durch Polymerisation von synthetischen Harzmonomeren und färbenden Materialien nach der Verfahrensweise der Suspensionspolymerisation bekannt. Die dabei erhaltenen Polymerteilchen sind aufgrund ihrer Teilchengröße und sonstigen Eigenschaften in erster Linie für die Verwendung als Trockenentwickler geeignet.DE-A 2 026 390 describes the production of toner particles by polymerizing synthetic resin monomers and coloring materials by the process known as suspension polymerization. The polymer particles obtained in this way are primarily suitable for use as dry developers due to their particle size and other properties.
In der GB-A 868 974 wird ein flüssiger elektrostatographischer Entwickler, enthaltend Tonerteilchen, die mit einem Polymeren eines Acryl- oder Methacrylsäureesters von hydriertem Abietylalkohol vorbeschichtet sind, beschrieben. Das Polymerisat wird getrennt hergestellt oder in Anwesenheit des Pigmentes nach einem Massepolymerisationsverfahren synthetisiert. Das Teilchengrößenspektrum des Entwicklers ist relativ breit, was sich bei der Wiedergabe der Tonwerte störend bemerkbar macht.GB-A 868 974 describes a liquid electrostatographic developer containing toner particles which are precoated with a polymer of an acrylic or methacrylic acid ester of hydrogenated abietyl alcohol. The polymer is prepared separately or synthesized in the presence of the pigment by a bulk polymerization process. The T eilchengrößenspektrum Developer is relatively wide, which becomes disturbing when playing the tonal values.
Der Erfindung liegt die Aufgabe zugrunde, einen elektrostatographischen Suspensionsentwickler, der feinteilige polymerumhüllte Pigmentteilchen enthält, eine verbesserte Lagerstabilität aufweist und mit Vorteil für Farbkopierverfahren verwendet werden kann, bereitzustellen.The invention is based on the object includes an electrostatographic suspension developer which finely divided polymer-coated pigment particles having an improved storage stability and can be used with advantage for arbkopierverfahren F to provide.
Die Aufgabe wird erfindungsgemäß durch einen elektrostatographischen Suspensionsentwickler gelöst, der in einer elektrisch isolierenden Trägerflüssigkeit mit einem Volumenwiderstand von mindestens 109 Ohm'cm und einer Dielektrizitätskonstanten unter 3 polymerumhüllte Pigmentteilchen als Toner suspendiert, sowie gegebenenfalls einen Steuerstoff gelöst enthält, und der dadurch gekennzeichnet ist, daß der Toner eine Teilchengröße von 0,2 bis 2 µm und eine Hülle aus einem vernetzten Fällungspolymerisat hat, das aus
- (A) mindestens 25 Gew.-Teilen eines (Meth)acrylsäureesters mit 8-24 C-Atomen im Alkoholteil,
- (B) 2-50 Gew.-Teilen eines Vernetzers,
- (C) 2-50 Gew.-Teilen eines (Meth)acrylsäureesters mit 1-7 C-Atomen im Alkoholteil und
- (D) 0-25 Gew.-Teilen eines Vinyl- oder Vinylidenmonomeren, das mit (A) und (C) copolymerisierbar und von (A) und (C) verschieden ist,
- ( A ) at least 25 parts by weight of a (meth) acrylic acid ester with 8-24 C atoms in the alcohol part,
- (B) 2-50 parts by weight of a crosslinking agent,
- ( C ) 2-50 parts by weight of a (meth) acrylic acid ester with 1-7 C atoms in the alcohol part and
- ( D ) 0-25 parts by weight of a vinyl or vinylidene monomer which is copolymerizable with (A) and (C) and different from (A) and (C),
Ein weiterer Gegenstand der Erfindung ist ein Verfahren zur Herstellung eines elektrostatographischen Suspensionsentwicklers durch Fällungspolymerisation in einer wie oben definierten Trägerflüssigkeit in Anwesenheit des Pigmentes.Another object of the invention is a method for producing an electrostatographic suspension developer by precipitation polymerization in a carrier liquid as defined above in the presence of the pigment.
Das erfindungsgemäß gebildete Fällungspolymerisat ist fest auf der Pigmentoberfläche verankert und weist die für Fällungspolymerisate typische Feinstruktur auf, die beispielsweise durch Rasterelektronenmikroskopische Aufnahmen sichtbar gemacht werden kann.The precipitation polymer formed according to the invention is firmly anchored on the pigment surface and has the fine structure typical of precipitation polymers, which can be made visible, for example, by scanning electron microscope images.
Die erfindungsgemäßen Suspensionsentwickler besitzen eine hervorragende Dispersionsstabilität, die sich beim Gebrauch und bei Lagerung nicht verändert.The suspension developers according to the invention have excellent dispersion stability, which does not change during use and storage.
Das Verfahren zur Herstellung der erfindungsgemäßen Suspensionsentwickler hat gegenüber den bisher üblichen Verfahren den Vorteil, daß die getrennt durchzuführenden Arbeitsgänge: Polymerisatherstellung, Pigmentumhüllung, Mahlen und Dispergieren zahlenmäßig reduziert und in einen Arbeitsgang zusammengefaßt werden.The method for preparing the suspension developer according to the invention has the advantage over the previously used method has the advantage that the operations to be carried out separately: Polymerisatherstellung, P igmentumhüllung, milling and dispersion are reduced in number and are combined into a single operation.
