EP0331125B1 - Aufzeichnungsmaterial und Tintenstrahlaufzeichnungsverfahren mit diesem Material - Google Patents

Aufzeichnungsmaterial und Tintenstrahlaufzeichnungsverfahren mit diesem Material Download PDF

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Publication number
EP0331125B1
EP0331125B1 EP89103526A EP89103526A EP0331125B1 EP 0331125 B1 EP0331125 B1 EP 0331125B1 EP 89103526 A EP89103526 A EP 89103526A EP 89103526 A EP89103526 A EP 89103526A EP 0331125 B1 EP0331125 B1 EP 0331125B1
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EP
European Patent Office
Prior art keywords
ink
recording medium
aluminum oxide
oxide particles
surface layer
Prior art date
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EP89103526A
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English (en)
French (fr)
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EP0331125A2 (de
EP0331125A3 (en
Inventor
Mamoru Sakaki
Masako Shimomura
Megumi Munakata
Tomomi Nakatsugawa
Horoshi Sato
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Canon Inc
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Canon Inc
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Priority claimed from JP1014042A external-priority patent/JP2694771B2/ja
Priority claimed from JP1018004A external-priority patent/JPH02198889A/ja
Application filed by Canon Inc filed Critical Canon Inc
Publication of EP0331125A2 publication Critical patent/EP0331125A2/de
Publication of EP0331125A3 publication Critical patent/EP0331125A3/en
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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
    • 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
    • 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

