EP0712735B1 - Enregistrement par jet d'encre, méthodes pour former des images et matériau d'enregistrement - Google Patents

Enregistrement par jet d'encre, méthodes pour former des images et matériau d'enregistrement Download PDF

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Publication number
EP0712735B1
EP0712735B1 EP95118081A EP95118081A EP0712735B1 EP 0712735 B1 EP0712735 B1 EP 0712735B1 EP 95118081 A EP95118081 A EP 95118081A EP 95118081 A EP95118081 A EP 95118081A EP 0712735 B1 EP0712735 B1 EP 0712735B1
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Prior art keywords
ink
pigment
recording
jet recording
water
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German (de)
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EP0712735A1 (fr
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Akio C/O Canon Kabushiki Kaisha Kashiwazaki
Eiichi C/O Canon Kabushiki Kaisha Suzuki
Mifune C/O Canon Kabushiki Kaisha Hirose
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Canon Inc
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Canon Inc
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    • 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

Definitions

  • the present invention relates to an ink-jet recording method employing a pigment-based ink, a method for the formation of an image and a recording medium preferably used for an ink-jet recording system.
  • An ink-jet recording method is a method which performs recording by generating and ejecting ink droplets to apply a part or all of them to a recording medium such as paper or plastic films coated with an ink reception layer using various ink ejection methods, for example, electrostatic suction methods, methods using piezoelectric elements to apply mechanical vibrations and displacement to inks, or methods to heat a ink until it foams to generate a pressure.
  • various ink ejection methods for example, electrostatic suction methods, methods using piezoelectric elements to apply mechanical vibrations and displacement to inks, or methods to heat a ink until it foams to generate a pressure.
  • Inks for the ink-jet recording method mainly comprise water to provide safety and good recording characteristics and contain polyhydric alcohol to prevent blocking of nozzles and improve an ejection stability.
  • Such inks contain various water-soluble dyes dissolved in water or a mixture of water and an organic solvent. Due to its inherently low light fastness, the use of water-soluble dyes often results in a low light fastness of recorded images.
  • the ink is aqueous
  • recorded images often have a low water fastness. That is, if rain, sweat, or drinking water contacts recorded images, they may blot or be lost.
  • Japanese Patent Applications Laid-Open No. 58-80368, No. 61-200182, No. 61-247774, No. 61-272278, No. 62-568, No. 62-101671, No. 62-101672, No. 1-249869, and No. 1-301760 attempt to provide a dispersion stability, to prevent an agglomeration of an ink at the tip of a pen, or to prevent a ball in a ball-point pen from being worn, in order to put aqueous pigment-based inks to practical use.
  • Ball-point pens and markers employing an aqueous pigment-based ink have recently been on the market.
  • pigment-based inks making use of aqueous pigment-based inks pigment-based inks containing a specific water-soluble solvent and a specific polymer dispersant have been proposed in Japanese Patent Application Laid-Open No. 56-147859 and No. 56-147860. As listed above, a large number of proposals have been made for ink-jet pigment-based inks.
  • Recording media conventionally used for an ink-jet recording system consist of recording paper comprising base paper and a coating layer disposed thereon and containing fumed silica and a water-soluble binder such as polyvinyl alcohol, as described in Japanese Patent Publication No. 3-26665, glossy paper comprising cast-coated paper and a coating layer formed thereon and containing polyvinyl alcohol with a saponification degree of from 50 to 90% by mole and a crosslinking agent, as described in Japanese Patent Publication No.
  • a recording medium should have characteristics of:
  • the recording medium In recording sheets for an OHP and color filters, the recording medium is required also to be sufficiently transparent.
  • the pigment-based ink is disadvantageous in that it rapidly starts to flocculate when its pH reaches a certain value. This may cause an advantage in that a color density of resultant images is increased when the images are printed on an opaque substrate such as paper to observe light reflected therefrom.
  • the pigments may too rapidly be started to agglomerate, resulting in deviations of inherent color tones of the pigments, to disturb an appropriate color mixing.
  • Japanese Patent Application Laid-open No. 56-89594 discloses a method for setting a difference between a pH of an ink and a surface pH of a recording sheet to be not more than 2 to suppress a deviation of color tones.
  • this method there has not been solved a problem that a deviation from inherent color tones of pigment may be raised and then an appropriate color mixing cannot be performed, in case of using an ink for an ink-jet system comprising a pigment that brings a water fastness.
  • a degradation of color tones and an image quality is a serious problem, as a higher recording speed, a higher image density, a higher water fastness, and a capability of using multiple colors are being required.