Bei der Herstellung der erfindungsgemäßen Suspensionsentwickler geht man von einer Pigmentdispersion in einer als Trägerflüssigkeit geeigneten elektrisch isolierenden Flüssigkeit aus. Als Pigmentteilchen eignen sich die in den üblichen elektrostatographischen Suspensionsentwicklern verwendeten Pigmente. Dazu gehören z.B. Azofarbstoffe, Xanthenfarbstoff, Phthalocyaninfarbstoffe, wie sie u.a. in der DE-A 2 944 021 beschrieben werden, Triphenylmethanfarbstoffe, Acridinfarbstoffe, Chinolinfarbstoffe, Chinoniminfarbstoffe, Thiazinfarbstoffe oder Azinfarbstoffe. Gut geeignet sind beispielsweise Spiritschwarz (C.I. Nr. 50415), Anilinschwarz (C.I. Nr. 50440), Cyaninblau (C.I. Nr. 74250), Brillant Carmine 6 B (C.I. 15850), Echtrot (C.I. Nr.In the preparation of the suspension developers according to the invention, a pigment dispersion in an electrically insulating liquid suitable as a carrier liquid is assumed. The pigments used in the customary electrostatographic suspension developers are suitable as pigment particles. These include e.g. Azo dyes, xanthene dye, phthalocyanine dyes, such as DE-A 2 944 021 describes triphenylmethane dyes, acridine dyes, quinoline dyes, quinonimine dyes, thiazine dyes or azine dyes. Spirit black (C.I. No. 50415), aniline black (C.I. No. 50440), cyanine blue (C.I. No. 74250), brilliant carmine 6 B (C.I. 15850), real red (C.I. No.
15865), Benzidinorange (C.I. Nr. 21110) oder Permanentgelb GR 52 (C.I. 21100). Besonders bevorzugt sind Ruß (C.I. Nr. 77266), Helioechtblau HG (C.I. Nr. 74160), Fanalrosa B (C.I. Nr. 45160) und Helioechtgelb GRN (C.I. Nr. 21100)15865), benzidine orange (C.I. No. 21110) or permanent yellow GR 52 (C.I. 21100). Carbon black (C.I. No. 77266), Helio real blue HG (C.I. No. 74160), Fanalrosa B (C.I. No. 45160) and Helio real yellow GRN (C.I. No. 21100) are particularly preferred.
Als flüssige Komponente oder Trägerflüssigkeit für die Pigmentdispersion werden elektrisch isolierende Flüssigkeiten mit einem Volumenwiderstand von mindestens 109 Ohm'cm und einer Dielektrizitätskonstanten unter 3 vorzugsweise auf Kohlenwasserstoffbasis, verwendet, beispielsweise aromatische Kohlenwasserstoffe wie Benzol, Toluol oder Xylole oder aliphatische C6-C15 Kohlenwasserstoffe, wie n-Hexan, Cyclohexan, n-Heptan, n-Oktan oder Dekalin. Auch Mischungen unterschiedlicher Kohlenwasserstoffe können verwendet werden. Besonders geeignet sind verzweigte aliphatische Kohlenwasserstoffe wie Isodecan und Isododecan.Electrically insulating liquids with a volume resistance of at least 10 9 ohm'cm and a dielectric constant below 3, preferably based on hydrocarbons, are used as the liquid component or carrier liquid for the pigment dispersion, for example aromatic hydrocarbons such as benzene, toluene or xylenes or aliphatic C 6 -C 15 hydrocarbons such as n-hexane, cyclohexane, n-heptane, n-octane or decalin. Mixtures of different hydrocarbons can also be used. Branched aliphatic hydrocarbons such as isodecane and isododecane are particularly suitable.
Der Gewichtsanteil des Pigmentes soll 0,5 bis 50 %, vorzugsweise 5-30 % bezogen auf die Pigmentdispersion betragen.The proportion by weight of the pigment should be 0.5 to 50%, preferably 5-30%, based on the pigment dispersion.
Die Pigmentdispersion kann ohne Stabilisierungszusätze verwendet werden. In vielen Fällen ist es jedoch günstig durch geringe Zusätze (0,05-15 Gew.-% bezogen auf den Pigmentanteil) eines löslichen Polymerisates die Dispersion vorzustabilisieren. Zu diesem Zweck eignen sich Homo- oder Copolymerisate aus (Meth)acrylsäureestern, beispielsweise ein 1:1 Copolymerisat aus Isobutylmethacrylat und Laurylmethacrylat. Gut geeignet sind auch Copolymerisate mit einem Anteil von 0,1 - 10 Gew.-% an copolymerisierten Monomeren mit -OH, -COOH, -NH2, -NHR, -NR2-Gruppen, wie z.B. 2-Hydroxyethylmethacrylat, (Meth)acrylsäure, (Meth)acrylamid, NN-Dimethylacrylamid, N,N-Dimethylaminoethylmethacrylat und N-Vinylpyrrolidon. Das bevorzugte Molekulargewicht liegt im Bereich von 50 000 bis 250 000.The pigment dispersion can be used without stabilizing additives. In many cases, however, it is advantageous to pre-stabilize the dispersion by adding small amounts (0.05-15% by weight, based on the pigment content) of a soluble polymer. Homopolymers or copolymers of (meth) acrylic acid esters are suitable for this purpose, for example a 1: 1 copolymer of isobutyl methacrylate and lauryl methacrylate. Copolymers with a proportion of 0.1-10% by weight of copolymerized monomers with -OH, -COOH, -NH 2 , -NHR, -NR 2 groups, such as 2-hydroxyethyl methacrylate, (meth), are also very suitable. acrylic acid, (meth) acrylamide, NN-dimethylacrylamide, N, N-dimethylaminoethyl methacrylate and N-vinylpyrrolidone. The preferred molecular weight is in the range of 50,000 to 250,000.
