EP0743193A1 - Moyen d'impression et méthode d'impression à jet d'encre l'utilisant - Google Patents

Moyen d'impression et méthode d'impression à jet d'encre l'utilisant Download PDF

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Publication number
EP0743193A1
EP0743193A1 EP96107934A EP96107934A EP0743193A1 EP 0743193 A1 EP0743193 A1 EP 0743193A1 EP 96107934 A EP96107934 A EP 96107934A EP 96107934 A EP96107934 A EP 96107934A EP 0743193 A1 EP0743193 A1 EP 0743193A1
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EP
European Patent Office
Prior art keywords
ink
printing
printing medium
surface layer
pigment
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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.)
Ceased
Application number
EP96107934A
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German (de)
English (en)
Inventor
Mifune C/O Canon K.K. Hirose
Mamoru C/O Canon K.K. Sakaki
Akio C/O Canon K.K. Kashiwazaki
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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
    • 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
    • B41M5/506—Intermediate layers
    • 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

Definitions

  • the present invention relates to a printing medium which has excellent ink absorbency and provides an image excellent in coloring, gloss and fastness properties, a printing method using such a printing medium, and a method of producing a print.
  • Ink-jet printing systems have attracted attention because of ready attainment of high-speed, full-color and high-density printing.
  • Printing apparatus making good use of an ink-jet printing system have also spread.
  • printing paper applied to such an ink-jet printing system may be mentioned exclusive coated paper described in, for example, Japanese Patent Application Laid-Open No. 59-35977.
  • such inks are water-soluble, so that the water fastness of the image printed also often becomes a problem. Namely, when the printed image is exposed to the rain or splashed with sweat or drinking water, the image may become blurred or faded.
  • Ballpoint pens and markers using a water-based pigment ink have recently come to be marketed as commercial products.
  • pigment inks using a water-based pigment ink pigment inks using a specific water-soluble solvent and a polymeric dispersant have been proposed in Japanese Patent Application Laid-Open Nos. 56-147859 and 56-147860, etc.
  • printing media for ink-jet are also required to have higher and wider properties. More specifically, they are required to simultaneously satisfy, for example, the following properties:
  • a printing medium comprising a surface layer having liquid permeability and an ink-retaining layer, wherein a pore volume of pores corresponding to a peak not greater than 100 nm in a pore diameter distribution curve of the printing medium is at most 0.015 cc/g, a pore volume of pores corresponding to at least one of peaks greater than 100 nm is at least 0.015 cc/g, and the pH of the surface layer is at least 8.
  • a printing process comprising ejecting inks, which each comprise pigment particles having an average particle diameter within a range of from 100 nm to 500 nm, from ejection orifices in response to printing signals to apply the inks in the form of droplets to the printing medium described above.
  • a process of producing a print comprising applying inks, which each comprise pigment particles having an average particle diameter within a range of from 100 nm to 500 nm, to the surface layer of the printing medium described above by an ink-jet system, thereby forming an image on the ink-retaining layer through the surface layer.
  • Fig. 1 is a longitudinal cross section, taken along the flow path of ink, illustrating an example of the construction of a head of an ink-jet printing apparatus suitable for use in conducting printing on a printing medium according to the present invention.
  • Fig. 2 is a transverse cross section, taken along line 2-2, of the head shown in Fig. 1.
  • Fig. 3 is a perspective view of the appearance of an illustrative multi-head.
  • Fig. 4 illustrates an exemplary ink-jet printing apparatus in which the head has been incorporated.
  • a principal feature of the present invention resides in that printing is conducted with inks each comprising, as a principal component of a printing agent, a pigment on a printing medium, in which the printing surface and the viewing surface have an opposite relation to each other, unlike the conventional printing media in which the printing surface is identical with the viewing surface.
  • the printing is conducted with the inks on the surface layer which is a printing side, and an image printed is viewed from the side of the ink-retaining layer, which is a viewing side.
  • the surface layer has good liquid permeability, i.e., a function of rapidly absorbing and transmitting the ink applied to the surface thereof.
  • the surface layer must have high affinity for a liquid medium in the ink and at the same time have rather low affinity for the pigment as the printing agent, and must be so constructed that the pigment can pass through pores in the surface layer. If the pores are smaller than the particle diameter of the pigment, the pigment cannot pass through the pores and remains on the printing surface side, which causes a problem that an image formed becomes low in optical density and poor in coloring when the image is viewed from the viewing surface side.
  • the surface layer must be constructed in such a manner that materials which have no properties of wetting, penetration, diffusion and the like to the liquid medium in the ink are selected, and its pores become greater than the particle diameter of the pigment, while the pH of the surface layer must be adjusted to such a moderate pH (within a stable pH region) that the pigment in the ink undergoes no aggregation when the ink passes through the pores in the surface layer.
  • the ink-retaining layer must have ink absorptivity stronger than the surface layer for the purpose of absorbing and capturing the ink temporarily absorbed in the surface layer therein.
  • the ink-retaining layer must have high affinity not only for the liquid medium in the ink but also for the printing agent in the ink. It is more preferable that the pH of the ink-retaining layer should fall within a pH region (be lower than any pH within the stable pH region) in which the pigment in the ink aggregates, because the water fastness and moisture fastness of the resulting image is more improved.
  • the pH of the surface layer or ink-retaining layer in the present invention is a value measured in accordance with the Surface pH Measurement of Paper (J. TAPPI Test Methods for Paper and Pulp, No. 6-A).