Definitions

  • This invention relates to a recording medium suitably used for the ink jet recording method, particularly to a recording medium having excellent absorptivity and color forming characteristic of an aqueous ink, as well as excellent sharpness of the recorded image obtained.
  • the present invention relates to a recording medium which can provide a recorded image with little in-room decoloration of the image and excellent storability of the image and a recording method which can provide the above recorded image.
  • the present invention relates to a recording medium having excellent water resistance and light resistance of the recorded image, while having various characteristics as mentioned above.
  • the recording medium to be used is required to have the following characteristics, namely:
  • EP-A-0 275 711 (claiming a priority of 29 December 1986 and designating the Contracting States DE, FR, GB, IT), which document was published on 27 July 1988.
  • Said document relates to a recording medium comprising a substrate and an ink-receiving layer.
  • the ink-receiving layer contains a silicon-type pigment and a binder.
  • the pigment has a specific surface area in the range of 10 to 200 m2/g and may, in addition, contain aluminum oxide particles which may have, according to a further specifically claimed embodiment, article sizes in the range of 0.001 to 10 ⁇ m.
  • the recording medium exhibits an improved discoloration value for an important black dye often employed in ink-jet recording (C. I. Food Black 2) in the ozone test of 20 or less.
  • C. I. Food Black 2 an important black dye often employed in ink-jet recording
  • Said document constitutes prior art according to Art. 54 (3) and (4) EPC with respect to the designated Contracting States DE, FR, GB and IT so that a separate set of claims was drafted for said Contracting States.
  • the problem of light resistance which has been the problem in the prior art is a problem of fading of the image by irradiation of, for example, UV-ray or visible light, etc., which is raised on any image printed on any kind of paper from papers for PPC in general or fine quality paper to coated papers for ink jet.
  • the problem of in-room decoloration as herein mentioned is a problem separate from light resistance which is raised in the image also stored in, for example, a place where no direct sunlight is irradiated, but not raised in the image printed on a non-coated paper such as paper for PPC, etc.
  • JP-A-60-49990 is a method for improving light resistance, and no effect can be seen for in-room decoloration.
  • the problem of in-room decoloration is a problem inherent in coated paper, and it may be estimated to be a problem caused by the pigment forming the coated layer.
  • the coated paper by use of highly active silica as dislosed in JP-A-56-185690 can give an image with high optical density, while it involves a marked problem of in-room decoloration.
  • fillers in general for paper with low specific surface area such as calcium, kaolin, talc, silica, etc. are used, although in-room decoloration may be suppressed, there is now the problem that the image density is lowered.
  • an object of the present invention is to provide a recording medium which can give an image of high quality and high resolution which is high in density of the recorded image, and yet excellent in ink absorptivity and color forming characteristic of dye.
  • Another object of the present invention is to provide a recording medium which can give a recorded image with good storability, particularly a recorded image with little deterioration due to in-room decoloration and an ink jet recording method for forming such image.
  • Still another object of the present invention is to provide a recording medium which has excellent water resistance and light resistance of the recorded image, while having various characteristics as mentioned above.
  • a recording medium comprising a surface layer composed mainly of aluminum oxide particles and a lower layer having ink absorptivity, wherein the aluminum oxide particles have a BET surface area within the range of from 60 to 170 m2/g and an average particle size of 5 ⁇ m or less and wherein the amount of the surface layer coated is within the range of from 0.3 to 7 g/m2 as the total amount of the pigment.
  • a recording medium comprising a surface layer composed mainly of aluminum oxide particles and a lower layer having ink absorptivity , said lower layer being formed of paper including fibrous material, wherein the aluminum oxide particles have a BET surface area within the range from 60 to 170 m2/g and an average particle size of 5 ⁇ m or less and wherein the amount of the surface layer coated is within the range of from 0,3 to 7 g/m2 as the total amount of the pigment, wherein the aluminum oxide particles of the surface layer are in a mixture with the paper fibrous material of the lower layer.
  • the present invention also provides a recording medium, comprising a surface layer composed mainly of aluminum oxide particles and a lower layer having ink absorptivity, and having a Stockigt sizing degree according to JIS-P-8122 of 0 to 15 sec.
  • the present invention also provides a recording medium comprising a surface layer composed mainly of aluminum oxide particles and a lower layer having ink absorptivity, said lower layer being formed of paper including fibrous material, wherein the aluminum oxide particles have a BET surface area within the range from 60 to 170 m2/g and an average particle size of 5 ⁇ m or less and wherein the amount of the surface layer coated is within the range of from 0,3 to 7 g/m2 as the total amount of the pigment, wherein the recording medium has a Stöckigt sizing degree according to JIS-P-8122 of 0 to 15 sec.
  • the present invention also provides an ink jet recording method which performs recording by imparting small droplets of an aqueous ink to a recording medium as described above and further illustrated below, wherein said aqueous ink contains an acidic and/or a direct dye.
  • the present invention also provides an ink jet recording method which performs recording by imparting small droplets of an aqueous ink to a recording medium, wherein said aqueous ink contains an acidic dye and/or a direct dye, and said recording medium comprises a surface layer composed mainly of aluminum oxide particles and a lower layer having ink absorptivity.
  • the present invention provides a recording medium, comprising a surface layer composed mainly of aluminum oxide particles containing polyaluminum hydroxide and/or polyaluminum chloride and a lower layer having ink absorptivity.