Unter (Meth)acrylsäureestern (A) mit 8-24 C-Atomen im Alkoholteil werden die Ester aus Acrylsäure bzw. Methacrylsäure und gradkettigen und verzweigten C8-C24-Alkanen verstanden, beispielhaft seien genannt: 2-Ethylhexylmethacrylat, Decylmethacrylat, Dodecylmethacrylat, Laurylmethacrylat und Stearylmethacrylat.(Meth) acrylic acid esters (A) with 8-24 carbon atoms in the alcohol part are understood to mean the esters of acrylic acid or methacrylic acid and straight-chain and branched C 8 -C 24 alkanes, examples being: 2-ethylhexyl methacrylate, decyl methacrylate, dodecyl methacrylate, Lauryl methacrylate and stearyl methacrylate.
Als Vernetzer (B) sind z.B. polyfunktionelle (Meth)-acrylate, wie Ethylendi(meth)acrylat, Ethylenglykol- di(meth)acrylat, Diethylenglykoldi(meth)acrylat, Glycerintrimethacrylat und Trimethylolpropantrimethacrylat, aber auch Divinylbenzol und Allylmethacrylat geeignet.Crosslinkers (B) are e.g. polyfunctional (meth) acrylates, such as ethylene di (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, glycerol trimethacrylate and trimethylolpropane trimethacrylate, but also divinylbenzene and allyl methacrylate are suitable.
Als Komponente (C) sind prinzipiell (Meth)acrylsäureester mit 1-7 C-Atomen im Alkoholteil geeignet. Als Komponente (D) geeignete Verbindungen sind z.B. Hydroxy-und (gegebnenfalls N-alkylsubstituierten) Aminoalkylmethacrylate wie 2-Hydroxyethylmethacrylat oder N,N-Dimethylaminoethylmethacrylat, weiter Styrol, Vinyltoluol, α-Methylstyrol, Maleinsäureanhydrid, Vinylacetat, Allylalkohol und Vinylpyrrolidon.In principle, (meth) acrylic acid esters with 1-7 C atoms in the alcohol part are suitable as component (C). Compounds suitable as component (D) are, for example, hydroxy and (optionally N-alkyl-substituted) aminoalkyl methacrylates such as 2-hydroxyethyl methacrylate or N, N-dimethylaminoethyl methacrylate, further styrene, vinyl toluene, α-methylstyrene, maleic anhydride, vinyl acetate, allyl alcohol and vinyl pyrrolidone.
Besonders gute Ergebnisse erhält man mit Tonern, die 1-15 Gew.-Teile der Komponente (D) enthalten.Particularly good results are obtained with toners which contain 1-15 parts by weight of component (D).
Das Verhältnis von Pigment zur Gesamtmenge an Monomeren (Summe von (A), (B), (C) und (D) soll 3:1 bis 1:10, vorzugsweise 2:1 bis 1:5 betragen.The ratio of pigment to the total amount of monomers (sum of (A), (B), (C) and (D) should be 3: 1 to 1:10, preferably 2: 1 to 1: 5.
Als Startkomponente für die Herstellung der Toner der erfindungsgemäßen Suspensionsentwickler sind übliche Radikalbildner, insbesondere Peroxide und Azoverbindüngen geeignet. Beispielhaft seien genannt: Aliphatische Azodicarbonsäurederivate wie Azobisisobuttersäurenitril oder Azodicarbonsäureester, Peroxide wie Lauroylperoxid, Succinylperoxid, Dibenzoylperoxid, p-Chlorbenzoylperoxid, Ketonperoxide wie Methylethylketonperoxid, Methylisobutylketonperoxid, Cyclohexanonperoxid, Alkylester von Persäuren wie tert.-Butylperpivalat, tert,-Butylperoctoat, tert.-Butylperbenzoat, Mono-tert.-Butylpermaleinat, Percarbonate wie Dicyclohexyl- und Diisopropylpercarbonat, Dialkylperoxide, wie Di-tert.-Butylperoxid, Dicumylperoxid, Hydroperoxide wie tert.-Butyl- oder Cumolhydroperoxide. Im allgemeinen werden 0,1 bis 10 Gew.-%, vorzugsweise 1-5 Gew.-% Startkomponente bezogen auf die Monomeren (A) bis (D) verwendet.As the starting component for the production of the toner of the suspension developer according to the invention conventional R adikalbildner, particularly peroxides and Azoverbindüngen are suitable. Examples include: aliphatic azodicarboxylic acid derivatives such as azobisisobutyronitrile or azodicarboxylic acid esters, peroxides such as lauroyl peroxide, succinyl peroxide, dibenzoyl peroxide, p-chlorobenzoyl peroxide, ketone peroxides such as methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, tert-butyl peroxide, cyclohexanone peroxide, cyclohexanone peroxides, Mono-tert-butyl permaleinate, percarbonates such as dicyclohexyl and diisopropyl percarbonate, dialkyl peroxides such as di-tert-butyl peroxide, dicumyl peroxide, hydroperoxides such as tert-butyl or cumene hydroperoxides. In general, 0.1 to 10% by weight, preferably 1-5% by weight, of starting component, based on the monomers (A) to (D), are used.
Auch eine Kombination verschiedener Startkomponenten, beispielsweise Startkomponenten mit unterschiedlicher Zerfalltemperatur kann in vielen Fällen mit Vorteil angewandt werden.A combination of different starting components, for example starting components with different decay temperatures, can also be used with advantage in many cases.