  • an ink-jet recording method employing a pigment-based ink, in which ink droplets are ejected from an orifice in a recording head in accordance with recording signals to conduct recording on a recording medium comprising a base material and a coating layer disposed thereon, wherein a surface pH of the recording medium is within a stable pH range of the pigment-based ink.
  • a method for the formation of images by applying a pigment-based ink to a recording medium provided with a coating layer by means of an ink-jet recording system, wherein a surface pH of the recording medium is within a stable pH range of the pigment-based ink.
  • a recording medium used for an ink-jet recording system employing a pigment-based ink, comprising a coating layer provided on its surface, the surface pH of which is adjusted so as to be within a stable pH range of the pigment-based ink.
  • ink-jet recording methods suitable for an ink-jet recording system and capable of providing high water and light fastnesses, as well as inks and recording media such as recording paper and transparent sheets for overhead projectors
  • the inventors have found that an ink-jet recording method and a recording medium that can mix the colors appropriately without a deviation of the original color tones of the pigments and is superior in a light transparency at portions printed by an ink-jet recording system, even when a transparent base material such as an OHP film is used, and then the inventors have thus completed this invention.
  • the stable pH region of a pigment-based ink refers to a pH range in which a pigment in an ink does not agglomerate or precipitate.
  • Pigment-based inks for an ink-jet recording system used in the present invention are not particularly limited, but the outline is as follows.
  • an amount of pigment contained in a pigment-based ink is from 1 to 20% by weight, preferably from 2 to 12% by weight.
  • the carbon black used in a black ink is prepared by a furnace method or a channel method, and has a primary particle size of from 15 to 40 m ⁇ , a specific surface area of from 50 to 300 m 2 /g according to the BET method, a DBP oil absorption of from 40 to 150 ml/100 g, a volatile matter of from 0.5 to 10%, and a pH value of from 2 to 9.
  • Commercially available carbon blacks of the above properties include No. 2300, No. 900, MCF 88, No. 33, No. 40, No. 45, NO. 52, MA 7, MA 8, No.
  • the pigments used in a yellow ink include C.I. Pigment Yellow 1, C.I. Pigment Yellow 2, C.I. Pigment Yellow 3, C.I. Pigment Yellow 13, C.I. Pigment Yellow 16, and C.I. Pigment Yellow 83.
  • the pigments used as a magenta ink include C.I. Pigment Red 5, C.I. Pigment Red 7, C.I. Pigment Red 12, C.I. Pigment Red 48 (Ca), C.I. Pigment Red 48 (Mn), C.I. Pigment Red 57 (Ca), C.I. Pigment Red 112, and C.I. Pigment Red 122.
  • the pigments used as a cyan ink include C.I. Pigment Blue 1, C.I. Pigment Blue 2, C.I. Pigment Blue 3, C.I. Pigment Blue 15:3, C.I. Pigment Blue 16, C.I. Pigment Blue 22, C.I. Pigment Blue 4, C.I. Vat Blue 4, and C.I. Vat Blue 6.
  • the present invention is not limited to the above pigments, and those pigments which are newly manufactured for the present invention can also be used.
  • any dispersant for the pigments can be used to the pigment-based inks according to the present invention so far as it is a water-soluble resin, but preferably has a weight average molecular weight of from 1,000 to 30,000, more preferably, from 3,000 to 15,000.
  • the dispersants include a block copolymer obtained from two or more types of monomers (at least one of them is a hydrophilic monomer) selected from the group consisting of styrene and derivatives thereof, vinylnaphthalenes and derivatives thereof, aliphatic alcohol esters of ⁇ , ⁇ -ethylenically unsaturated carboxylic acid, acrylic acid and derivatives thereof, maleic acid and derivatives thereof, itaconic acid and derivatives thereof, and fumaric acid and derivatives thereof; or a random copolymer, a graft copolymer; or salts thereof.
  • a block copolymer obtained from two or more types of monomers (at least one of them is a hydrophilic monomer) selected from the group consisting of styrene and derivatives thereof, vinylnaphthalenes and derivatives thereof, aliphatic alcohol esters of ⁇ , ⁇ -ethylenically unsaturated carboxylic acid, acrylic acid and derivatives thereof, maleic acid and derivative
  • These resins are alkali-soluble resins soluble in a solution, in which a base is dissolved. Furthermore, they may be homopolymers obtained from a hydrophilic monomer and their salts.
  • the dispersants may also be water-soluble resins such as polyvinyl alcohol, carboxymethyl cellulose, condensates of a naphthalene sulfonate with formaldehyde.