  • the present invention further provides a recording medium, comprising a surface layer composed mainly of aluminum oxide particles with particle sizes of 5 ⁇ m or less provided on a liquid absorptive base paper.
  • the present inventors investigated about the relationship between the pigment forming the coated layer which becomes the ink receiving layer and in-room decoloration on the basis of recognition that in-room decoloration is a phenomenon which does not occur on non-coated paper but is generated only on coated paper, and consequently found that the problem of in-room decoloration can occur with difficulty when a specific pigment is used as the pigment which forms the ink receiving layer, particularly the recording surface which captures the dye.
  • the first specific feature of the recording medium of the present invention resides in that the surface layer which is the recording surface is formed mainly of aluminum oxide particles.
  • the aluminum oxide particles as herein mentioned is produced by the method generally called the Bayer method by calcining aluminum hydroxide obtained by hot caustic soda treatment of bauxite which is a natural ore. Otherwise, there can be also used those produced by the method in which metallic aluminum pellets are subjected to arc discharging in water and then the resultant aluminum hydroxide is calcined, or the method in which aluminum chloride is gasified at high temperature and oxidized in gas phase, or the method in which an inorganic aluminum salt (alum, etc.) is decomposed.
  • the crystal structures of the aluminum oxide particles have been known to be transitioned depending on the temperature for heat treatment from aluminum hydroxide of the giftsite type, the boehmite type to aluminum oxide of ⁇ , ⁇ , ⁇ , ⁇ type.
  • any of these preparation methods and crystal structures may be available.
  • the purity of aluminum oxide particles may be different depending on the preparation method, the degree of purification, but those available in the present invention are not limited to one containing 99.99% of aluminum oxide (Al2O3) generally called as high purity alumina, but those containing 80 to 90% or more of Al2O3 may be sufficiently available.
  • Al2O3 aluminum oxide
  • the aluminum oxide particles to be used in the present invention have a BET specific surface area within the range of from 60 to 170 m2/g, preferably from 90 to 170 m2/g. If the BET specific surface area of the aluminum oxide particles exceeds 170 m2/g, the in-room decoloration of the recorded image will become undesirably and markedly deteriorated.
  • in-room decoloration of recorded image is due to oxidation decomposition of the dye, and when the dye is captured on the surface layer of the recording medium, the dye will be correspondingly susceptible to oxidation by contact with air. Particularly when the dye is captured with a pigment with large specific surface area, the contact area with air becomes the maximum, whereby the in-room decoloration is caused excessively.
  • aluminum oxide particles among various inorganic pigments can provide an image with excellent optical density as described above remains to be not clarified, but according to the imagination by the present inventors, it may be considered because aluminum oxide particles have positive charges on their surfaces and also can readily absorb electrically acidic dyes and/or direct dyes, and the paper by use of such aluminum oxide particles can capture more dyes near the surface, namely at the surface layer of the ink receiving layer, and also because the dyes and the aluminum oxide particles are electrically bonded, and therefore the dyes existing near the surface layer are stabilized to be decomposed with difficulty, etc.
  • silica is used as the pigment forming the recording surface (surface layer)
  • the relationships between the specific surface area of silica and image density and between the specific surface area and in-room decoloration is strong, prevention of in-room decoloration and improvement of image density cannot be compatible with each other, whereby it has been difficult to improve both at the same time.
  • the tendency of the both characteristics to be antagonistic to each other may be similar also in the case of aluminum oxide particles as silica, but when aluminum oxide particles are used, the elevating tendency of image density relative to the specific surface area of the pigment is more marked than silica, having the advantage that a desired image density can be achieved with particles having lower specific surface area (170 m2/g or less) as compared with silica. This is the reason why both prevention of in-room decoloration and improvement of image density can be improved by the present invention.
  • the aluminum oxide particles to be used in the present invention have an average particle size of 5 ⁇ m or less, preferably 3 ⁇ m or less, further preferably 1 ⁇ m or less.
  • the image density and the in-room storability can be improved to considerable extent, but yet the image density and the in-roam storability have the trade-off relationship.
  • the above aluminum oxide particles having an average particle size of 5 ⁇ m or less, preferably 3 ⁇ m or less, further preferably 1 ⁇ m or less.
  • An average particle size exceeding 5 ⁇ m is insufficient for inhibiting in-room decoloration.
  • the average particle size as herein mentioned is the particle size under the state where the ink receiving layer is formed.
  • the primary particle size of aluminum oxide particle is about 1 nm to 1 ⁇ m, particles forming no secondary particle are preferred in the present invention.
  • the average primary particle size of aluminum oxide particles should be preferably 0.5 ⁇ m or less. Those exceeding 0.5 ⁇ m have insufficient ink absorptivity.
  • the second specific feature of the present invention resides in that the recording medium of the present invention is constituted of a surface layer containing the above aluminum oxide particles and a lower layer having ink absorptivity.
  • the surface layer as herein mentioned is a layer constituting the recording surface, and cannot itself retain all the ink amount attached, but has the function of adsorbing primarily the dye in the ink and permeating most of the ink solvent to migrate it to the ink absorptive lower layer.
  • the recording medium of the present invention includes the embodiment of having a recording surface in which the pigment forming the surface layer and the fibrous material of base paper exist in mixture and/or the embodiment of having a recording surface covered with a surface layer with the maximum thickness of 20 ⁇ m, more preferably 15 ⁇ m or less.