Die Verwendung von einpolymerisierbaren Radikalstartern ist dann günstig, wenn die Abgabe von Zerfallprodukten des Starters in die flüssige Phase verhindert werden soll. Geeignete Startkomponenten dieses Typs sind beispielsweise Dimethacryloylperoxid und p,p'-Divinyl- benzoylperoxid (US-A 2 593 399).The use of polymerizable radical starters is advantageous if the release of decomposition products of the starter into the liquid phase is to be prevented. Suitable starting components of this type are, for example, dimethacryloyl peroxide and p, p'-divinylbenzoyl peroxide (US Pat. No. 2,593,399).
Die Reaktionstemperatur richtet sich nach der Art der angewendeten Startkomponente, sie liegt im allgemeinen im Bereich von 50-150°C. Die Polymerisationsreaktion kann sowohl bei Normaldruck als auch bei überdruck durchgeführt werden. Die Anwendung von Unterdruck, kann nach Abschluß der Reaktion als Entgasungsstufe angezeigt sein.The reaction temperature depends on the type of starting component used, it is generally in the range of 50-150 ° C. The polymerization reaction can be carried out either under normal pressure or under positive pressure. The use of negative pressure can be indicated as a degassing stage after the reaction has ended.
Die Fällungspolymerisationsreaktion kann nach einem "Batch-Verfahren" durchgeführt werden. In diesem Falle werden die Monomeren und die Startkomponente auf einmal der Pigmentdispersion zugesetzt und die Reaktion durch Temperaturerhöhung eingeleitet. Auf diese Weise werden Pigmentteilchen mit weitgehend einheitlicher Polymerhülle erhalten.The precipitation polymerization reaction can be carried out by a "batch process". In this case, the monomers and the starting component are added to the pigment dispersion all at once and the reaction is initiated by increasing the temperature. In this way, pigment particles with a largely uniform polymer shell are obtained.
In einer bevorzugten Ausführungsform werden die Monomeren und die Startkomponenten während der Polymerisation zudosiert. Diese Ausführungsform eröffnet eine Reihe technisch sehr interessanter Möglichkeiten. So kann man z.B. die Monomerzusammensetzung über den Dosierzeitraum hinweg verändern und auf diese Weise eine schalenförmige Polymerisathülle aufbauen. Es ist möglich, und in bestimmten Fällen sinnvoll, den Vernetzeranteil zunächst hoch einzustellen und dann während des Dosierzeitraumes zu erniedrigen. Bei dieser Verfahrensweise wird eine wenig vernetzte, im Vergleich zur inneren Hülle stärker quellbare, äußere Hülle erhalten. Derartig aufgebaute Pigmentteilchen zeichnen sich durch eine hohe Dispersionsstabilität aus.In a preferred embodiment, the monomers and the starting components are metered in during the polymerization. This embodiment opens up a number of technically very interesting possibilities. So you can ignore change and build in this way a cup-shaped Polymerisathülle as the monomer composition over the D osierzeitraum. It is possible, and in certain cases sensible, to first set the crosslinker content high and then to lower it during the metering period. With this procedure, a slightly crosslinked outer shell is obtained which is more swellable than the inner shell. Pigment particles constructed in this way are notable for high dispersion stability.
Zum Erreichen hoher Stabilitäten ist es weiterhin günstig, die Monomeren (D), insbesondere wenn (D) polare Gruppen wie -OH, -NH2, -COOH enthält, vorzugsweise zu Beginn der Polymerisation zuzudosieren und damit diese Monomeren in der Nähe der Pigmentoberfläche einzupolymerisieren.To achieve high stabilities, it is also advantageous to meter in the monomers (D), in particular if (D) contains polar groups such as -OH, -NH 2 , -COOH, preferably at the start of the polymerization, and thus to polymerize these monomers in the vicinity of the pigment surface .
Die Startkomponente wird mit Vorteil ebenfalls über den Reaktionszeitraum zudosiert. Feste Startkomponenten werden zweckmäßigerweise in Lösungsmitteln oder Monomeren gelöst.The starting component is also advantageously metered in over the reaction period. Solid starting components are expediently dissolved in solvents or monomers.
Während der gesamten Reaktion wird die Pigmentdispersion durch Schütteln oder Rühren gemischt, auch dieDuring the entire reaction, the pigment dispersion is mixed by shaking or stirring, including that
Anwendung von Ultraschall ist eine gute Methode. Insbesondere Pigmentdispersionen, die nicht mit löslichem Polymerisat vorstabilisiert sind, müssen zu Beginn der Reaktion durch ausreichend hohe Scherkräfte dispergiert werden. Im Laufe der Reaktion setzt eine zunehmende Stabilisierung durch das gebildete Polymerisat ein, so daß die angewendete Mischenergie reduziert werden kann.Ultrasound is a good method. In particular, pigment dispersions that are not pre-stabilized with soluble polymer must be dispersed by sufficiently high shear forces at the start of the reaction. In the course of the reaction, increasing stabilization by the polymer formed sets in, so that the mixing energy used can be reduced.
Es ist von Vorteil, bei der Polymerisationsreaktion einen möglichst vollständigen Umsatz zu erreichen, um eine Beeinträchtigung der Funktionsfähigkeit des Suspensionsentwicklers durch nicht umgesetzte Monomere auszuschließen. Der Umsatz sollte deshalb mindestens 80 % betragen. Er läßt sich in bekannter Weise durch die Reaktionszeit, die Reaktionstemperatur und die Konzentration der Startkomponente beeinflussen.It is advantageous to achieve as complete a conversion as possible in the polymerization reaction in order to rule out any impairment of the functionality of the suspension developer by unreacted monomers. The turnover should therefore be at least 80%. It can be influenced in a known manner by the reaction time, the reaction temperature and the concentration of the starting component.