  • the printing medium comprises a base material as a substrate, an ink-retaining layer formed on the substrate and serving to substantially absorb and capture an ink or a printing agent therein, and a surface layer formed on the ink-retaining layer and serving to directly receive the ink and substantially not retain the ink therein.
  • a pore volume of pores corresponding to a peak not greater than 100 nm in a pore diameter distribution curve of the printing medium is at most 0.015 cc/g
  • a pore volume of pores corresponding to at least one of peaks greater than 100 nm is at least 0.015 cc/g.
  • the base material is not always necessary if the surface layer or the ink-retaining layer combines the function as the substrate.
  • Any conventionally known base material may be used as the base material used in the present invention.
  • Specific examples thereof include light-transmitting base materials such as plastic films, sheets or plates composed of polyester resins, diacetate resins, triacetate resins, polystyrene resins, polyethylene resins, polycarbonate resins, polymethacrylate resins, cellophane, celluloid, polyvinyl chloride resins, polyimide resins and the like, and glass sheets or plates.
  • the base material may be subjected to any processing so far as the processed base material retains its good light transmitting properties.
  • the surface layer making up the printing medium according to the present invention is required to have good liquid permeability.
  • liquid permeability refers to a nature that an ink is rapidly passed through so as substantially not to retain a printing agent in the ink in the surface layer.
  • a preferred embodiment for improving the liquid permeability is to have the surface layer have a porous structure with cracks or communicating pores in the interior of the surface layer.
  • the average particle diameter of pigment particles in an ink to be used in the present invention is generally within a range of from 100 nm to 500 nm, it is also essential that a pore volume of pores corresponding to a peak not greater than 100 nm in a pore diameter distribution curve of the printing medium be at most 0.015 cc/g, and a pore volume of pores corresponding to at least one of peaks greater than 100 nm be at least 0.015 cc/g. If the pore volume of the pores corresponding to the peak not greater than 100 nm is greater than 0.015 cc/g, the pigment particles in the ink are retained in the surface layer, so that an image having sufficient optical density and brightness cannot be formed. Similarly, the diameter of pores corresponding to the peak greater than 100 nm in the pore diameter distribution curve must be greater than the average particle diameter of the pigment particles.
  • the resulting printing medium becomes deteriorated in liquid permeability and can provide only an image lowered in optical density and brightness.
  • the pore diameter distribution curve referred to in the present invention is determined by the mercury intrusion porosimetry.
  • Porosimeter Poresizer 9320 (trade name, manufactured by Shimadzu Corporation).
  • the surface layer Since a reflection image printed is viewed from the opposite side to the printing surface in the present invention as described above, it is preferable that the surface layer have good light diffusing properties.
  • the surface layer satisfying the above properties is composed principally of resin particles and a binding agent.
  • At least one of organic pigments such as thermoplastic resins and thermosetting resins having no adsorptivity to printing agents, for example, powders and emulsions of resins such as polyethylene, polymethacrylates, elastomers, ethylene-vinyl acetate copolymers, styrene-acrylic copolymers, polyesters, polyacrylates and polyvinyl ethers, may be used as desired.
  • resins such as polyethylene, polymethacrylates, elastomers, ethylene-vinyl acetate copolymers, styrene-acrylic copolymers, polyesters, polyacrylates and polyvinyl ethers
  • the resin particles used in the present invention are not limited to the above resin particles, and any well-known material may be used so far as it has no adsorptivity to the printing agents.
  • the preferable particle diameter of the resin particles is within a range of from 0.3 to 20 ⁇ m, more preferably from 0.5 to 12 ⁇ m. If the particle diameter is smaller than the lower limit of the above range, the penetrability of the pigment particles in the ink becomes insufficient, so that difficulty is encountered on the formation of an image having a sufficient optical density. If the particle diameter is greater than the upper limit of the above range on the other hand, the roundness of dots to be formed on the resulting surface layer tends to be impaired, and so the resulting image gives a rough feeling.
  • the binding agent used in the present invention has a function of binding the resin particles to each other and/or to the ink-retaining layer and is required to have no adsorptivity to the printing agents like the resin particles.
  • any conventionally-known material may be used so far as it has the above function.
  • resins such as polyvinyl alcohol, acrylic resins, styrene-acrylic copolymers, ethylene-vinyl acetate copolymers, starch, polyvinyl butyral, gelatin, casein, ionomers, gum arabic, carboxymethylcellulose, polyvinyl pyrrolidone, polyacrylamide, phenol resins, melamines, epoxies and styrene-butadiene rubber may be used as desired.
  • resins such as polyvinyl alcohol, acrylic resins, styrene-acrylic copolymers, ethylene-vinyl acetate copolymers, starch, polyvinyl butyral, gelatin, casein, ionomers, gum arabic, carboxymethylcellulose, polyvinyl pyrrolidone, polyacrylamide, phenol resins, melamines, epoxies and s
  • the materials as described above are used to adjust the pH of the surface layer to at least 8, preferably within a range of from 8 to 10.
  • the pH of the surface layer is lower than 8
  • the pigment in the ink tends to aggregate in the surface layer, so that the optical density of the resulting image becomes insufficient when viewed from the side of the ink-retaining layer.
  • the coloring of the resulting image tends to be lowered.
  • anionic surfactants may be mentioned alkylbenzenesulfonates, salts of alkylsulfates, alkylnaphthalenesulfonates, alkylphosphates, alkylsulfosuccinates, naphthalenesulfonic acid-formalin condensates and polyoxyethylene alkylphosphates.
  • Amphoteric surfactants such as alkylbetaine, imidazolinium betaine and alanine type surfactants containing an anionic part may also be included.