  • This dispersant may also be a cationic dispersant such as an acrylic copolymer containing monomer units formed by quaternizing N,N-dimethylaminoethyl methacrylate, N,N-dimethylaminoethyl acrylate, N,N-dimethyl acrylamide, N,N-dimethyl methacrylamide, N,N-dimethylaminopropyl acrylamide, N,N-dimethyl aminopropyl methacrylamide or the like with methyl chloride, dimethyl sulfate, benzyl chloride, or epichlorohydrin.
  • a cationic dispersant such as an acrylic copolymer containing monomer units formed by quaternizing N,N-dimethylaminoethyl methacrylate, N,N-dimethylaminoethyl acrylate, N,N-dimethyl acrylamide, N,N-dimethyl methacrylamide, N,N-dimethyl
  • Alkali-soluble resins are rather advantageous in that a viscosity of a dispersant can be made lower and a dispersion can be performed easily. Furthermore, resins that start to agglomerate at a pH of 6 or less are particularly preferable for improving a recording density.
  • An amount of the water-soluble resin contained in the ink is preferably from 0.1 to 5% by weight based on the total amount of the ink.
  • the pigment-based ink used in the present invention preferably has its entirety regulated so as to be neutral or alkaline in order to improve the solubility of the water-soluble resin and to enable the ink to be stored for a longer period of time.
  • the ink since the ink may cause corrosion at various members in the ink-jet recording apparatus, it desirably has a pH value of from 7 to 10.
  • a pH regulator there may be exemplified various organic amines such as diethanol amine, triethanol amine and the like; inorganic alkali agents such as hydroxides of alkali metal such as sodium hydroxide, lithium hydroxide, potassium hydroxide and the like; organic acids; and mineral acids.
  • organic amines such as diethanol amine, triethanol amine and the like
  • inorganic alkali agents such as hydroxides of alkali metal such as sodium hydroxide, lithium hydroxide, potassium hydroxide and the like
  • organic acids such as sodium hydroxide, lithium hydroxide, potassium hydroxide and the like
  • mineral acids such as sodium hydroxide, lithium hydroxide, potassium hydroxide and the like.
  • the pigments and water-soluble resins are dispersed or dissolved in an aqueous medium.
  • a preferable aqueous medium for the pigment-based ink used in the present invention is a mixed solvent of water and a water-soluble organic solvent, and it is preferably to use an ion exchanged water (deionized water) instead of a common water containing various ions.
  • the water-soluble organic solvents used with water include alkyl alcohols having 1 to 4 carbon atoms such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol and the like; amides such as dimethyl formamide and dimethyl acetamide; ketone or ketoalcohols such as acetone and diacetone alcohol, ethers such as tetrahydrofuran and dioxane; polyalkylene glycols such as polyethylene glycol and polypropylene glycol; alkylene glycols whose alkylene moiety has 2 to 6 carbon atoms such as ethylene glycol, propylene glycol, butylene glycol, triethylene glycol, hexylene glycol and diethylene glycol; 1,2,6-hexanetriol; thiodiglycol; glycerol; lower alkyl ethers of polyhydric alcohol such as
  • polyhydric alcohols such as diethylene glycol and a lower alkyl ethers of polyhydric alcohol such as triethylene glycol monomethyl (or ethyl) ether are preferable.
  • ethanol or isopropyl alcohol not less than 1% to the ink for obtaining an ejection stability. This may be considered because bubbling of a recording liquid can be performed more stably on a thin film resistor by the addition of these solvents.
  • An amount of the water-soluble organic solvent contained in the pigment-based ink used in the present invention is within the range of from 3 to 50% by weight, preferably from 3 to 40% by weight based on the total weight of the recording liquid.
  • An amount of water used is from 10 to 90% by weight, preferably from 30 to 80% by weight based on the total weight of the recording liquid.
  • a surfactant, an antifoaming agent, or a preservative as well as a commercially available water-soluble dye can also be added to the pigment-based ink used in the present invention to provide a recording liquid having desired physical properties as required.
  • the surfactant is not limited unless it affects the storage stability of the ink, and includes anionic surfactants such as fatty acid salts, higher alcohol sulfonate salts, liquid fatty oil sulfonate salts, and alkyl allyl sulfonate salts, and non-ionic surfactants such as polyoxy ethylene alkyl esters, polyoxy ethylene sorbitan alkyl esters, acetylene alcohol, and acetylene glycol. One or two or more of them can be selected as needed appropriately.
