Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
  • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
  • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
  • B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
  • B41M5/52—Macromolecular coatings
• • D—TEXTILES; PAPER
  • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
  • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
  • D21H19/00—Coated paper; Coating material
  • D21H19/36—Coatings with pigments
  • D21H19/44—Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
  • D21H19/56—Macromolecular organic compounds or oligomers thereof obtained by reactions only involving carbon-to-carbon unsaturated bonds
• • D—TEXTILES; PAPER
  • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
  • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
  • D21H19/00—Coated paper; Coating material
  • D21H19/36—Coatings with pigments
  • D21H19/44—Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
  • D21H19/62—Macromolecular organic compounds or oligomers thereof obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
  • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
  • B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
  • B41M5/502—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording characterised by structural details, e.g. multilayer materials
  • B41M5/508—Supports
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
  • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
  • B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
  • B41M5/52—Macromolecular coatings
  • B41M5/5218—Macromolecular coatings characterised by inorganic additives, e.g. pigments, clays
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
  • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
  • B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
  • B41M5/52—Macromolecular coatings
  • B41M5/5236—Macromolecular coatings characterised by the use of natural gums, of proteins, e.g. gelatins, or of macromolecular carbohydrates, e.g. cellulose
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
  • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
  • B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
  • B41M5/52—Macromolecular coatings
  • B41M5/5245—Macromolecular coatings characterised by the use of polymers containing cationic or anionic groups, e.g. mordants
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
  • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
  • B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
  • B41M5/52—Macromolecular coatings
  • B41M5/5254—Macromolecular coatings characterised by the use of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers

Definitions

• the present invention relates to a recording sheet suitaole for use in ink jet recording.
• InK jet recording processes nave emerged as one of the most important tecnnologies for hign speed electronic printing. With tneir emergence there has arisen a need for recording papers having designed recording properties.
• the basic imaging technique in inK jet recording involves the use of one or more inK jet assemblies connected to a source of ink.
• Each ink jet includes a small orifice whicn is electromagnetically energized by magneto- restrictive, piezoelectric, thermal, or similar means to emit uniform droplets of inK as a continuous stream or as individual droplets on demand. Tne droplets are directed onto tne surface of a moving we D and controlled to form printed characters.
• Tne ink must be capable of forming stable ink droplets under pressure and must readily emerge from the ink jet orifice.
• the absorption of these inks by the recording sheet has been somewhat problematic, particularly in the area of multicolor printing where two or more inK drops may overlap on the surface of the recording sheet.
• tne recording sneet must absorb tne ink rapidly and at the same time insoluoil- ize the ink dye on the sneet surface.
• Tne former property reduces tne tendency for set-off (i.e., transfer of tne inK from tne paper to sneet hanaling rollers and tne like) whereas tne latter property insures tnat images having high optical density are obtained.
• these two properties are in conflict with one another. Papers having high absorbency draw the ink deeply into the paper, and as a result, the optical density of the image formed at tne paper surface is reduced.
• Tney also suffer from feathering, poor edge acuity, and show-through.
• Papers with low absorbency such as hignly sized papers, provide good optical density by retaining tne ink at the paper surface but nave a nigh tendency to set-off because tne ink venicle is not absorbed rapidly.
• Tne perfect ink jet recording sheet nas been described as a blotter witn a magic film.
• the blotter rapidly absorbs the ink venicle while tne magic film insures that the colorant is retained at tne surface of tne sheet where its lignt absorbing and reflecting properties are greatest. If tne colorant is carried deeply into the paper web, its absorbing strength is reduced, web fibers conduct the ink laterally and poor image sharpness and show-through occurs. See P.A. McManus et al, *Paper Requirements for Color Imaging with InK Jets", TAPPI, Vol. 66, No. 7, July, 1983, pp. 81-5.
• the ink receptive layer is formed of white pigments and an aqueous binder.
• Tne pigments ennance the quality of tne image by imparting a high level of whiteness to tne copy and reflecting incident lignt and also serve as a substrate whicn binds the inK jet recording ink.
• Aqueous binders are used to enhance tne absorption of the ink vehicle.
• Crooks et al IBM Technical Disclosure Bulletin, Vol. 21, No. 6, Novem D er 1978 discloses a recording paper coated with a layer of a water soluble polymer such as starch, gelatin, polyvinyl pyrrolidone and polyvinyl alcohol.
• a water soluble polymer such as starch, gelatin, polyvinyl pyrrolidone and polyvinyl alcohol.
• U.S. Patent 4,446,174 describes a recording paper having an ink-receptive layer including a dye-absorbing pigment such as zeolite, clay, attapulgite, and diatomaceous earth and a binder.
• a dye-absorbing pigment such as zeolite, clay, attapulgite, and diatomaceous earth and a binder.
• a number of binders are disclosed in the patent including binders having dissociable dye-absorbing groups such as polyacrylates, styrene-maleic annydride copolymer, sodium alginate, ethylene-maleic anhydride copolymer and cationic search; and binders not having dissociable groups such as starch, polyvinyl alcohol, polyvinyl pyrrolidone and styrene-butadiene latex.
• Murakami et al U.S. Patent 4,425,405 discloses an inK-jet recording sheet in which the ink receptive layer contains polyvinylpyrrolidone and/or vinylpyrrolidone-vinyl acetate copolymer and a white filler.
• tne layer may also include a water insoluble binder to impart moisture resistance.
• Ink jet recording papers are also Known in wnich the dye-absoroing characteristics of tne paper itself are beneficially modified by incorporating certain polymers or sizing agents into the paper itself.
• Maekawa et al, U.S. Patent 4,308,542, and Minagawa, U.S. Patent 4,269,891 describe inK jet recording papers prepared from syntnetic paper. Tne papers are designed to enable viewing tne images by reflection or by transmission of lignt through tne recording sheet.
• Certain water soluble adhesives having a highly nydrophilic cnaracters, including among tnem polyetnylene oxide, are added to tne pulp to improve surface strengtn and improve tne inK aosorption properties. While tnere are numerous examples of inK jet recording papers in the art, tnere is a need for alternative papers and there is particularly a need for coated papers suitable in hign quality printing.
• Still another object of the present invention is to provide a pigmented ink jet recording layer that is useful with botn aqueous and solvent based inks.
• Tnese and otner objects are acnieved in accordance with the present invention which provides an ink jet recording paper comprising a paper support and an inK-receptive coating on at least one surface of said support, said inK-receptive coating including a wnite pigment dispersed in polyethylene oxide.
• Tne inK-receptive layer used in the present invention in its simplest form includes a white pigment and polyethylene oxide.