  • An essential amount of the surface layer coated as herein mentioned may be within the range of from 0.3 to 7 g/m2 as the total amount of the pigment.
  • the coated amount is less than 0.3 g/m2
  • there is no effect as compared with the case when no surface layer is provided while if it is provided in excess of 7 g/m2 or the maximum thickness of the surface layer exceeds 20 ⁇ m, similarly as in the case of the above recording medium (2), there ensue such problems as remarkable lowering in ink absorptivity, lowering in in-room decoloration prevention or generation of paper powder even when the above aluminum oxide particles may be used.
  • a preferable amount of the pigment coated on the surface layer is within the range of from 1 to 7 g/m2, further preferably from 2 to 7 g/m2.
  • the maximum thickness of the surface layer as herein mentioned refers to the maximum value in the depth direction of the surface layer in the cross-section of the recording medium, and the amount of the pigment coated is the amount of the pigment coated as the surface layer.
  • the amount of the pigment coated in the surface layer is determined according to the method of JIS-P-8128, and can be obtained as the value of the amount of the ash in the whole recording medium from which the amount of ash in the base paper is removed.
  • the surface layer is formed mainly of the above aluminum oxide particles, but may also use inorganic pigments known in the art, such as silica, aluminum silicate, magnesium silicate, calcium silicate, calcium carbonate, clay, kaolin, talc, diatomaceous earth, etc., or organic pigments such as urea resin, etc. mixed in the pigment in an amount within the range which does not exceed 20% by weight.
  • inorganic pigments such as silica, aluminum silicate, magnesium silicate, calcium silicate, calcium carbonate, clay, kaolin, talc, diatomaceous earth, etc.
  • organic pigments such as urea resin, etc. mixed in the pigment in an amount within the range which does not exceed 20% by weight.
  • the pigment for forming the surface layer as described above should desirably contain 80% by weight or more of aluminum oxide particles, and when aluminum oxide particles are contained in an amount less than 80% by weight, the image density will be lowered, and also the problem of in-room storability may not be cancelled depending on the kind of the pigment used in combination.
  • a recording medium which can satisfy the respective requisite performances can be obtained by providing a relatively minute amount of the surface layer, because it is used in combination with an ink absorptive lower layer as described below.
  • the present invention is distinct in its constitutional aspect from, for example, a prior art example comprising an ink receiving layer in an amount as much as 15 g/m2 with the use of aluminum particles having a particle size of 30 ⁇ m on a polyethyleneterephthalate film as shown in Example 2 in JP-A-58-110287 or an example comprising aluminum particles filled internally in pulp fibers during sheet making as disclosed in JP-A-58-110288.
  • preferable recording medium having ink absorptive lower layer in the present invention may include:
  • the embodiment (1) is the most preferred embodiment in the present invention in view of the problems of in-room decoloration, paper powder, etc., stability in production or cost.
  • the surface layer of this embodiment is constituted of a pigment containing the above aluminum oxide particles and a binder.
  • the binder to be used in the present invention may include water-soluble polymers such as polyvinyl alcohol, starch, oxidized starch, cationized starch, casein, carboxymethyl cellulose, gelatin, hydroxyethyl cellulose, acrylic resin, etc. and aqueous dispersion type polymers such as SBR latex, polyvinyl acetate emulsion, etc. known in the art, which can be used either singly or as a mixture of two or more kinds.
  • a preferable use ratio (weight ratio) of all the pigments to the binder may be 1/4 to 20/1, more preferably 1/2 to 4/1. If the binder amount is more than the amount corresponding to a pigment/binder weight ratio of 1/4, the ink absorptivity possessed by the coated layer is lowered, while, if it is lower than the amount corresponding to a pigment/binder weight ratio of 20/1, powder drop-off of the above pigment from the coated layer becomes undesirably excessive.
  • the base paper on which the above surface layer is provided is required to be ink absorptive, having a preferable Stockigt sizing degree of within the range of from 0 to 15 sec., more preferably from 0 to 10 sec., further preferably from 0 to 8 sec.
  • a base paper having a Stöckigt sizing degree in excess of 15 is used, the ink absorptivity of the recording medium as a whole is undesirably deficient.
  • the recording medium having the above coated layer provided on the base paper should desirably have a Stöckigt sizing degree within the range of from 0 to 15 sec., more preferably from 0 to 10 sec., further preferably from 0 to 5 sec. If it exceeds 15 sec., most of ink absorptivity depend on the coated layer within the above range, whereby ink absorptivity will be deficient.
  • the pulp constituting the base paper is not particularly limited, but it may be composed mainly of wood pulp as represented by LBKP or NPKP known in the art, but synthetic fibers or glass fibers may be also mixed therein, if desired.
  • fillers in the base paper to be used in the present invention may include clay, talc, kaolinite, titanium oxide, calcium carbonate, etc. generally employed, and particularly in the present invention, these fillers are contained in an amount of 1 to 20 g/m2, more preferably 2 to 10 g/m2 as calculated on the ash content.
  • calcium carbonate is particularly preferable, because the dot shape and the color forming characteristic become good.
  • the ash content in the base paper in the above embodiment (1) can be determined by, for example, eliminating the ink receiving layer from the recording medium by use of a good solvent for the binder and determining only the ash content in the base paper according to the method of JIS-P-8128, as the mass of the ash content per unit area of the paper at that time.
  • a good solvent for the binder for example, polyvinyl alcohol is used as the binder, and in this case, the coated layer is eliminated by dipping the recording medium in stationary hot water, and then the ash content as the base paper can be determined.
  • the base paper to be used in the above embodiment (1) can be made with the use of the above materials optionally together with sheet making aids, sizing agents, yield enhancers, paper force strengthening agents, etc. known in the art, if desired.