  • An amount of the surfactant used in the present invention depends on the dispersant, but is preferably from 0.01 to 5% by weight based on the total amount of the ink.
  • a pigment is added first to a solution containing at least a disperse resin and water.
  • the mixture is agitated, then dispersed using a dispersing means described below, and then centrifuged as needed to obtain a desired dispersion.
  • the compounds used in the present invention and the components mentioned above are then added to the dispersion, and agitated to obtain a recording liquid.
  • the solution containing the pigment can be effectively pre-mixed for thirty minutes or longer before a dispersing treatment. This pre-mixing operation improves a wettability of a surface of pigment in order to facilitate adsorption thereto.
  • the base added to the dispersion in a case of the using an alkali-soluble resin is preferably an organic amine such as monoethanol amine, diethanol amine, triethanol amine, and aminomethyl propanol, or ammonia, or an inorganic base such as potassium hydroxide or sodium hydroxide.
  • Dispersing devices for preparing a pigment-based ink used in the present invention may be any dispersing device generally used, and include a ball mill, a roll mill, or a sand mill. Among them, a high speed sand mill is preferable, and preferable sand mills include Super Mill, Sand Grinder, Beads Mill, Agitator Mill, Glenn Mill, Dyno Mill, Pearl Mill, and Cobol Mill (all of them are trade names).
  • Components used for the coating layer (the ink receiving layer) in the recording medium used in the present invention are not limited as long as it can produce the effects according to the present invention, that is, it can receive an aqueous ink, shows solubility to or affinity for the aqueous ink, and can maintain the surface pH of the recording medium within the stable pH region of the pigment-based ink in which the pigment in the ink does not precipitate when coated on the base material.
  • a single material meeting these conditions may be used, or two or more types of materials may be mixed without causing a problem even if each of them does not meet the conditions, as long as they can be regulated so as to do so.
  • Materials for the ink receiving layer used in the present invention include a synthetic resin such as polyvinyl alcohol, polyvinyl acetal, polyurethane, carboxyethyl cellulose, polyester, polyacrylic acid (ester), hydroxyethyl cellulose, melamine resin, or modifications thereof, or a natural resin such as albumin, gelatin, casein, starch, cationic starch, gum arabic, or sodium alginate, but is not limited to these resins.
  • a synthetic resin such as polyvinyl alcohol, polyvinyl acetal, polyurethane, carboxyethyl cellulose, polyester, polyacrylic acid (ester), hydroxyethyl cellulose, melamine resin, or modifications thereof, or a natural resin such as albumin, gelatin, casein, starch, cationic starch, gum arabic, or sodium alginate, but is not limited to these resins.
  • a plurality of them can also be used simultaneously. Furthermore, in a case of not satisfying conditions that the surface pH of the recording medium with the coating liquid coated thereon is maintained within the stable pH region of the pigment-based ink, i.e., the pigment in the ink does not precipitate, various cationic active agents and anionic active agents, various cationic or anionic polymers or oligomers, and various pH regulators can be mixed. These may be general and publicly known compounds.
  • the anionic compounds are not particularly limited as long as they have an anionic part in its molecules.
  • the anionic surfactants may include, for example, alkylbenzene sulfonic acid salts, alkyl sulfonate salts, alkylnaphthalene sulfonic acid salts, alkyl phosphates, alkyl sulfosuccinic acid salts, condensation products of naphthalene sulfonic acid with formalin, and polyoxyethylenealkyl phosphates.
  • the surfactants may also be ampholytic surfactants of alkylbetaine-, imidazolimiumbetaine-, and alanine- series that include an anionic part.
  • the anionic polymers and oligomers include those having in its molecules a sulfonic group, a carboxylic group, a sulfonate group, a phosphate group, a phenolic hydroxyl group, an alcoholic hydroxyl group.
  • carboxylic radical terminated polyester obtained by reacting a polycarboxylic acid with a polyhydric alcohol, acidic cellulose derivatives modified with various polyhcarboxylic acids, a homopolymer of a vinyl ether ester monomer with a polycarboxylic acid or a copolymer of such a monomer with other general monomer, a homopolymer of (meth)acrylic acid or a copolymer of such a monomer with other general monomer, a homopolymer of ⁇ , ⁇ -unsaturated vinyl monomer with maleic anhydride or itaconic acid and a copolymer of such monomer with other general monomer, a sulfonic acid-modified polymer made from a polyvinyl alcohol or a vinyl alcohol copolymer using a sulfonic acid compound, a compound with a hydroxyl group such as ethyl cellulose, benzyl cellulose, hydroxyethyl cellulose, or
  • the cationic compounds are not particularly limited as long as they include a cationic part in its molecules.