• polyethylene oxide does not provide sufficient binding strength to satisfy all the requirements of the recording process.
• Ink receptive layers consisting of polyethylene oxide and pigment tend to dust, i.e., lose pigment more readily and sometimes crack. For this reason it is preferred to include an additional resin in the composition to ennance binding strength and thereby reduce dusting and improve the integrity of the layer.
• the molecular weight of the polyethylene oxide used in the present invention may range from about 100,000 to 900,000 and preferably from about 100,000 to 300,000.
• Suitable resins useful in ennancing tne binding strength of polyetnylene oxide can be selected from among a number of hign molecular materials conventionally used in papers or paper coatings.
• a binder snoula be selected whicn is compatible with the polyethylene oxide.
• useful polymers include polyvinyl acetate, ethylene-vinyl acetate copolymer, polymetn- acrylates, polyacrylates, polyvinyl alcohol, oxidized starch, carboxymethyl cellulose, hydroxyethyl cellulose, styrene-maleic acid copolymer, styrene- D utadiene copolymer and the like.
• Polyvinyl alcohol and starch are usually used because they are relatively inexpensive and tney provide good binding strength.
• Tne polyethylene oxide is usually used in the inK-receptive layer in an amount of about 5 to 70% by weight and preferably 10 to 40% by weight based on the dry weight of tne ink-receptive layer.
• Tne amount of otner resin included- in the ink-receptive layer to enhance binding strength will vary with its nature, the amount and nature of the filler used and other factors. Typically, these other resins may be incorporated into the coating in an amount of about 0 to 60% by weight (dry) or in weight ratio to the polyethylene oxide of about 1:10 to 10:1.
• fillers which can be used in the practice of the invention in combination with polyetnylene oxide include clay, talc, calcium caroonate, alumina and alumina hydrate, zeolite, synthetic silica, calcium sulfate, diatomaceous earth, magnesium silicate, barium carbonate, barium sulfate, aluminum silicate, magnesium oxide, magnesium carbonate, calcium silicate, satin wnite, etc.
• Tne preferred filler is synthetic silica (e.g., Syloid 244 from W. R. Grace Co.). It may be desiraole to dilute the silica with another white filler in some cases.
• Tne filler is generally used in an amount of about 5 to 90% and preferably 40 to 90% by weight based on the dry weight of tne recording layer.
• Tne recording cnaracteristics of tne ink jet recording paper of the present invention are generally improved by the addition of a cationic resin and/or polyvalent metal salt.
• aqueous ink compositions containing acid or direct dyes are used in ink jet recording. These dyes advantageously react with the cations provided by the resin or tne metal salt and become more rapidly set in the inK receptive layer. Tnis tends to prevent off-set and further reduce featnering and dot spread.
• Useful cationic polymers are cnaraccerized by a hign cationic cnaracter. Such polymers are typically made up of at least 3 mol % cationic monomer units and preferably at least 10 mol % and up to 100%.
• Polymeric amines such as polymers of quaternary amines or amines converted to quaternary amines under acid conditions can be used.
• the cationic character of these polymers can oe expressed as a nitrogen concentration since the nitrogen present in the polymers generally is in the form of cationic quaternary ammonium groups.
• tne polymeric cationic amines used in the present invention can be characterized as having a nitrogen content in excess of about 0.1%, preferably in excess of 1.5 % and still more preferably in excess of 3.0% by weight.
• a useful class of cationic polymers are so-called electroconductive polymers which are conventionally used in electrophotographic, electrographic or electrostato- graphic processes. Examples of such polymers are described in U.S. Patents 3,011,918; 3,544,318; 4,148,639; 4,171,417; 4,316,943; and 3,813,264. Tnese polymers are characterized by the presence of a high percentage of cationic groups such as tertiary amino and quaternary ammonium cationic groups.
• Representative polymers are nomopolymers or copolymers of cationic monomers such as quaternary diallyl- diakylammonium chlorides such as diallyldimethylammonium chloride, N-alkylammonium chlorides, methacrylamidopropyl- trimethylammonium chloride, methacryloxyethyl trimetnylammonium chloride, 2-hydroxy-3-methacryloxypropyl trimethylammonium chloride, methacryloxyethyl trimethylammonium me L hosulfate, vinylbenzyl trimetnylammonium chloride and quaternized 4-vinylpyridine.
• quaternary diallyl- diakylammonium chlorides such as diallyldimethylammonium chloride, N-alkylammonium chlorides, methacrylamidopropyl- trimethylammonium chloride, methacryloxyethyl trimetnylammonium chloride, 2-hydroxy-3
• Warcofix 808 a guanidine-formaldehyde polymer available from Sun Chemical Corp.
• Calgon 261 LV and Calgon Conductive Polymer 7091 RV polydimethydiallylammonium chlorides available from Calgon Corp.
• Nalco 8674 a cationic polyamine available from Nalco Corp.
• CAT Floc C available from Calgon Corp.
• the polyvalent metal salts used in the present invention are polyvalent water soluble salts of polyvalent cations from Group II, Group III or the Transition Metals of the Periodic Table of Elements. Typically, these salts can be dissolved in water in an amount greater than 5 g/ 100ml at 23°C. Tne most readily available and cost effective salts are Zn 2+ , Al 3+ , Mg , Ca and Ba 2+ salts.