  • a preferable basis weight of the base paper to be used in the embodiment (1) may be within the range of from 60 to 120 g/m2.
  • the recording medium of the embodiment (1) absorbs ink through the base paper, if the basis weight of the base paper is less than 60 g/m2, there may ensue problems such as generation of strike-through or cockling, etc. when high density printing is performed. On the contrary, if it exceeds 120 g/m2, the paper becomes too firm, whereby a problem is involved in conveyability within the recording device.
  • the recording medium of the embodiment (2) absorbs ink only with the pigment layer, and therefore is excellent in ink absorptivity and dot shape, thus being suitable for providing images of high resolution and high quality.
  • the ink receiving layer comprises a layer constitution of two or more layers and contains an ink holding layer formed primarily of a pigment with larger particle size than the above aluminum oxide particles.
  • the ink holding layer is preferably formed mainly of a pigment having an (average) particle size of 5 to 30 ⁇ m, more preferably a silicon containing type pigment, further preferably a synthetic silica, and is arranged lower than the layer containing the aluminum oxide particles constituting the recording surface as described above.
  • the specific surface area of the pigment forming the ink holding layer should be preferably larger than the pigment forming primarily the surface layer, more preferably 200 m2/g or higher, also in aspect of ink absorptivity. Also, in aspect of color forming characteristic and ink absorptivity, a constitution with the ink absorption speed of the surface layer which is slow to the extent that ink droplets may be blurred in appropriate sizes and with the ink absorptivity of the ink holding layer being large is preferable.
  • the use ratio of the pigment to the binder in the surface layer constituting the recording surface may be preferably 1/3 to 5/1, more preferably 1/2 to 3/1, preferably 1/1 to 10/1 as the total of the ink receiving layer.
  • any of the binders known in the art can be used for formation of the ink holding layer.
  • the amount of the total ink receiving layer coated may be preferably within the range of from 2 to 50 g/m2, more preferably from 8 to 30 g/m2, with the coated amount of the ink holding layer being preferably larger than that of the surface layer.
  • porous silica particles having spherical particle shapes as disclosed in JP-A-62-183382 can be used.
  • porous silica particles having an average particle size of 5 to 30 ⁇ m is used for the ink holding layer, an ink receiving layer with higher void volume as compared with that by use of amorphous pigment of the prior art can be formed, whereby a recording medium having excellent ink absorptivity can be provided.
  • a coating solution containing the components as described above is coated on the substrate surface according to the method known in the art, such as the roll coater method, the blade coater method, the air knife coater method, the gate roll coater method, the size press method, etc.
  • the coating can be dried according to the method known in the art by using, for example, hot air drying furnace, hot drum, etc. to give the recording medium of the present invention.
  • a super calender may be used in the steps.
  • the recording medium of the present invention formed as described above has high image density, excellent ink absorptivity and yet excellent characteristics without occurrence of in-room decoloration.
  • the polyaluminum hydroxide as herein mentioned is a compound having two or more compounds represented by [Al(OH) 3-a ] in the molecule, including, for example, compounds represented by: [Al(OH)3] n AlCl3 (n ⁇ 2), and the above compounds are commercially availabe under the trade name of paho#2S® from Asada Kagaku Kogyo.
  • the polyaluminum chloride is a compound having two or more compounds represented by [AlCl 3-b ] in the molecule, including, for example, compounds represented by the formula: [Al2(OH) l Cl 6-l ] m (m ⁇ 1), and the compounds are commercially available under the trade name of PAC® from Taki Kagaku Kogyo.
  • the recording medium of the present invention should preferably contain these compounds in an amount within the range of from 0.01 g/m2 to 5 g/m2. If it is less than 0.01 g/m2, water resistance is insufficient, while if it is contained in excess of 5 g/m2, there are problems such as lowering in ink absorptivity and image density.
  • the dye fixing agent available in recording medium for ink jet there may be included those disclosed in JP-A-56-84992, 59-20696, 59-33176, 60-11389, 61-58788, 61-252189, etc., and all of them are of the amine type, but cannot sufficiently satisfy both of water resistance and light resistance, although improved.
  • the recording medium of the present invention which uses an aluminum type compound as different from the amine type as in the prior art as the dye fixing agent, has the effect of improving water resistance of the dye, and also has no deleterious effect on light resistance.
  • the polyaluminum compound can be used with an amine type dye fixing agent as described above mixed therein, the amine type water resistant agent in this case should be preferably within the range of 70% by weight or less, more preferably 25% by weight or less, of the polyaluminum compound. If it is contained in excess of 70%, the bad influence by use of the amine type water resistance-affording agent will appear to lower undesirably light resistance.
  • the ink receiving layer may also contain fluorescent brighteners, surfactants, defoaming agents, pH controllers, antifungal agents, UV-absorbers, antioxidants, etc., if necessary.
  • the ink jet recording system for the recording medium of the present invention with a constitution as described above, for example, according to the recording method of the present invention which performs recording with a multi-colour aqueous ink such as yellow (Y), magenta (M), cyan (C), black (Bk), etc., no in-room decoloration occurs on the image obtained to give a recorded image with excellent storability.
  • a multi-colour aqueous ink such as yellow (Y), magenta (M), cyan (C), black (Bk), etc.
  • the method of the present invention is a recording method by use of the recording medium of the present invention as described above, and the ink itself which is imparted by the ink jet recording method to the specific recording medium as described above in the recording method may be also known.
  • its recording agent may be water soluble dyes as represented by direct dyes, acidic dyes, basic dyes, reactive dyes, dyes for foods, etc.