Die umhüllten Pigmentteilchen besitzen eine mittlere Teilchengröße von 0,2 bis 2 µm. Die nach dem vorliegenden Verfahren durch Fällungspolymerisation erhaltene Dispersion kann durch Zugabe von weiterer Trägerflüssigkeit auf die gewünschte Arbeitskonzentration, beispielsweise auf 0,01 % bis 1 % verdünnt werden. Bei dieser Gelegenheit kann, falls dies erwünscht sein sollte, die vorliegende Trägerflüssigkeit gegen eine andere ausgetauscht werden.The coated pigment particles have an average particle size of 0.2 to 2 μm. The dispersion obtained by precipitation polymerization according to the present process can be diluted to the desired working concentration, for example to 0.01% to 1%, by adding further carrier liquid. On this occasion, if desired, the present carrier liquid can be exchanged for another.
Zur Regulierung der elektrischen Ladung der Tonerteilchen in den Suspensionsentwicklern der Erfindung können die bekannten Steuerstoffe verwendet werden. Dies sind z.B. öllösliche ionogene Verbindungen wie etwa Metallsalze langkettiger organischer Säuren. Es können auch Gemische von verschiedenen Steuerstoffen z.B. ein Gemisch von verschiedenen Steuerstoffen mit entgegengesetzten Ladungseffekten verwendet werden, so daß die Stärke der Ladung auf dem Toner oder deren Polarität durch Änderung des Mischungsverhältnisses der beiden Steuerstoffe eingestellt werden kann (GB-A 1 411 287, 1 411 537 und 1 411 739). Besonders geeignete, positiv arbeitende Steuerstoffe werden in der GB-A 1 151 141 beschrieben. Diese Steuerstoffe sind zwei- oder dreiwertige Metallsalze einer von Phosphor abgeleiteten, einen organischen Rest enthaltenden Oxysäure, im einzelnen Salze der Metalle Zink, Kupfer, Cadmium, Aluminium oder Eisen von
- (a) einem Mono- oder Diester einer von Phosphor abgeleiteten Oxysäure,
- (b) einer von Phosphor abgeleiteten Oxysäure, welche eine oder zwei durch ein Kohlenstoffatom an den Phosphor gebundene organische Gruppe enthält, oder
- (c) einer von Phosphor abgeleiteten Oxysäure, die eine Estergruppe und eine über ein Kohlenstoffatom an den Phosphor gebundene organische Gruppe enthält, wobei diese organische Gruppe aliphatisch, cycloaliphatisch oder aromatisch ist.
- (a) a mono- or diester of an oxyacid derived from phosphorus,
- (b) a phosphorus-derived oxyacid containing one or two organic groups attached to the phosphorus through a carbon atom, or
- (c) an oxyacid derived from phosphorus, which contains an ester group and an organic group bonded to the phosphorus via a carbon atom, this organic group being aliphatic, cycloaliphatic or aromatic.
Die organische Gruppe enthält vorzugsweise eine Kette von mindestens 4 Kohlenstoffatomen, insbesondere von 10 bis 18 Kohlenstoffatomen, und sie kann auch durch ein oder mehrere Heteroatome substituiert und/oder unterbrochen sein, z.B. durch Sauerstoff, Schwefel oder Stickstoff.The organic group preferably contains a chain of at least 4 carbon atoms, in particular 10 to 18 carbon atoms, and it can also be substituted and / or interrupted by one or more heteroatoms, e.g. through oxygen, sulfur or nitrogen.
Besonders gute Ergebnisse werden mit den Zinksalzen erzielt. Es können jedoch auch andere Salze verwendet werden, z.B. Magnesium-, Calcium-, Strontium-, Barium-, Eisen-, Kobalt-, Nickel-, Kupfer-, Cadmium-, Aluminium-und Bleisalze.Particularly good results are achieved with the zinc salts. However, other salts can also be used, e.g. Magnesium, calcium, strontium, barium, iron, cobalt, nickel, copper, cadmium, aluminum and lead salts.
Die Löslichkeit der beschriebenen Metallsalze in der elektrisch isolierenden Trägerflüssigkeit kann durch eine oder mehrere organische Gruppen von verzweigter Struktur, z.B. durch verzweigte aliphatische Gruppen, wie eine 2-Butyloctylgruppe, gefördert werden.The solubility of the metal salts described in the electrically insulating carrier liquid can be determined by one or more organic groups of branched structure, e.g. are promoted by branched aliphatic groups such as a 2-butyloctyl group.
Andere geeignete positiv arbeitende Ladungssteuermittel enthalten ein Metallalkylsulfonat, in welchem das Metallion eines der zweiwertigen Metallionen Zink(II), Blei(II), Cadmium(II) oder Kupfer(II) oder ein dreiwertiges Metallion aus der VIII. Gruppe des Periodensystems, z.B. Eisen(III), oder aus der Gruppe VIB, z.B. Chrom(III), ist und worin die Sulfonatgruppe direkt an einer geradkettigen Alkylkette mit mindestens 6 Kohlenstoffatomen vorliegt.Other suitable positive charge control agents contain a metal alkyl sulfonate in which the metal ion is one of the divalent metal ions zinc (II), lead (II), cadmium (II) or copper (II) or a trivalent metal ion from group VIII of the periodic table, for example iron (III), or from the group VIB, for example chromium (III), and in which the sulfonate group is present directly on a straight-chain alkyl chain with at least 6 carbon atoms.
Der Steuerstoff wird entweder dem Konzentrat des Suspensionsentwicklers oder bei der Verdünnung des Entwicklers auf die gewünschte Arbeitskonzentration zugesetzt. Die günstigste Menge läßt sich durch einfache Versuche leicht ermitteln.The control substance is either added to the concentrate of the suspension developer or when the developer is diluted to the desired working concentration. The cheapest amount can easily be determined by simple experiments.