  • the anionic polymers or oligomers include those having a sulfonic group, carboxyl group, sulfate group, phosphate group, phenolic hydroxyl group, alcoholic hydroxyl group and/or the like in their molecules. All polymers and oligomers having a sulfonic group, carboxyl group, sulfate group, phosphate group, phenolic hydroxyl group, alcoholic hydroxyl group and/or the like, for example, carboxyl group-terminated polyesters obtained by reacting a polycarboxylic acid with a polyhydric alcohol; acid cellulose derivatives modified by various polycarboxylic acids; homopolymers of vinyl ether ester monomers and the like of polycarboxylic acids, or their copolymers with other common monomers, homopolymers of (meth)acrylic acid and the like, or their copolymer with other common monomers; homopolymers of ⁇ , ⁇ -unsaturated vinyl monomers such as maleic anhydride and ita
  • cationic surfactants examples include quaternary ammonium salt type cationic surfactants such as monoalkylammonium chlorides, dialkylammonium chlorides, tetramethylammonium chloride, trimethylphenylammonium chloride and ethylene oxide-added ammonium chlorides; and amine salt type cationic surfactants.
  • Amphoteric surfactants such as alkylbetaine, imidazolinium betaine and alanine type surfactants containing an cationic part may also be included.
  • cationic polymers and oligomers examples include cationically modified products of polyacrylamide, copolymers of acrylamide with a cationic monomer, polyallylamine, polyamine-sulfone, polyvinylamine, polyethylene-imine, polyamide-epichlorohydrin resins and polyvinylpyridinium halides.
  • Homopolymers of vinylpyrrolidone type monomers or their copolymers with other common monomers homopolymers of vinyloxazolidone type monomers or their copolymers with other common monomers; and homopolymers of vinylimidazole type monomers or their copolymers with other common monomers may also be included.
  • Examples of the common monomers include methacrylates, acrylates, acrylonitrile, vinyl ether, vinyl acetate, ethylene and styrene. Cationically modified polyvinyl alcohol, cellulose and the like may also be used. It goes without saying that the cationic substances are not limited to these surfactants and polymers or oligomers.
  • pH adjustors examples include ammonia, various organic amines such as diethanolamine and triethanolamine, inorganic alkalizing agents such as alkali metal hydroxides such as sodium hydroxide, lithium hydroxide and potassium hydroxide, organic acids, and inorganic acids.
  • Two of more of these various compounds may be used at the same time.
  • additives for example, a surfactant, penetrant, crosslinking agent and/or the like, may be added to the surface layer.
  • a mixing ratio by weight of the resin particles to the binding agent is preferably within a range of from 1:2 to 50:1, more preferably from 3:1 to 20:1.
  • the mixing ratio is lower than 1:2, the cracks or communicating pores in the resulting surface layer become small, so that its ink-absorbing effect is lessened. If the mixing ratio exceeds 50:1 on the other hand, the resin particles cannot be sufficiently bonded to each other and/or to the ink-retaining layer, resulting in a failure to form the surface layer.
  • the thickness of the surface layer may vary depending upon the quantity of ink droplets to be applied, but is preferably within a range of from 1 to 200 ⁇ m, more preferably from 3 to 50 ⁇ m.
  • the ink-retaining layer which substantially captures the ink or printing agent therein, serves to absorb and capture the ink coming to pass through the surface layer, thereby substantially permanently retaining them therein.
  • the ink-retaining layer is required to have ink absorptivity stronger than that of the surface layer because if the absorptivity of the ink-retaining layer is weaker than that of the surface layer, the ink applied to the surface of the surface layer is partially retained in the surface layer at the time the ink passes through the surface layer, and the leading end of the ink reaches the ink-retaining layer, so that the ink penetrates and diffuses in a lateral direction of the surface layer at the interface between the surface layer and the ink-retaining layer. As a result, the resolving power of an image printed is reduced, resulting in a failure to form a high-quality image.
  • the ink-retaining layer is also required to have good light transmitting properties because the image formed is viewed from the opposite side to the printing surface as described above.
  • the ink-retaining layer satisfying the above requirements is preferably composed of a light-transmitting cationic resin, which adsorbs the printing agent, and/or a light-transmitting hydrophilic resin having good solubility and swelling properties in the ink.
  • the thickness of the ink-retaining layer is preferably sufficient to absorb and capture the ink.
  • the thickness is preferably within a range of from 1 to 50 ⁇ m, more preferably from 3 to 20 ⁇ m though it may varies according to the quantity of ink droplets to be applied.
  • the pH of the ink-retaining surface is preferably not higher than 6, more preferably within a range of from 4 to 6.
  • the pH of the ink-retaining layer falls within this range, the pigment which has reached the ink-retaining layer undergoes moderate aggregation on the surface of the ink-retaining layer or in the interior thereof, so that an image which causes little bleeding and has excellent water fastness and moisture fastness can be formed.
  • the above-described various cationic or anionic surfactants, various cationic or anionic polymers or oligomers, and various pH adjustors may be used in combination.
  • the ink-retaining layer and the surface layer on the substrate it is preferable to use a process in which the above-described respective materials are separately dispersed in a proper solvent to prepare coating formulations, and the coating formulations are applied to the substrate in that order by means of the conventionally-known method, for example, a roll coating, rod bar coating, spray coating or air knife coating process, and then quickly dried.
  • a process in which the materials are applied by hot melt coating, or a process in which individual single sheets are formed from the materials, and the thus-formed sheets are laminated on the substrate may be used.
  • the ink-receiving layer is provided on the substrate, it is necessary to firmly bond the substrate to the ink-retaining layer so as to annihilate space.