  • the dyes particularly suitable for the ink in the ink jet recording system which can give images satisfying requisite performances in combination with the above recording medium such as color forming characteristic, sharpness, stability, light resistance and others may include: Direct dyes such as C.I. Direct Black 17, 19, 32, 51, 71, 108, 146, C.I.
  • dyes set forth above are particularly preferred for the ink applicable to the recording method of the present invention, and the dyes for the ink to be used in the present invention are not limited to these dyes.
  • Such water soluble dyes are used generally in the ink of the prior art at a ratio about 0.1 to 20% by weight of the ink, and the same ratio may be used also in the present invention.
  • the solvent to be used for the aqueous ink to be used in the present invention is water or a solvent mixture of water with a water soluble organic solvent, particularly preferably a solvent mixture of water and a water soluble organic solvent.
  • a water soluble organic solvent one containing a polyhydric alcohol having drying prevention effect on ink is preferred.
  • the water it is preferable to use deionized water instead of water in general containing various ions.
  • the content of the water soluble organic solvent in the ink may be generally within the range of from 0 to 95% by weight, preferably from 2 to 80% by weight, more preferably from 5 to 50% by weight.
  • a preferable water content may be 20 to 98%, more preferably 50 to 90%, based on the total weight of the ink.
  • the ink to be used in the present invention can also include surfactants, viscosity controllers, surface tension controllers, etc., if desired, in addition to the above components.
  • the method for performing recording by imparting the above ink to the above recording medium in the method of the present invention may be any recording method, but preferably the ink jet recording method, and said method may be any system, provided that it is a system capable of eliminating effectively the ink from the nozzle and imparting the ink to the recording medium which is the target of injection.
  • the ink jet system which discharges ink through nozzle by the acting force due to the state change by the abrupt volume change of ink having received the action of heat energy according to the method disclosed in JP-A-54-59936 can be effectively used.
  • the recording medium of the present invention as described above is suitable as the recording medium for ink jet recording, particularly by use of aqueous ink, and exhibits the following effects.
  • a coating solution having the composition shown below was coated according to the bar coater method to a coated amount on drying of 5 g/m2 and dried at 110 o C for 3 minutes to obtain a recording medium of the present invention.
  • the pigments used are shown below in Table 1.
  • a recording medium was prepared in the same manner as in Example 1 except for using a paper for PPC having a Stöckigt sizing degree of 24 sec. and a basis weight of 66 g/m2 (paper for Canon NP dry) as the base paper.
  • a coating solution with the same composition as in Example 1 was coated by the bar coating method to a coated amount on drying of 7 g/m2 and dried at 110 o C to obtain the recording media of the present invention and Comparative example.
  • the mixtures of alumina with other pigments as shown in Table 2 were used.
  • the ink jet recording adaptability of the above recording medium was evaluated by performing the ink jet recording with an ink having the composition shown below by means of an ink jet printer having ink jet heads equipped with 128 nozzles with nozzle interval of 1 mm/16 nozzles corresponding to the four colors of Y, M, C and Bk.
  • Synthetic silica (spherical silica, BET specific surface area 700m2/g, average particle size 20 ⁇ m, produced by Asahi Glass) 18 parts Polyvinyl alcohol (PVA-117/R-1130, produced Kuraray) 6 parts Water 76 parts
  • Porous alumina RG-40, produced by Iwatani Kagaku Kogyo specific surface area 48m2/g
  • Fine particulate alumina (Aerosil®, aluminum oxide-C, produced by Nihon Aerosil, BET specific surface area 100m2/g) 13 parts Polyvinyl alcohol (PVA-110, produced by Kuraway) 10 parts Water 77 parts
  • Fine powder silica (Syloid 74, produced by Fujidevison, BET specific surface area 300m2/g) 13 parts Polyvinyl alcohol (PVA-110, produced by Kuraray) 10 parts Water 77 parts
  • Zinc oxide active zinc white AZO, produced by Seido Kagaku BET specific surface area 64m2/g
  • Polyvinyl alcohol PVA-110, produced by Kuraray 10 parts Water 77 parts
  • Example 9 On the same base paper as in Example 9, by use of a coating solution III shown below, it was coated by the bar coater method to a coated amount on drying of 20 g/m2, followed by drying at 110 o C for 5 minutes, to form an ink holding layer, and on the ink holding layer was coated a coating solution IV shown below to a coated amount on drying of 7 g/m2, followed by drying at 110 o C for 3 minutes to form a surface layer, thus providing a recording medium of the present invention.
  • a coating solution III shown below it was coated by the bar coater method to a coated amount on drying of 20 g/m2, followed by drying at 110 o C for 5 minutes, to form an ink holding layer, and on the ink holding layer was coated a coating solution IV shown below to a coated amount on drying of 7 g/m2, followed by drying at 110 o C for 3 minutes to form a surface layer, thus providing a recording medium of the present invention.
  • Example 10 On the same base paper as used in Example 10 was coated a coating solution shown below by the bar coater method to a coated amount of 15 g/m2, followed by drying at 140 o C for 5 minutes to form a lower layer with low ink absorptivity. On the lower layer was applied coating by use of the coating solution used in Example 10 in the same manner as in Example 10, followed by drying, to obtain a recording medium 6 for comparison.
  • Pigment 20 Polyvinyl alcohol (PVA-110, produced by Kuraray) 10 parts Water-resistant agent 3.6 parts Water 266 parts
  • Light resistance was evaluated by irradiating the printed product of (1) by use of Xenon Fade-Ometer (manufactured by Ci-35 Atlas Co.) under the conditions of a black panel temperature of 63 o C and a humidity of 70% RH for 100 hours, and determining the ratio of the image density at the M printed portion after irradiation relative to the image density before irradiation.
  • Example 13 o 1.60 95% 83% 3.4 14 o 1.48 94% 78% 2.3 15 o 1.59 98% 80% 3.2 16 o 1.48 99% 74% 2.1 Reference Example 1 o 1.62 72% 88% 4.4 Comparative Example 7 o 1.63 80% 76% 26.3 8 o 1.59 102% 43% 3.1 9 o 1.48 99% 38% 1.9