  • the cationic surfactants include quaternary ammonium salt type cationic surfactants such as monoalkyl ammonium chloride, dialkyl ammonium chloride, tetramethyl ammonium chloride, trimethyl phenylammonium chloride, and ethylene oxide-added ammonium chloride, or amine salt type cationic surfactants.
  • the surfactant may also be ampholytic one of alkylbetaine-, imidazolimiumbetaine-, and alanine- series that include an anionic part.
  • the cationic polymers or oligomers include cation-modified polyacrylamide or a copolymer of acrylamide with a cationic monomer, polyallyl amine, polyamine sulfone, polyvinyl amine, polyethylene imine, polyamide-epichlorohydrin resin, and polyvinyl pyridinium halide and the like.
  • the above general monomers include methacrylates, acrylates, acrylonitrile, vinylether, vinyl acetate, ethylene, styrene and the like. They may also be cation-modified polyvinyl alcohol or cellulose. Of course, they are not limited to these compounds.
  • the pH regulators also include ammonia, various organic amines such as diethanol amine and triethanol amine; inorganic alkali agents such as hydrides of alkali metal such as sodium hydroxide, lithium hydroxide, and potassium hydroxide; and organic acids, as described above, as well as inorganic acids.
  • various organic amines such as diethanol amine and triethanol amine
  • inorganic alkali agents such as hydrides of alkali metal such as sodium hydroxide, lithium hydroxide, and potassium hydroxide
  • organic acids as described above, as well as inorganic acids.
  • pH regulators are not particularly limited as long as they satisfy conditions that the surface pH of the recording medium coated with the coating liquid thereon is maintained within the stable pH region of the pigment-based ink in which the pigment in the ink does not precipitate.
  • a composition satisfying the above condition is applied on at least one surface of the base material to obtain a recording medium comprising a base material and an ink receiving layer disposed thereon, and various fillers and additives may be added to the composition to an extent that the object of the present invention is not prevented from being achieved.
  • the fillers include silica, alumina, aluminum silicate, magnesium silicate, basic magnesium carbonate, talc, clay, hydrotalcite, calcium carbonate, titanium oxide, zinc oxide, and plastic pigments such as polyethylene, polystyrene, or polyacrylate, but are not limited to these compounds.
  • the additives include various surfactants, dye fixing agents, antifoaming agents, antioxidants, optical whitening agents, ultraviolet ray absorbent, dispersants, viscosity regulators, mildewproof agents, and plasticizers. These additives can be arbitrarily selected from conventionally publicly known compounds.
  • the base materials constituting the recording medium according to the present invention include paper such as wood free paper, printing paper, art paper, bond paper, recycled paper, baryta paper, cast-coated paper, and corrugated boards; plastic films and plates such as polyethylene terephthalates, diacetates, triacetates, cellophane, celluloid, polycarbonates, polyimides, polyvinyl chlorides, polyvinylidene chlorides, polyacrylates, polyethylene, and polypropylene; glass plates; cloths such as cotton, rayon, acrylic fiber, nylon, silk, and polyester.
  • the base material can be selected from the above materials as appropriate depending on the object of the recording medium, the usage of recorded images, or the adhesion to the components coated on the recording medium.
  • the composition is first dissolved or dispersed in water, alcohol, polyhydric alcohol, or other adequate organic solvents together with other additives as needed, thereby forming a coating liquid.
  • the coating liquid obtained is allied on the surface of the base material using, for example, a roll coater method, a blade coater method, an air knife coater method, a gate roll coater method, a bar coater method, a size press method, a spray coating method, a gravure coater method, or a curtain coater method. Thereafter, for example, a hot air drying furnace or a heat drum is used to dry the coating layer to obtain the recording medium according to the present invention.
  • a super calendar processing can further be performed as required in order to smooth the ink receiving layer or increase the surface intensity.
  • the total amount of the ink receiving layer on the medium is from 0.2 to 50 g/m 2 , preferably from 1 to 30 g/m 2 . If, however, this amount is small, a part of the base material may be exposed.
  • the total coating amount is preferably from 0.5 to 100 ⁇ m in terms of thickness.
  • the method for the recording by applying the ink to the recording medium is preferably an ink-jet recording method, and may be any ink-jet recording method as long as it enables inks to be effectively released from orifices and applied to a recording medium that is a target.
  • FIG. 1 An example of the construction of a head, which is a main component of such an apparatus, is illustrated in Figs. 1, 2 and 3.