Bevorzugt wird Zink-mono(2-butyl)-octylphosphat als Steuerstoff.Zinc mono (2-butyl) octyl phosphate is preferred as the control substance.
Obwohl der erfindungsgemäße Suspensionsentwickler bereits über eine ausreichende Haftfähigkeit verfügt, können für besondere Anwendungen der Suspensionsentwickler, z.B. zur Entwicklung von Ladungsbildern auf elektrophotographischen Bindemittelschichten, dem fertigen Entwickler sogenannte Fixiermittel einverleibt werden. Als fixierende Substanzen eignen sich Harze, die mit dem Bindematerial des photoleitfähigen Aufzeichnungsmaterials verträglich sein sollen, z.B. mit dem Bindemittel einer photoleitfähigen Zinkoxidschicht, damit nach der Entwicklung eine gute Haftung des erzeugten Bildes auf der Unterlage erhalten wird. Beispiele für geeignete Harze sind Ester von hydrogeniertem Kolophonium und fettem öllack ("long-oil"), kolophoniummodifiziertes Phenol-Formaldehydharz, Pentaerythritolester von Kolophonium, Glycerinester von hydrogeniertem Kolophonium, Ethylcellulose, verschiedene Alkydharze, Polyacryl- und Polymethacrylharz, Polystyrol, Polyketonharz und Polyvinylacetat. Spezifische Beispiele solcher Harze sind in der Literatur über elektrostatographische Suspensionsentwickler zu finden, z.B. in der BE-A 699 157 und in der GB-A 1 151 141.Although the suspension developer according to the invention already has sufficient adhesiveness, for special applications of the suspension developer, e.g. for the development of charge images on electrophotographic binder layers, so-called fixatives are incorporated into the finished developer. Suitable fixing substances are resins which are said to be compatible with the binding material of the photoconductive recording material, e.g. with the binder of a photoconductive zinc oxide layer, so that good adhesion of the generated image to the base is obtained after development. Examples of suitable resins are esters of hydrogenated rosin and fatty oil varnish ("long-oil"), rosin-modified phenol-formaldehyde resin, pentaerythritol esters of rosin, glycerol esters of hydrogenated rosin, ethyl cellulose, various alkyd resins, polyacrylic and polymethacrylic resin, polystyrene, poly (vinyl acetate), poly (vinyl acetate). Specific examples of such resins can be found in the literature on electrostatographic suspension developers, e.g. in BE-A 699 157 and in GB-A 1 151 141.
Mit den folgenden Beispielen wird die Umhüllung von Pigmentteilchen in einer Trägerflüssigkeit durch Fällungspolymerisation, sowie die Herstellung erfindungsgemäßer Suspensionsentwickler im einzelnen erläutert.The following examples explain in detail the coating of pigment particles in a carrier liquid by precipitation polymerization, and the preparation of suspension developers according to the invention.
In einem 1 1 Rührtopf mit Blattrührer, Rückflußkühler, Tropftrichter, Gaseinlaß- und Gasauslaßrohr wurde eine Pigmentdispersion, hergestellt mit Hilfe einer Kugelmühle aus 30 g Helioechtgelb GRN (C.I. 21100) 270 g Isododecan und 0,3 g Polylaurylmethacrylat (MG 150000), vorgelegt und auf 80°C aufgeheizt. Die Dispersion wurde mit N2- begast, mit 500 UpM gerührt und mit 0,5 g Azoisobuttersäuredinitril (AIBN) versetzt.In a 1 1 stirring pot with blade stirrer, reflux condenser, dropping funnel, gas inlet and gas outlet tube, a pigment dispersion, prepared with the aid of a ball mill made of 30 g helio-real yellow GRN (CI 21100), 270 g isododecane and 0.3 g polylauryl methacrylate (MW 150000), was introduced and heated to 80 ° C. The dispersion was gassed with N 2 , stirred at 500 rpm, and 0.5 g of azoisobutyronitrile (AIBN) was added.
Nach beendeter Zugabe wurde 1 Stunde bei 80°C und anschließend eine weitere Stunde bei 90°C nachgerührt.After the addition had ended, the mixture was stirred at 80 ° C. for 1 hour and then at 90 ° C. for a further hour.
Es entstand eine stabile Dispersion. Vor dem Einsatz der Dispersion als Entwickler in einem elektrostatographischen Gerät bekannter Art wurde die Dispersion mit Isododecan auf 4 Gew.-% Feststoffgehalt verdünnt und mit 12 mg Zink-mono-(2-butyl)-octylphosphat pro Gramm Feststoff versetzt. Die Ladung der Tonerteilchen war nach 24 Stunden Lagerung stabilisiert. Die Teilchengröße betrug 0,8 - 1,2 pm.A stable dispersion resulted. Before the dispersion was used as a developer in a known electrostatographic device, the dispersion was diluted with isododecane to a solids content of 4% by weight and 12 mg of zinc mono- (2-butyl) octyl phosphate per gram of solid were added. The charge of the toner particles was stabilized after 24 hours of storage. The particle size was 0.8-1.2 pm.
In der in Beispiel 1 beschriebenen Apparatur wurde eine Dispersion aus 35 g Helioechtblau HG (C.I. 74160) und 315 g Isododecan vorgelegt. Zu der Dispersion wurden bei 60°C unter Rühren mit 600 UpM
Nach dem Verdünnen der Dispersion auf 4 Gew.-% Feststoffgehalt wurden 6 mg Zink-mono-(2-butyl)-octyl- phosphat pro Gramm Feststoff zugegeben. Der Entwickler war nach 24 Stunden einsatzfähig. Die Teilchengröße war 0,86 pm. Der Suspensionsentwickler zeigte eine sehr gute Lagerstabilität. Die Teilchengröße war noch nach 6 monatiger Lagerung unverändert.After the dispersion had been diluted to a solids content of 4% by weight, 6 mg of zinc mono- (2-butyl) octyl phosphate were added per gram of solid. The developer was operational after 24 hours. The particle size was 0.86 pm. The suspension developer showed very good storage stability. The particle size was unchanged after 6 months of storage.