Claims (11)

  1. Aufzeichnungsmedium mit einer hauptsächlich aus Aluminiumoxidteilchen bestehenden Oberflächenschicht und einer Tintenabsorptionsvermögen aufweisenden unteren Schicht, wobei die untere Schicht aus einem Papier unter Einschluß eines fasrigen Materials gebildet ist und die Aluminiumoxidteilchen ein BET-Oberflächengebiet innerhalb des Bereiches von 60 bis 170 m²/g und eine mittlere Teilchengröße von 5 µm oder weniger haben und wobei die Menge der aufgebrachten Oberflächenschicht innerhalb des Bereiches von 0,3 bis 7 g/m² als Pigment-Gesamtmenge liegt, wobei die Aluminiumoxidteilchen der Oberflächenschicht sich in einer Mischung mit dem fasrigen Papiermaterial der unteren Schicht befinden.
  2. Aufzeichnungsmedium mit einer hauptsächlich aus Aluminiumoxidteilchen bestehenden Oberflächenschicht und einer Tintenabsorptionsvermögen aufweisenden unteren Schicht, wobei die untere Schicht aus ein fasriges Material einschließendem Papier gebildet ist und wobei die Aluminiumoxidteilchen ein BET-Oberflächengebiet im Bereich von 60 bis 170 m²/g und eine mittlere Teilchengröße von 5 µm oder weniger haben und wobei die Menge der aufgebrachten Oberflächenschicht innerhalb des Bereiches von 0,3 bis 7 g/m² als Pigment-Gesamtmenge liegt, wobei das Aufzeichnungsmedium einen Stöckigt-Leimungsgrad entsprechend JIS-P-8122 von 0 bis 15 s hat.
  3. Aufzeichnungsmedium nach Anspruch 1 oder 2, wobei die Alumiumoxidteilchen eine mittlere Teilchengröße von 1 µm oder weniger haben.
  4. Aufzeichnungsmedium nach einem der vorangehenden Ansprüche, wobei die untere Schicht ein Papier mit einem Stöckigt-Leimungsgrad entsprechend JIS-P-8122 von 0 bis 15 s ist.
  5. Aufzeichnungsmedium nach einem der vorangehenden Ansprüche, dadurch gekennzeichnet, daß die Tintenaufnahmeschicht eine primär aus einem Pigment gebildete Tintenhalteschicht umfaßt, die zwischen einem Basis-Papier und der hauptsächlich aus Aluminiumoxidteilchen bestehenden Oberflächenschicht vorgesehen ist.
  6. Aufzeichnungsmedium nach einem der vorangehenden Ansprüche, wobei die hauptsächlich aus Aluminiumoxidteilchen bestehende Oberflächenschicht Polyaluminiumhydroxid und/oder Polyaluminiumchlorid enthält.
  7. Aufzeichnungsmedium nach Anspruch 6, wobei das Polyaluminiumhydroxid und/oder Polyaluminiumchlorid in einer Menge innerhalb des Bereiches von 0,01 bis 5 g/m² enthalten ist.
  8. Tintenstrahlaufzeichnungsverfahren, das eine Aufzeichnung durch Aufbringen kleiner Tröpfchen einer wäßrigen Tinte auf ein Aufzeichnungsmedium nach einem der Ansprüche 1 bis 7 ausführt, wobei die wäßrige Tinte einen acidischen und/oder einen Direktfarbstoff enthält.
  9. Tintenstrahlaufzeichnungsverfahren nach Anspruch 8, wobei die kleinen Tröpfchen der Tinte dadurch gebildet werden, daß Wärmeenergie auf die Tinte einwirken gelassen wird.
EP89103526A 1988-03-04 1989-02-28 Aufzeichnungsmaterial und Tintenstrahlaufzeichnungsverfahren mit diesem Material Expired - Lifetime EP0331125B1 (de)