  • the presence of a space between the substrate and the ink-retaining layer is not preferred because irregular reflection occurs on the surface of a printed image, so that the optical density of a substantial image is reduced.
  • the printing surface and the viewing surface have an opposite relation to each other.
  • characters are printed, it is therefore necessary to use an apparatus capable of printing reflected-image characters unlike the conventional apparatus.
  • the amount of a pigment contained in each of the pigment inks used in the present invention is preferably within a range of from 1 to 20 % by weight, preferably from 2 to 12 % by weight based on the total weight of the ink. Any pigments may be used in the present invention.
  • carbon black used in, for example, a black ink there may be used those produced in accordance with the furnace process or channel process and having such properties that the primary particle diameter is within a range of from 15 to 40 nm, the specific surface area is within a range of from 50 to 300 m 2 /g as determined in accordance with the BET method, the oil absorption is within a range of from 40 to 150 ml/100 g as determined by using DBP, the volatile matter is within a range of from 0.5 to 10 %, and the pH is within a range of from 2 to 9.
  • commercially-available carbon black products such as No. 2300, No. 900, MCF 88, No. 33, No. 40, No. 45, No.
  • Pigment Yellow 16 and C.I. Pigment Yellow 83 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; and 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. Vat Blue 4 and C.I. Vat Blue 6, respectively.
  • the pigments are not limited to these pigments. It goes without saying that those newly prepared for the practice of the present invention may also be used in addition to the above pigments.
  • any resin may be used without any particular limitation so far as it is a water-soluble resin.
  • those having a weight average molecular weight ranging from 1,000 to 30,000, more preferably from 3,000 to 15,000 may preferably be used.
  • dispersants include block copolymers, random copolymers and graft copolymers composed of at least two monomers (at least one monomer being hydrophilic) selected from the group consisting of styrene, styrene derivatives, vinylnaphthalene, vinylnaphthalene derivatives, aliphatic alcohol esters of ⁇ , ⁇ -ethylenically unsaturated carboxylic acids, acrylic acid, acrylic acid derivatives, maleic acid, maleic acid derivatives, itaconic acid, itaconic acid derivatives, fumaric acid, fumaric acid derivatives, and the like, and salts of these copolymers.
  • These resins are alkali-soluble resins which dissolve in an aqueous solution of a base. Further, homopolymers composed of a hydrophilic monomer, or salts thereof may be used. It is also possible to use water-soluble resins such as polyvinyl alcohol, carboxymethylcellulose and naphthalenesulfonic acid-formaldehyde condensates.
  • Cationic dispersants such as acrylic copolymers containing monomer units composed of N,N-dimethylaminoethyl methacrylate, N,N-dimethylaminoethyl acrylate, N,N-dimethylaminoacrylamide, N,N-dimethylaminomethacrylamide, N,N-dimethylaminopropylacrylamide, N,N-dimethylaminopropylmethacrylamide or the like, which has been quaternized with methyl chloride, dimethylsulfuric acid, benzyl chloride, eqichlorohydrin or the like, may also be used.
  • the ink used in the present invention be adjusted to neutrality or alkalinity as the whole because the solubility of the water-soluble resin is enhanced, so that the ink can be provided as an ink far excellent in long-term storability.
  • the pH be adjusted to a range of from 7 to 10 because too high alkalinity forms the cause that various parts used in an ink-jet printing apparatus may be corroded.
  • the pigment and the water-soluble resin as described above are dispersed or dissolved in an aqueous medium.
  • An aqueous medium suitable for use in the inks used in the present invention is a mixed solvent of water and a water-soluble organic solvent.
  • water it is preferable to use ion-exchanged water such as deionized water instead of tap water containing various ions.
  • 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 and tert-butyl alcohol; amides such as dimethylformamide and dimethylacetamide; ketones and keto-alcohols such as acetone and diacetone alcohol; ethers such as tetrahydrofuran and dioxane; polyalkylene glycols such as polyethylene glycol and polypropylene glycol; alkylene glycols the alkylene moiety of which has 2 to 6 carbon atoms, such as ethylene glycol, propylene glycol, butylene glycol, triethylene glycol, thiodiglycol, hexylene glycol and diethylene glycol; 1,2,6-hexanetriol; glycerol; lower alkyl ethers of polyhydric
  • the content of the water-soluble organic solvent in the ink used in the present invention is generally within a range of from 3 to 50 %, preferably from 3 to 40 % by weight based on the total weight of the ink, while the content of water used is within a range of from 10 to 90 % by weight, preferably from 30 to 80 % by weight based on the total weight of the ink.
  • Each of the inks used in the present invention is prepared in the following manner.
  • the pigment is first added to an aqueous solution containing at least the water-soluble resin as a dispersant and water, and the mixture is stirred.
  • a dispersion treatment is then conducted in accordance with a dispersing means described below, and as needed, a centrifugation is carried out to obtain a desired dispersion.
  • Optional additive components usable in the present invention are then added to the dispersion, and the resultant mixture is stirred to prepare an ink.
  • premixing it is more effective to conduct premixing for at least 30 minutes before the aqueous solution containing the pigment is subjected to the dispersion treatment.
  • This premixing serves to improve the wettability of the surface of the pigment and facilitate adsorption of the dispersant on the pigment surface.
  • Any dispersing machine commonly used may be employed as a dispersing machine used in the present invention.
  • a dispersing machine used in the present invention may be mentioned ball mills, roll mills and sand mills.
  • a high-speed sand mill may preferably be used.