  • a head 13 is formed by bonding a glass, ceramic or plastic plate having a groove 14 through which an ink is passed, to a heating head 15, which is used for thermal recording (the drawings show a head to which it, however, the present invention is not limited).
  • the heating head 15 is composed of a protective film 16 made of silicon oxide, aluminum electrodes 17-1 and 17-2, a heating resistor layer 18 made of nichrome, a heat accumulating layer 19, and a substrate 20 made of alumina having a good heat radiating property.
  • An ink 21 comes up to an ejection orifice (a minute opening) 22 and forms a meniscus 23 due to a pressure P.
  • the heating head 15 rapidly generates heat at the region shown by "n” to form bubbles in the ink 21 which is in contact with this region.
  • the meniscus 23 of the ink is projected by the action of the pressure thus produced, and the ink 21 is ejected from the orifice 22 to a recording medium 25 in the form of recording droplets 24.
  • Fig. 3 illustrates a multi-head composed of an array of a number of heads as shown in Fig. 1.
  • the multi-head is formed by bonding a glass plate 27 having a number of grooves 26 to a heating head 28 similar to the head illustrated in Fig. 1.
  • Fig. 1 is a cross section of the head 13 taken along an ink flow passage
  • Fig. 2 is a cutaway view taken along the line 2-2 of Fig. 1.
  • Fig. 4 illustrates an exemplary ink-jet recording apparatus in which this head has been incorporated.
  • reference numeral 61 designates a blade serving as a wiping member, one end of which is a stationary end held by a blade-holding member to form a cantilever.
  • the blade 61 is provided at a position adjacent to a region in which the recording head operates, and in this embodiment, is held in such a form that it protrudes to the course through which the recording head is moved.
  • Reference numeral 62 indicates a cap that is provided at a home position adjacent to the blade 61, and is so constituted that it moves in a direction perpendicular to a direction in which the recording head is moved and comes into contact with the face of the ink-ejecting openings to cap it.
  • Reference numeral 63 denotes an ink-absorbing member provided adjacent to the blade 61 and, similar to the blade 61, held in such a form that it protrudes to the course through which the recording head is moved.
  • the above blade 61, cap 62, and absorbing member 63 constitute an ejection recovery portion 64, where the blade 61 and absorbing member 63 remove water or dust from the face of the ink-ejecting openings.
  • Reference numeral 65 designates the recording head having an ejection-energy-generating means and serving to eject the ink onto the recording medium set in an opposing relation with an ejection opening face provided with ejection openings to conduct recording.
  • Reference numeral 66 indicates a carriage on which the recording head 65 is mounted so that the recording head 65 can be moved.
  • the carriage 66 is slidably interlocked with a guide rod 67 and is connected (not illustrated) at its part to a belt 69 driven by a motor 68.
  • the carriage 66 can be moved along the guide rod 67 and hence, the recording head 65 can be moved from a recording region to a region adjacent thereto.
  • Reference numerals 51 and 52 denote a feeding part from which the recording media are inserted, and feed rollers driven by a motor (not illustrated), respectively. With such a construction, the recording medium is fed to the position opposite to the ejection opening face of the recording head, and discharged from discharge rollers 53 with the progress of recording.
  • the cap 62 in the head recovery portion 64 is receded from the moving course of the recording head 65 when the recording head 65 is returned to its home position, for example, after completion of recording, and the blade 61 remains protruded to the moving course.
  • the ejection opening face of the recording head 65 is wiped.
  • the cap 62 comes into contact with the ejection opening face of the recording head 65 to cap it, the cap 62 is moved so as to protrude to the moving course of the recording head 65.
  • the cap 62 and the blade 61 are at the same positions as the positions upon the wiping as described above. As a result, the ejection opening face of the recording head 65 is also wiped at the time of this movement.
  • the above movement of the recording head to its home position is made not only when the recording is completed or the recording head is recovered for ejection, but also when the recording head is moved between the recording regions for the purpose of recording, during which it is moved to the home position adjacent to each recording region at given intervals, where the ejection opening face is wiped in accordance with this movement.
  • Styrene-acrylic acid-acrylic acid ethyl copolymer (Acid value: 140, weight average molecular weight: 5,000) 1.5 parts, Monoethanol amine 1 part, Ion exchanged water 81.5 parts, and Diethylene glycol 5 parts were mixed and heated to 70°C using a water bath to completely dissolve the resin. 10 parts of C.I. Pigment Red 112 and 1 part of isopropyl alcohol were added to the solution, pre-mixed for 30 minutes, and then dispersed under the following conditions.