• tne salts are salts of one of the aforesaid polyvalent cations and an anion of a weak acid such as an anion of an acid naving a pKa value greater than 2.0 and, more preferably, greater than 3.0.
• Salts of strong acid anions such as alum are capable of insolubilizing an ink jet dye but are generally undesirable because they impart high acidity to the paper wnicn accelerates degradation.
• chlorides, sulfates, chlorates, and nitrates are useful, tne preferred salts are acetates, formates, chlorohydrates, malonates, succinates, and salts of other weak organic acids.
• salts useful in the present invention are alum, calcium formate, and aluminum cnloro- hydrate.
• Certain zirconium Zr 3+ , Zr 4+ , and Zr 5+ salts are also believed to be useful such as zirconium oxychloride and zirconium hydroxychloride.
• the ink-receptive layer of the present invention may contain about 5 to 50% by weight of the aforementioned cationic resins and/or about 1 to 25% by weight of the polyvalent metal salt.
• the ink-receptive layer is typically formed by preparing an aqueous dispersion of polyetnylene oxide, filler and any other additive(s) and coating it onto a support in a conventional manner.
• Conventional paper coating machines such as blade coaters, air knife coaters, roll coaters, brush coaters, gravure coaters, size presses, rod coaters, and curtain coaters may be used for this purpose.
• the coating composition may be applied to the support in an amount of about 1 to 40 g/m 2 on a dry basis and preferably 5 to 20 g/m 2 , The upper limit on the thickness is not as critical. After the coating is dried it may be smoothed by calendering if desired.
• tne paper support typically are a product of the recording application or the recording apparatus rather than the coating composition.
• papers having a basis weight of about 12 to 30 pounds per 1300 sq. ft., an apparent density in the- range of 0.3 to 1.2 and filler content of 0 to 40% are useful.
• conventional D leached Kraft and bleached sulfite pulps can be used in tne present invention.
• Waterleaf, low size, hign size and bond paper can be used.
• the coating can also be used with certain synthetic papers or applied to polymeric films.
• the preferred support tnickness is about 30 to 150 microns.
• thermoplastic films whicn can be used in the present invention include polyester films sucn as polyethylene terephthalate, polystyrene, polyvinyl chloride, polymetnylmethacrylate and cellulose acetate.
• the ink jet recording paper of the present invention is preferably used in conjunction witn aqueous inK jet recording inks but it can also be used with certain solvent-based inks.
• useful dyes include acid dyes such as Tartrazine (CI 19140), Quinoline Yellow (CI 47005), Eosin (CI 45380), Erytnrosine (CI 45430), Brilliant Cyanine 6B (CI 42660), Acid Black 1 (CI 20470), Acid Black 36 (CI 27275) and Acid Blue Black 10B (CI 20470), Acid Blue 193 (CI 15707), Acid Blue 194 (CI 17941), Acid Blue 249 (CI 74220); and direct dyes sucn as Direct Black 19, Direct BlacK 49, Direct Black 56, Direct Black 74, Direct Black 103, Direct Black GW, Cap- amine Black ESA, Deep BlacK XA (CI Direct BlacK 154), Black G (CI 35255), Pnthalocyanine Blue (CI 74180), Direct Blue 78, Direct Blue 239, Direct Blue
• a coating composition was prepared by comDining the following:
• the coating was drawn down on a hard size raw stock using a .0.5 ml bird bar.
• the ink-receptive layer contained 12.5% polyvinyl alcohol, 12.5% polyethylene oxide, 25% aluminum silicate and 50% barium sulfate.
• the ink displayed no tendency to feather.
• Example 1 Three ink jet recording papers were prepared as in Example 1 except the molecular weight of the polyethylene oxide was varied.
• Sample A was prepared using a 100,000 molecular weight polyetnylene oxide.
• Sample B was prepared using a 200,000 molecular weight polyethylene oxide and
• Sample C was prepared using a 300,000 molecular weight polyethylene oxide.
• a solvent based magenta recording ink was applied to the.ink-receptive layer of each of tne sneers with an Advanced Color Technology ACT-1 Printer. Tne dot area, parameter and shape were measured. Tne results are shown in Table I. For comparison, dot size is shown for the same ink as applied to a commercial oond paper.
• Ink jet recording papers were prepared by coating the compositions shown in Table 2 below on a commercial rawstock using a rod coater.
• Samples 1-3 correspond to samples prepared according to the teachings in U.S. Patent 4,425,405 containing polyvinyl pyrrolidone in tne inK-receptive layer.
• Samples 4-6 are papers prepared in accordance with the present invention.

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• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Ink Jet Recording Methods And Recording Media Thereof (AREA)
• Paper (AREA)
• Duplication Or Marking (AREA)

Applications Claiming Priority (2)

Publications (1)

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Family Applications (1)

Country Status (4)

Cited By (45)

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Citations (6)

• 1985
  • 1985-11-18 EP EP85308392A patent/EP0199874A1/de not_active Withdrawn
  • 1985-12-30 KR KR1019850009975A patent/KR860006349A/ko not_active Application Discontinuation
• 1986
  • 1986-01-10 JP JP61003378A patent/JPS61209190A/ja active Pending
  • 1986-01-14 CN CN198686100080A patent/CN86100080A/zh active Pending

Patent Citations (6)

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