  • examples thereof include Super Mill, Sand Grinder, Beads Mill, Agitator Mill, Grain Mill, Dyno Mill, Pearl Mill and Coball Mill (all, trade names).
  • a pigment having a desired particle size distribution may be mentioned techniques in which the size of a grinding medium in a dispersing machine is made smaller, in which the packing rate of a grinding medium is made higher, in which processing time is made longer, in which discharging rate is made lower, and in which classification is conducted by filter, centrifugal separator or the like after grinding. Any combination thereof may also be included.
  • the average particle diameter of the pigment particles in the pigment inks used in the present invention is within a range of from 100 to 500 nm, preferably from 100 to 200 nm in terms of aggregates of primary particles.
  • the average particle diameter of the pigment particles can be measured by any conventionally-known method such as a centrifugal precipitation method, X-ray transmission method, laser diffractiometry or sieving method.
  • FIG. 1 An illustrative example of an ink-jet printing apparatus, which is suitable for use in conducting printing with the printing medium according to the present invention, will hereinafter be described.
  • Examples of the construction of a head, which is a main part of such an apparatus, are illustrated in Figs. 1, 2 and 3.
  • a head 13 is formed by bonding a glass, ceramic or plastic plate or the like 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, however, the invention is not limited).
  • the heating head 15 is composed of a protective film 16 made of silicon oxide or the like, aluminum electrodes 17-1 and 17-2, a heating resistor layer 18 made of nichrome or the like, a heat accumulating layer 19, and a substrate 20 made of alumina or the like 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.
  • Fig. 3 illustrates an appearance of a multi-head composed of an array of a number of heads as shown in Fig. 1.
  • the multi-head is formed by closely bonding a glass plate 27 having a number of grooves 26 to a heating head 28 similar to the head as illustrated in Fig. 1.
  • Fig. 1 is a cross-sectional view of the printing head 13 taken along the flow path of ink
  • Fig. 2 is a cross-sectional view taken along line 2-2 in Fig. 1.
  • Fig. 4 illustrates an example of an ink-jet printing apparatus in which such a 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 a printing head operates, and in this embodiment, is held in such a form that it protrudes into the course through which the printing head is moved.
  • Reference numeral 62 indicates a cap, which is provided at a home position adjacent to the blade 61, and is so constructed that it moves in a direction perpendicular to a direction in which the printing head is moved, and comes into contact with the face of ejecting openings to cap it.
  • Reference numeral 63 denotes an ink-absorbing member provided adjoiningly to the blade 61 and, similar to the blade 61, held in such a form that it protrudes into the course through which the printing head is moved.
  • the above-described blade 61, cap 62 and absorbing member 63 constitute an ejection-recovery portion 64, where the blade 61 and absorbing member 63 remove water, dust and/or the like from the face of the ink-ejecting openings.
  • Reference numeral 65 designates the printing head having an ejection-energy-generating means and serving to eject the ink onto a printing medium set in an opposing relation to the ejection opening face provided with the ejection openings to conduct printing.
  • Reference numeral 66 indicates a carriage on which the printing head 65 is mounted so that the printing 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 printing head 65 can be moved from a printing region to a region adjacent thereto.
  • Reference numerals 51 and 52 denote a feeding part from which the printing media are separately inserted, and feed rollers driven by a motor (not illustrated), respectively. With such a construction, the printing medium is fed to the position opposite to the ejection opening face of the printing head 65, and discharged from a discharge section provided with discharge rollers 53 with the progress of printing.
  • the cap 62 in the head recovery portion 64 is receded from the path of motion of the printing head 65 when the printing head 65 is returned to its home position, for example, after completion of printing, and the blade 61 remains protruded into the path of motion. As a result, the ejection opening face of the printing head 65 is wiped. When the cap 62 comes into contact with the ejection opening face of the printing head 65 to cap it, the cap 62 is moved so as to protrude into the path of motion of the printing head 65.
  • the cap 62 and the blade 61 are at the same positions as the positions for the wiping as described above. As a result, the ejection opening face of the printing head 65 is also wiped at the time of this movement.
  • the above movement of the printing head 65 to its home position is made not only when the printing is completed or the printing head is recovered for ejection, but also when the printing head 65 is moved between printing regions for the purpose of printing, during which it is moved to the home position adjacent to each printing region at given intervals, where the ejection opening face is wiped in accordance with this movement.
  • Styrene-acrylic acid-ethyl acrylate copolymer (acid value: 140, weight average molecular weight: 5,000) 1.5 parts Ethanolamine 1 part Deionized water 81.5 parts Diethylene glycol 5 parts.
  • the dispersion was further subjected to a centrifugal treatment (12,000 rpm, 20 minutes) to remove coarse particles into a dispersion.
  • the above components were mixed to prepare a pigment ink of a magenta color.
  • the average particle diameter of the pigment particles in the ink was measured by a coulter counter and was found to be 120 nm.
  • a stable pH region to this pigment ink was 7.2 or higher.
  • the stable pH region to the pigment ink was determined by changing the pH of the pigment ink kept in a good dispersion state using monoethanolamine and hydrochloric acid to measure a pH region in which the pigment neither precipitated nor aggregated.
  • a pigment ink of a cyan color was prepared in exactly the same manner as in the magenta ink except that the pigment was changed to C.I. Pigment Blue 22.
  • a stable pH region as determined in the same manner as described above was 7.4 or higher.
  • the average particle diameter of the pigment particles in the ink was measured by a coulter counter and was found to be 130 nm.
  • a pigment ink of a yellow color was prepared in exactly the same manner as in the magenta ink except that the pigment was changed to C.I. Pigment Yellow 13.