  • the solution was further centrifuged at 12,000 rpm for 20 minutes to remove coarse particles, thereby obtaining a dispersed solution.
  • the stable pH region of this pigment-based ink was 7.2 or more.
  • a pH range of the pigment-based ink in which the pigment was sufficiently dispersed was measured by varying a pH value upon adding monoethanol amine and hydrochloric acid where neither precipitation nor agglomeration occurs.
  • the coating liquid obtained was applied on polyethylene terephthalate films having each a thickness of 100 ⁇ m (Lumirror, trade-name, produced by Toray Co) using a wire bar so as to have a dry coating thickness of 10 ⁇ m. Thereafter, the films were then dried at 120°C for five minutes to prepare transparent recording media for the Examples 1 to 4 and Comparative Example 1.
  • the surface pH of the ink receiving layer thus prepared was measured using a paper surface pH meter (produced by Kyoritsu Kagaku Kenkyusho KK). The surface pH values of are also shown in Table 1. Testing Example No. Formulating ratio Surface pH Component (i) Component (ii) Example 1 99.9 0.1 7.5 Example 2 99.5 0.5 8.7 Example 3 99 1 9.6 Example 4 95 5 10.2 Comparative Example 1 100 0 6.8
  • Recording media were prepared as in Example 1 except for the use of following ink, and recording was performed by means of an ink-jet recording apparatus which ejects ink droplets by bubbling an ink upon an application of thermal energy.
  • Example 5 a Cyan Ink was used.
  • Styrene-maleic acid-maleic acid half ester copolymer (Acid value: 70, weight average molecular weight: 12,000) 4 parts, Aminomethyl propanol 2 parts, Ion exchanged water 74 parts, and Diethylene glycol 5 parts were mixed and heated to 70°C using a water bath to completely dissolve the resin. 15 parts of C.I. Pigment Blue 22 was added to the solution, pre-mixed for 30 minutes, and then dispersed under the following conditions.
  • the solution was further centrifuged at 12,000 rpm for 20 minutes to remove coarse particles, thereby obtaining a dispersed solution.
  • This pigment-based ink was stable in a pH range of 7.4 or more.
  • Cyan Ink was prepared as in Example 5 except that the pigment was replaced with C.I. Pigment Blue 3.
  • the stable pH region of this Cyan ink was 7.9 or more.
  • Magenta Ink was prepared as in Example 1 except that the pigment was replaced with C.I. Pigment Red 7.
  • the stable pH region of this Magenta Ink was 7.7 or more.
  • Yellow Ink was prepared as in Example 5 except that the pigment replaced with C.I. Pigment Yellow 13.
  • the stable pH region of this Yellow Ink was 8.0 or more.
  • Black Ink was prepared as in Example 1 except that the pigment was replaced with carbon black (MCF88, trade-name, produced by Mitsubishi Kasei Co).
  • MCF88 carbon black
  • the stable pH region of this Black Ink was 7.8 or more.
  • the coating liquid obtained was applied to polyethylene terephthalate films (Lumirror, trade-name, thickness: 100 ⁇ m, produced by Toray) using a wire bar so as to have each a dry thickness of 15 ⁇ m.
  • the films were then dried at 120°C for five minutes to prepare transparent recording media for Examples 6 to 9 and Comparative Examples 2 and 3.
  • the surface pH values of respective ink receiving layer thus prepared were measured using the paper surface pH meter (produced by Kyoritsu Kagaku Kenkyusho KK). The surface pH values are also shown in Table 2.
  • Glossy recording media according to the present invention were prepared as in Example 6 except for the use of art paper and wood free paper.
  • a density of the black (Bk) solid paints obtained by the above printer (200% duty) was evaluated by means of a Macbeth densitometer RD-918.
  • Image irregularity on each solid paint obtained by the above printer was measured visually and ranked as "A” where no image irregularity of was observed; "C” where image irregularity could be observed when the sample was seen 50 cm away from naked eyes; and "B” where an image irregularity was between "A” and "C".
  • the paints obtained above were projected by a transparent-type overhead projector, and color tones and light transmittance of images were ranked as "A” where no problem was observed; "B” where color tone was somewhat changed against a color tone of used ink, or projected images were somewhat darkened; and "C” where color tone was evidently changed against a color tone of used ink, or projected images were darkened.