Applications Claiming Priority (8)

Application Number Priority Date Filing Date Title
JP4967688 1988-03-04
JP49676/88 1988-03-04
JP11060588 1988-05-09
JP110605/88 1988-05-09
JP1014042A JP2694771B2 (ja) 1988-03-04 1989-01-25 被記録材及びそれを用いた記録方法
JP14042/89 1989-01-25
JP1018004A JPH02198889A (ja) 1989-01-27 1989-01-27 被記録材及びこれを用いたインクジェット記録方法
JP18004/89 1989-01-27

Publications (3)

Publication Number Publication Date
EP0331125A2 EP0331125A2 (de) 1989-09-06
EP0331125A3 EP0331125A3 (en) 1990-09-05
EP0331125B1 true EP0331125B1 (de) 1994-09-21

Family

ID=27456129

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Application Number Title Priority Date Filing Date
EP89103526A Expired - Lifetime EP0331125B1 (de) 1988-03-04 1989-02-28 Aufzeichnungsmaterial und Tintenstrahlaufzeichnungsverfahren mit diesem Material

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EP (1) EP0331125B1 (de)
AT (1) ATE111818T1 (de)
AU (1) AU626290B2 (de)
CA (1) CA1337388C (de)
DE (1) DE68918307T2 (de)
DK (1) DK172062B1 (de)
ES (1) ES2059591T3 (de)
FI (1) FI97345C (de)
NO (1) NO301410B1 (de)

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2670454B2 (ja) * 1989-04-03 1997-10-29 キヤノン株式会社 被記録材及びこれを用いた記録方法
JP2686670B2 (ja) * 1990-04-02 1997-12-08 キヤノン株式会社 インクジェット用被記録材
JP2877740B2 (ja) * 1994-10-27 1999-03-31 キヤノン株式会社 被記録媒体及びこれを用いた画像形成方法、印字物
US6000794A (en) * 1994-10-27 1999-12-14 Canon Kabushiki Kaisha Image forming method
DE19618607C2 (de) * 1996-05-09 1999-07-08 Schoeller Felix Jun Foto Aufzeichnungsmaterial für Tintenstrahl-Druckverfahren
US6159581A (en) * 1997-09-24 2000-12-12 Kuraray Co., Ltd. Leather-like sheet
FR2795366B1 (fr) * 1999-06-22 2001-08-10 Rhodia Chimie Sa Support d'enregistrement par jet d'encre
AU1006001A (en) * 2000-01-06 2001-07-12 Westvaco Corporation Glossy inkjet coated paper
US6696118B2 (en) * 2000-09-27 2004-02-24 Canon Kabushiki Kaisha Recording medium and image forming method utilizing the same
EP1329330B2 (de) † 2000-10-24 2012-12-26 Mitsubishi Paper Mills Limited Tintenstrahlaufzeichungsmaterial
FR2876384B1 (fr) * 2004-10-13 2008-01-04 Honnorat Rech S & Services Sar Composition liquide de traitement de supports

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS60232990A (ja) * 1984-05-02 1985-11-19 Mitsubishi Paper Mills Ltd インクジエツト記録媒体
JPS61280983A (ja) * 1985-06-07 1986-12-11 Teijin Ltd 記録シ−ト
US5041328A (en) * 1986-12-29 1991-08-20 Canon Kabushiki Kaisha Recording medium and ink jet recording method by use thereof

Also Published As

Publication number Publication date
CA1337388C (en) 1995-10-24
FI891040A0 (fi) 1989-03-03
FI891040A (fi) 1989-09-05
EP0331125A2 (de) 1989-09-06
DK103789A (da) 1989-09-05
EP0331125A3 (en) 1990-09-05
ES2059591T3 (es) 1994-11-16
DK103789D0 (da) 1989-03-03
AU626290B2 (en) 1992-07-30
ATE111818T1 (de) 1994-10-15
NO890925L (no) 1989-09-05
FI97345B (fi) 1996-08-30
DE68918307D1 (de) 1994-10-27
NO890925D0 (no) 1989-03-03
DE68918307T2 (de) 1995-05-18
FI97345C (fi) 1996-12-10
NO301410B1 (no) 1997-10-27
DK172062B1 (da) 1997-10-06
AU3098789A (en) 1989-09-07

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