  • a stable pH region as determined in the same manner as described above was 8.0 or higher.
  • the average particle diameter of the pigment particles in the ink was measured by a coulter counter and was found to be 125 nm.
  • a pigment ink of a black color was prepared in exactly the same manner as in the magenta ink except that the pigment was changed to carbon black (MCF 88, trade name, product of Mitsubishi Chemical Industries Limited).
  • the average particle diameter of the pigment particles in the ink was measured by a coulter counter and was found to be 100 nm.
  • a stable pH region as determined in the same manner as described above was 7.8 or higher.
  • a polyethylene terephthalate film (thickness: 100 ⁇ m, product of Toray Industries, Inc.) was used as a light-transmitting base material, coated with the following composition A by a bar coater process so as to give a dry coating thickness of 8 ⁇ m, and then dried at 120°C for 5 minutes in a drying oven.
  • Composition A A:
  • Polyvinyl pyrrolidone (PVPK-90, trade name, product of GAF Corp., 10 % DMF solution) 78 parts Novolak type phenol resin (Resitop PSK-2320, trade name, product of Gun-ei Chemical Industry Co., Ltd., 10 % DMF solution) 12 parts Polyallylamine hydrochloride (PAA-HCl, product of Nitto Boseki Co., Ltd.). 10 parts
  • composition B was applied onto the thus-formed coating layer by the bar coater process so as to give a dry coating thickness of 15 ⁇ m, and then dried at 80°C for 10 minutes in the drying oven.
  • the pH of the resultant layer was 5.4.
  • Composition B is a composition of Composition B:
  • Fine powder of silicone resin (Tospearl 120, trade name, product of Toshiba Silicone Co., Ltd., particle diameter: 2 ⁇ m) 100 parts Ethylene-vinyl acetate copolymer resin (Chemipearl V-100, trade name, product of Mitsui Petrochemical Industries, Ltd., solids content: 40 %, particle diameter: 5 ⁇ m) 10 parts Sodium polycarbonate type surfactant (Demol EP, trade name, product of Kao Corporation). 1 part
  • the thus-obtained printing medium was white-opaque.
  • the pH of the resultant surface layer was 8.3.
  • Example 2 The same polyethylene terephthalate film as that used in Example 1 was used as a light-transmitting base material, coated with the following composition C by a bar coater process so as to give a dry coating thickness of 5 ⁇ m, and then dried at 110°C for 10 minutes in a drying oven.
  • Composition C is a composition having Composition C:
  • Polyvinyl pyrrolidone (PVPK-90, trade name, product of GAF Corp., 10 % DMF solution) 74 parts Styrene-acrylic acid copolymer (Oxylac SH-2100, trade name, product of Nippon Shokubai Kagaku Kogyo Co., Ltd., 10 % DMF solution) 16 parts Polyallylamine hydrochloride (PAA-HCl, product of Nitto Boseki Co., Ltd.). 10 parts
  • composition D was applied onto the thus-formed coating layer by the bar coater process so as to give a dry coating thickness of 20 ⁇ m, and then dried at 80°C for 10 minutes in the drying oven.
  • the pH of the resultant layer was 4.6.
  • Composition D is a composition of Composition D:
  • Benzoguanamine resin (Epostar M, trade name, product of Nippon Shokubai Kagaku Kogyo Co., Ltd., particle diameter: 1 to 2 ⁇ m) 100 parts Ionomer resin (Chemipearl SA100, trade name, product of Mitsui Petrochemical Industries, Ltd., solids content: 35 %) 30 parts Sodium sulfodiphenyl ether (Pelex SS-H, trade name, product of Kao Corporation) 2 parts Water 20 parts.
  • the thus-obtained printing medium was white-opaque.
  • the pH of the resultant surface layer was 8.2.
  • Example 2 The same polyethylene terephthalate film as that used in Example 1 was used as a light-transmitting base material, coated with the following composition E, to which acetic acid had been added to adjust its pH to 5.8, by a bar coater process so as to give a dry coating thickness of 10 ⁇ m, and then dried at 100°C for 12 minutes in a drying oven.
  • Composition E is a composition of Composition E:
  • Comb type polymer* (LHM-108, trade name, product of Soken Chemical & Engineering Co., Ltd., 25 % methyl cellosolve solution) 60 parts Methyl vinyl ether/maleic anhydride monoethyl ester (Ganterz EZ-425, trade name, product of GAF Corp., 10 % water/ethanol solution) 40 parts *: Obtained by graft-polymerizing 20 parts of MMA on 80 parts of a backbone (a copolymer of 64 parts of 2-hydroxyethyl methacrylate and 16 parts of dimethylacrylamide).
  • composition F was applied onto the thus-formed coating layer by the bar coater process so as to give a dry coating thickness of 10 ⁇ m, and then dried at 70°C for 10 minutes in the drying oven.
  • Composition F is a composition of Composition F:
  • Crosslinked polymethyl methacrylate (Microsphere M-305, trade name, product of Matsumoto Yushi-Seiyaku Co., Ltd., particle diameter: 10 to 12 ⁇ m) 100 parts Ionomer resin (Chemipearl SA100, trade name, product of Mitsui Petrochemical Industries, Ltd., solids content: 35 %) 10 parts Sodium alkylbenzenesulfonate (Neopelex, trade name, product of Kao Corporation). 1.5 parts
  • the thus-obtained printing medium was white-opaque.
  • the pH of the resultant surface layer was 8.7.