  • Example 3 The results of evaluation are shown in Table 3. Testing Example No. Evaluated items Image density Image irregularity Color tone and light transmittance of image Example 1 - A A Example 2 - A A Example 3 - A A Example 4 - A A Example 5 - A A Example 6 1.51 A A Example 7 1.49 A A Example 8 1.45 A A Example 9 1.44 A A Example 10 - A A (Tone only) Example 11 - A A (Tone only) Comparative Example 1 - B C Comparative Example 2 1.22 B C Comparative Example 3 1.35 B C
  • the present invention provides an ink-jet recording method and a recording medium that can perform color-mixing appropriately without deviations of the inherent tones of pigments even when pigment-based inks are used for improving the water and light fastness of images and that are excellent in a light transparency of printed portions by an ink-jet recording system, even when a transparent base material such as an OHP film is used. Therefore, the present invention is significantly effective.
  • an ink-jet recording method employing a pigment-based ink, in which ink droplets are ejected from an orifice in a recording head in accordance with recording signals to conduct recording on a recording medium comprising a base material and a coating layer disposed thereon, wherein a surface pH of the recording medium is within a stable pH range of the pigment-based ink.

Claims (11)

  1. Procédé d'enregistrement par jets d'encre utilisant une encre à base d'un pigment, dans lequel des gouttelettes d'encre sont éjectées par un orifice présent dans une tête d'enregistrement en fonction de signaux d'enregistrement pour effectuer un enregistrement sur un support d'enregistrement comprenant une matière de base et une couche de revêtement présente sur cette matière de base, le pH de surface du support d'enregistrement étant compris dans une plage de pH de stabilité de l'encre à base de pigment.
  2. Procédé d'enregistrement par jets d'encre suivant la revendication 1, dans lequel l'encre à base de pigment comprend un pigment, un dispersant et un milieu liquide.
  3. Procédé d'enregistrement par jets d'encre suivant la revendication 2, dans lequel le dispersant est une résine hydrosoluble.
  4. Procédé d'enregistrement par jets d'encre suivant la revendication 3, dans lequel la résine hydrosoluble a une moyenne pondérale du poids moléculaire comprise dans l'intervalle de 1000 à 30 000.
  5. Procédé d'enregistrement par jets d'encre suivant la revendication 3, dans lequel la résine hydrosoluble a une moyenne pondérale du poids moléculaire comprise dans l'intervalle de 3000 à 15 000.
  6. Procédé d'enregistrement par jets d'encre suivant la revendication 3, dans lequel la résine hydrosoluble est une résine soluble en milieu alcalin.
  7. Procédé d'enregistrement par jets d'encre suivant la revendication 1, dans lequel l'encre à base de pigment a un pH compris dans l'intervalle de 7 à 10.
  8. Procédé d'enregistrement par jets d'encre suivant la revendication 1, dans lequel la couche de revêtement contient une résine présentant une solubilité dans, ou une affinité pour, une encre aqueuse.
  9. Procédé d'enregistrement par jets d'encre suivant la revendication 1, dans lequel le support d'enregistrement est transparent.
  10. Procédé d'enregistrement par jets d'encre suivant la revendication 1, dans lequel le support d'enregistrement est brillant.
  11. Procédé d'enregistrement par jets d'encre suivant la revendication 1, dans lequel l'encre à base d'un pigment est éjectée par application d'énergie thermique.
EP95118081A 1994-11-17 1995-11-16 Enregistrement par jet d'encre, méthodes pour former des images et matériau d'enregistrement Expired - Lifetime EP0712735B1 (fr)

Applications Claiming Priority (2)

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JP283158/94 1994-11-17
JP28315894A JP3320224B2 (ja) 1994-11-17 1994-11-17 記録媒体の製造方法及びそれを用いたインクジェット記録方法

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EP0712735B1 true EP0712735B1 (fr) 1999-04-21

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EP2838736B1 (fr) 2012-04-17 2018-06-06 Hewlett-Packard Development Company, L.P. Support d'impression comprenant une couche supérieure
EP3532552B1 (fr) 2017-04-11 2020-10-28 Hewlett-Packard Development Company, L.P. Ensembles d'encres

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EP0657299A2 (fr) * 1993-10-27 1995-06-14 Canon Kabushiki Kaisha Méthode d'impression à jet d'encre et procédé d'impression

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JPS5880368A (ja) 1981-11-07 1983-05-14 Sakura Color Prod Corp 筆記具用顔料水性インキ組成物
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DE69509194T2 (de) 1999-11-18
JPH08142495A (ja) 1996-06-04
DE69509194D1 (de) 1999-05-27
JP3320224B2 (ja) 2002-09-03
EP0712735A1 (fr) 1996-05-22

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