In der in Beispiel 1 beschriebenen Apparatur wurde eine aus 30 g Fanalrosa B (C.I. Nr. 45160), 1,5 g Copolymerisat aus Isobutylmethacrylat und Laurylmethacrylat (1:1) und 268,5 g Isododekan hergestellte Dispersion vorgelegt. Der Dispersion wurde anschließend bei 60°C unter Rühren mit 500 UpM ein Gemisch ausA dispersion prepared from 30 g Fanalrosa B (C.I. No. 45160), 1.5 g copolymer of isobutyl methacrylate and lauryl methacrylate (1: 1) and 268.5 g isododecane was placed in the apparatus described in Example 1. The dispersion then became a mixture at 60 ° C. with stirring at 500 rpm
Es entstand eine stabile Dispersion (Teilchengröße ca. 0,6 µm). Nach Verdünnen mit Isododecan und nach Zugabe von Zink-mono-(2-butyl)-octyl-phosphat wurde ein Suspensionsentwickler mit guten Entwicklereigenschaften und hervorragender Lagerstabilität erhalten.A stable dispersion resulted (particle size approx. 0.6 µm). After dilution with isododecane and after adding zinc mono- (2-butyl) octyl phosphate, a suspension developer with good developer properties and excellent storage stability was obtained.
Gemäß dem im Beispiel 1 der DE-A 2 157 143 angegebenen Pfropfpolymerisationsverfahren wurden 50 g des Esters der Methacrylsäure mit Oleylalkohol, 50 g feingemahlenes Helioechtgelb GRN (C.I. 21100) und 1 g Azobisisobutyronitril in Benzol umgesetzt. Das Reaktionsprodukt wurde durch mehrmaliges Eingießen in Methanol von löslichen Bestandteilen befreit und in . dem in der genannten DE-A angegebenen isoparafinischen Lösungsmittel dispergiert.According to the graft polymerization process given in Example 1 of DE-A 2 157 143, 50 g of the ester of methacrylic acid were reacted with oleyl alcohol, 50 g of finely ground Helio real yellow GRN (C.I. 21100) and 1 g of azobisisobutyronitrile in benzene. The reaction product was freed from soluble constituents by repeated pouring into methanol and poured into. dispersed the isoparaffinic solvent specified in said DE-A.
Die erhaltene Dispersion zeigte eine für die praktische Verwendung ungenügende Stabilität. Die Tonerteilchen neigen zur Agglomeration und Sedimentation.The dispersion obtained showed insufficient stability for practical use. The toner particles tend to agglomerate and sediment.
Der Entwickler liefert unsaubere Bilder durch Tonerablagerung an den bildfreien Stellen.The developer delivers unclean images by depositing toner in the non-image areas.
Entsprechend Beispiel 1 der DE-B 1 933 362 wurde Helioechtblau HG (C.I. 74160) mit 2 Kunststoffschichten überzogen. Die erhaltenen Granalien wurden in einer Kugelmühle auf-0,09 mm Teilchengröße zerkleinert und in Isododecan dispergiert.According to Example 1 of DE-B 1 933 362, Helioechtblau HG (C.I. 74160) was coated with 2 plastic layers. The granules obtained were ground in a ball mill to a particle size of -0.09 mm and dispersed in isododecane.
Die erhaltene Suspension war zwar zum Entwickeln von latenten elektrostatischen Bildern prinzipiell geeignet, die mit dem Entwickler erreichte Auflösung der Bilder war jedoch mangelhaft und insbesondere für die Wiedergabe von Farbbildern unzureichend.The suspension obtained was suitable in principle for developing latent electrostatic images, but the resolution of the images achieved with the developer was inadequate and in particular inadequate for the reproduction of color images.