  • a white-opaque printing medium was obtained in exactly the same manner as in Example 3 except that the crosslinked polymethyl methacrylate in the composition F used in Example 3 was changed to a benzoguanamine resin (Epostar S, trade name, product of Nippon Shokubai Kagaku Kogyo Co., Ltd., particle diameter: 0.3 ⁇ m).
  • the pH of the resultant surface layer was 8.6.
  • Example 3 After the same compositions E and F as those used in Example 3 were applied onto a Teflon film in the same manner as in Example 3, the Teflon film was separated, thereby obtaining a white-opaque printing medium.
  • Example 2 The same polyethylene terephthalate film as that used in Example 1 was used as a light-transmitting base material, coated with the following composition G by a bar coater process so as to give a dry coating thickness of 6 ⁇ m, and then dried at 120°C for 5 minutes in a drying oven.
  • Composition G is a composition of Composition G:
  • Cationically modified polyvinyl alcohol (C-Polymer, trade name, product of Kuraray Co., Ltd., 10 % aqueous solution) 100 parts Blocked polyisocyanate (Elastlon BN-5, trade name, product of Dai-ichi Kogyo Seiyaku Co., Ltd., solids content: 30 %). 3 parts
  • composition H was applied onto the thus-formed coating layer by the bar coater process so as to give a dry coating thickness of 25 ⁇ m, and then dried at 80°C for 10 minutes in the drying oven.
  • Composition H is a composition having Composition H:
  • Urea-formalin resin (organic filler, product of Nippon Kasei Chemical Co., Ltd., primary particle diameter: 0.01 to 0.02 ⁇ m) 100 parts Acetalated polyvinyl alcohol (S-lec KX-1, trade name, product of Sekisui Chemical, Co., Ltd., nonvolatile content: 8 %) 500 parts Perfluoroalkylbetaine (Surflon S-131, trade name, Seimi Chemical Co., Ltd., solids content: 30 %). 0.3 part
  • the thus-obtained printing medium was white-opaque.
  • a white-opaque printing medium was obtained in exactly the same manner as in Comparative Example 1 except that the urea-formalin resin in the composition H used in Comparative Example 1 was changed to synthetic silica (Sylysia, trade name, product of Fuji Silysia K.K., primary particle diameter: 0.02 to 0.03 ⁇ m).
  • Ejection frequency 4 kHz Volume of ejection droplet: 45 pl Printing density: 360 DPI Maximum printing density of a single color ink: 8 nl/mm 2 .
  • the optical density of a solid printed area of a magenta (M) color as to each print sample obtained by conducting solid printing (100 % duty) by means of the above printer was measured by means of a Macbeth Densitometer RD-918 from the side of the light-transmitting base material.
  • Table 1 Diameter at peak not greater than 100 nm in a pore diameter distribution curve [nm] Pore volume of pores corresponding to the peak [cc/g] Diameter at peak greater than 100 nm in a pore diameter distribution curve [nm] Pore volume of pores corresponding to the peak [cc/g] Optical density Ex. 1 85 0.007 2100 0.082 1.51 Ex. 2 80 0.009 1700 0.085 1.50 Ex. 3 91 0.004 10800 0.090 1.52 Ex. 4 72 0.010 340 0.075 1.49 Ex. 5 93 0.003 11200 0.077 1.51 Comp. Ex. 1 15 0.070 104 0.004 1.18 Comp. Ex. 2 23 0.062 121 0.003 1.21 Note: When plural peaks are present, the value of a peak at which the pore volume is the greatest is shown.
  • an ink-jet printing process which can provide images having high optical density and excellent coloring
  • the printing medium comprising a surface layer having liquid permeability and an ink-retaining layer, in which the printing surface and the viewing surface have an opposite relation to each other, and pigment inks which each comprise pigment particles having a particle diameter within a specified range and develop fastness properties such as water fastness and light fastness, said printing medium having peaks in a pore diameter distribution curve, which correspond to the particle diameter of the pigment particles.
  • a printing medium comprising a surface layer having liquid permeability and an ink-retaining layer, wherein a pore volume of pores corresponding to a peak not greater than 100 nm in a pore diameter distribution curve of the printing medium is at most 0.015 cc/g, a pore volume of pores corresponding to at least one of peaks greater than 100 nm is at least 0.015 cc/g, and the pH of the surface layer is at least 8.