Claims (10)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19823232062 DE3232062A1 (en) | 1982-08-28 | 1982-08-28 | ELECTROSTATOGRAPHIC SUSPENSION DEVELOPER AND METHOD FOR THE PRODUCTION THEREOF |
| DE3232062 | 1982-08-28 |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| EP0102025A2 true EP0102025A2 (en) | 1984-03-07 |
| EP0102025A3 EP0102025A3 (en) | 1985-10-23 |
| EP0102025B1 EP0102025B1 (en) | 1987-09-23 |
Family
ID=6171935
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP83108097A Expired EP0102025B1 (en) | 1982-08-28 | 1983-08-17 | Dry electrostatographic toner and process for its preparation |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US4521505A (en) |
| EP (1) | EP0102025B1 (en) |
| JP (1) | JPS5958441A (en) |
| CA (1) | CA1248390A (en) |
| DE (2) | DE3232062A1 (en) |
Families Citing this family (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5264313A (en) * | 1984-12-10 | 1993-11-23 | Spectrum Sciences B.V. | Charge director composition |
| DE3514867A1 (en) * | 1985-04-25 | 1986-11-06 | Agfa-Gevaert Ag, 5090 Leverkusen | ELECTROSTATOGRAPHIC SUSPENSION DEVELOPER AND METHOD FOR THE PRODUCTION THEREOF |
| JPS63178258A (en) * | 1987-01-19 | 1988-07-22 | Mitsubishi Paper Mills Ltd | Liquid developer for electrostatic photography |
| US4758492A (en) * | 1986-04-30 | 1988-07-19 | Eastman Kodak Company | Weakly acidic crosslinked vinyl polymer particles and coating compositions and electrographic elements and developers containing such particles |
| DE3642212A1 (en) * | 1986-12-10 | 1988-06-23 | Espe Stiftung | POLYMERIZABLE MEASURES, METHOD FOR THEIR PRODUCTION AND THEIR USE AS DENTAL MEASURES |
| US4947201A (en) * | 1988-06-06 | 1990-08-07 | Spectrum Sciences | Imaging system |
| US4966824A (en) * | 1988-06-06 | 1990-10-30 | Spectrum Sciences | Liquid toner composition containing two different charge directors |
| US5155001A (en) * | 1989-03-06 | 1992-10-13 | Spectrum Sciences B.V. | Liquid developer method with replenishment of charge director |
| JP4122690B2 (en) * | 2000-07-28 | 2008-07-23 | 日本ゼオン株式会社 | Toner production method |
| EP1205815B1 (en) * | 2000-11-10 | 2009-12-23 | Samsung Electronics Co., Ltd. | Liquid inks comprising surface-treated colorant particles and manufacturing method thereof |
| JP2004002501A (en) * | 2002-05-27 | 2004-01-08 | Fuji Photo Film Co Ltd | Oil based ink composition for inkjet printer |
| JP2004018736A (en) * | 2002-06-18 | 2004-01-22 | Fuji Photo Film Co Ltd | Oil-base ink composition for inkjet printer |
| JP2004035592A (en) * | 2002-06-28 | 2004-02-05 | Fuji Photo Film Co Ltd | Production method for oily ink composition for inkjet printer, liquid developer for electrophotography, and colored resin particle |
| WO2009070148A1 (en) * | 2007-11-30 | 2009-06-04 | Hewlett-Packard Development Company, L.P. | Polymer coated toner pigments for electrophotographic printing |
| MX2015007705A (en) | 2012-12-21 | 2015-09-08 | Quarzwerke Gmbh | Thermotropic polymers. |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2026390A1 (en) * | 1969-05-28 | 1971-01-07 | Fuji Photo Film Co Ltd , Kanagawa (Japan) | Electrophotographic developer and method for making the same |
| DE2311598A1 (en) * | 1972-03-11 | 1973-09-20 | Ricoh Kk | LIQUID ELECTROPHOTOGRAPHIC DEVELOPER |
| DE2512112A1 (en) * | 1974-03-20 | 1975-10-02 | Hitachi Chemical Co Ltd | LIQUID DEVELOPER FOR ELECTROPHOTOGRAPHY |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3668127A (en) * | 1968-07-01 | 1972-06-06 | Ricoh Kk | Liquid developer for electrophotography |
| GB1411287A (en) * | 1972-07-12 | 1975-10-22 | Agfa Gevaert | Liquid electrophotographic developers |
| JPS5612868B2 (en) * | 1973-03-23 | 1981-03-25 | ||
| JPS548532A (en) * | 1977-06-22 | 1979-01-22 | Toray Industries | Wet toner with good fixability |
| DE2946465A1 (en) * | 1979-11-17 | 1981-06-11 | Agfa-Gevaert Ag, 5090 Leverkusen | NEW POLYMERS, METHOD FOR THEIR PRODUCTION AND THEIR USE FOR THE PRODUCTION OF PHOTOGRAPHIC EMULSIONS AND PHOTOGRAPHIC MATERIALS |
| JPS5858667B2 (en) * | 1979-12-03 | 1983-12-26 | 株式会社リコー | Liquid developer for electrostatography |
| JPS58150970A (en) * | 1982-03-04 | 1983-09-07 | Ricoh Co Ltd | Electrostatic photographic liquid developer |
-
1982
- 1982-08-28 DE DE19823232062 patent/DE3232062A1/en not_active Withdrawn
-
1983
- 1983-08-17 EP EP83108097A patent/EP0102025B1/en not_active Expired
- 1983-08-17 DE DE8383108097T patent/DE3373845D1/en not_active Expired
- 1983-08-23 JP JP58152606A patent/JPS5958441A/en active Pending
- 1983-08-23 US US06/525,625 patent/US4521505A/en not_active Expired - Fee Related
- 1983-08-26 CA CA000435473A patent/CA1248390A/en not_active Expired
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2026390A1 (en) * | 1969-05-28 | 1971-01-07 | Fuji Photo Film Co Ltd , Kanagawa (Japan) | Electrophotographic developer and method for making the same |
| DE2311598A1 (en) * | 1972-03-11 | 1973-09-20 | Ricoh Kk | LIQUID ELECTROPHOTOGRAPHIC DEVELOPER |
| DE2512112A1 (en) * | 1974-03-20 | 1975-10-02 | Hitachi Chemical Co Ltd | LIQUID DEVELOPER FOR ELECTROPHOTOGRAPHY |
Non-Patent Citations (1)
| Title |
|---|
| XEROX DISCLOSURE JOURNAL, Band 1, Nr. 11/12, November/Dezember 1976, Seiten 47-49, Stamford, Connecticut, US; Y. TAMAI u.a.: "Liquid developers" * |
Also Published As
| Publication number | Publication date |
|---|---|
| US4521505A (en) | 1985-06-04 |
| EP0102025A3 (en) | 1985-10-23 |
| JPS5958441A (en) | 1984-04-04 |
| EP0102025B1 (en) | 1987-09-23 |
| DE3373845D1 (en) | 1987-10-29 |
| CA1248390A (en) | 1989-01-10 |
| DE3232062A1 (en) | 1984-03-01 |
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