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  • Ink Jet Recording Methods And Recording Media Thereof (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Ink Jet (AREA)
EP96107934A 1995-05-18 1996-05-17 Moyen d'impression et méthode d'impression à jet d'encre l'utilisant Ceased EP0743193A1 (fr)

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JP120172/95 1995-05-18
JP12017295 1995-05-18

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19709735A1 (de) * 1997-03-10 1998-09-17 Sihl Gmbh Aufzeichnungsmaterial für das Tintenstrahlverfahren
EP0908324A1 (fr) * 1997-10-13 1999-04-14 Canon Kabushiki Kaisha Procédé d'enregistrement par jet d'encre et milieu d'enregistrement imprimé
EP0965459A2 (fr) * 1998-06-15 1999-12-22 Canon Kabushiki Kaisha Milieu d'enregistrement et méthode d'enregistrement l'utilisant
JP2002113944A (ja) * 2001-08-10 2002-04-16 Toyobo Co Ltd 記録材及び電飾用記録材
JP2002120455A (ja) * 2001-08-10 2002-04-23 Toyobo Co Ltd 記録材及び電飾用記録材
EP1400367A3 (fr) * 2002-09-18 2005-03-09 Fuji Photo Film Co., Ltd. Matériau d'enregistrement par jet d'encre et méthode de formation d'images
WO2007005232A1 (fr) 2005-07-01 2007-01-11 Eastman Kodak Company Impression a jet d'encre et procede d'impression
EP2402167A1 (fr) * 2010-07-02 2012-01-04 Omya Development AG Papier pour enregistrement à jet d'encre
US8096651B2 (en) * 2007-03-19 2012-01-17 Ricoh Company, Ltd. Ink-jet recording method, ink, ink cartridge, recording apparatus, and recorded matter

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JP3969255B2 (ja) * 2002-09-10 2007-09-05 コニカミノルタホールディングス株式会社 水性染料インク用インクジェット記録用紙
JP4155235B2 (ja) * 2004-06-28 2008-09-24 星光Ｐｍｃ株式会社 記録層保護コーティング剤およびそれを塗工した記録媒体
JP5773634B2 (ja) * 2010-01-28 2015-09-02 キヤノン株式会社 両面記録媒体
KR101853152B1 (ko) * 2011-03-07 2018-04-27 다이니폰 인사츠 가부시키가이샤 열전사 수상 시트 및 열전사 수상 시트의 제조 방법
CN103249571A (zh) * 2011-09-30 2013-08-14 Dic株式会社 受容层形成用树脂组合物以及使用它得到的受容基材、印刷物、导电性图案及电路
EP2671723B1 (fr) * 2012-06-06 2015-03-04 Canon Kabushiki Kaisha Support d'enregistrement

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US4460637A (en) * 1981-12-24 1984-07-17 Mitsubushi Paper Mills, Ltd. Ink jet recording sheet
US4785313A (en) * 1985-12-16 1988-11-15 Canon Kabushiki Kaisha Recording medium and image formation process using the same
EP0622244A1 (fr) * 1993-04-28 1994-11-02 Canon Kabushiki Kaisha Matériau d'enregistrement, méthode d'enregistrement l'utilisant, et dispersion d'hydrate d'alumine
EP0636489A1 (fr) * 1993-07-30 1995-02-01 Canon Kabushiki Kaisha Elément d'enregistrement, méthode d'enregistrement à jet d'encre en utilisant cela, empreinte obtenue selon cela, et dispersion et procédé de production d'élément d'enregistrement en utilisant la dispersion

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US4460637A (en) * 1981-12-24 1984-07-17 Mitsubushi Paper Mills, Ltd. Ink jet recording sheet
US4785313A (en) * 1985-12-16 1988-11-15 Canon Kabushiki Kaisha Recording medium and image formation process using the same
EP0622244A1 (fr) * 1993-04-28 1994-11-02 Canon Kabushiki Kaisha Matériau d'enregistrement, méthode d'enregistrement l'utilisant, et dispersion d'hydrate d'alumine
EP0636489A1 (fr) * 1993-07-30 1995-02-01 Canon Kabushiki Kaisha Elément d'enregistrement, méthode d'enregistrement à jet d'encre en utilisant cela, empreinte obtenue selon cela, et dispersion et procédé de production d'élément d'enregistrement en utilisant la dispersion

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5989701A (en) * 1997-03-10 1999-11-23 Sihl Gmbh Recording material for the inkjet process
DE19709735A1 (de) * 1997-03-10 1998-09-17 Sihl Gmbh Aufzeichnungsmaterial für das Tintenstrahlverfahren
US6550909B2 (en) 1997-10-13 2003-04-22 Canon Kabushiki Kaisha Ink-jet recording method and print
EP0908324A1 (fr) * 1997-10-13 1999-04-14 Canon Kabushiki Kaisha Procédé d'enregistrement par jet d'encre et milieu d'enregistrement imprimé
EP0965459A2 (fr) * 1998-06-15 1999-12-22 Canon Kabushiki Kaisha Milieu d'enregistrement et méthode d'enregistrement l'utilisant
US6605336B2 (en) 1998-06-15 2003-08-12 Canon Kabuskiki Kaisha Recording medium and recording method using the same
EP0965459A3 (fr) * 1998-06-15 2003-01-02 Canon Kabushiki Kaisha Milieu d'enregistrement et méthode d'enregistrement l'utilisant
JP2002113944A (ja) * 2001-08-10 2002-04-16 Toyobo Co Ltd 記録材及び電飾用記録材
JP2002120455A (ja) * 2001-08-10 2002-04-23 Toyobo Co Ltd 記録材及び電飾用記録材
EP1400367A3 (fr) * 2002-09-18 2005-03-09 Fuji Photo Film Co., Ltd. Matériau d'enregistrement par jet d'encre et méthode de formation d'images
US7128413B2 (en) 2002-09-18 2006-10-31 Fuji Photo Film Co., Ltd. Ink-jet recording medium and image forming method
WO2007005232A1 (fr) 2005-07-01 2007-01-11 Eastman Kodak Company Impression a jet d'encre et procede d'impression
US8096651B2 (en) * 2007-03-19 2012-01-17 Ricoh Company, Ltd. Ink-jet recording method, ink, ink cartridge, recording apparatus, and recorded matter
EP2402167A1 (fr) * 2010-07-02 2012-01-04 Omya Development AG Papier pour enregistrement à jet d'encre
WO2012001104A1 (fr) * 2010-07-02 2012-01-05 Omya Development Ag Papier pour impression par jet d'encre
US8974877B2 (en) 2010-07-02 2015-03-10 Omya International Ag Paper for inkjet recording
US10029276B2 (en) 2010-07-02 2018-07-24 Omya International Ag Paper for inkjet recording

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CN1054570C (zh) 2000-07-19
KR0163272B1 (ko) 1998-12-15
KR960040674A (ko) 1996-12-17
CN1136503A (zh) 1996-11-27

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