WO2006046463A1 - Dispersions de fines particules cationiques et papiers d’enregistrement à jet d’encre - Google Patents

Dispersions de fines particules cationiques et papiers d’enregistrement à jet d’encre Download PDF

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Publication number
WO2006046463A1
WO2006046463A1 PCT/JP2005/019296 JP2005019296W WO2006046463A1 WO 2006046463 A1 WO2006046463 A1 WO 2006046463A1 JP 2005019296 W JP2005019296 W JP 2005019296W WO 2006046463 A1 WO2006046463 A1 WO 2006046463A1
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Prior art keywords
water
fine particle
polyvalent metal
cationic
metal compound
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PCT/JP2005/019296
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English (en)
Japanese (ja)
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Yukako Taka
Toshihiko Iwasaki
Keiji Ohbayashi
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Konica Minolta Photo Imaging, Inc.
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Priority to JP2006543059A priority Critical patent/JPWO2006046463A1/ja
Publication of WO2006046463A1 publication Critical patent/WO2006046463A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/28—Compounds of silicon
    • C09C1/30—Silicic acid
    • C09C1/3045—Treatment with inorganic compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/28—Compounds of silicon
    • C09C1/30—Silicic acid
    • C09C1/3045—Treatment with inorganic compounds
    • C09C1/3054—Coating
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/28—Compounds of silicon
    • C09C1/30—Silicic acid
    • C09C1/3072—Treatment with macro-molecular organic compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/28—Compounds of silicon
    • C09C1/30—Silicic acid
    • C09C1/309—Combinations of treatments provided for in groups C09C1/3009 - C09C1/3081

Definitions

  • the present invention relates to a silica fine particle dispersion in which silica fine particles are dispersed in the presence of a water-soluble polyvalent metal compound, and an ink jet recording sheet using the dispersion for an ink absorption layer.
  • ink jet recording paper hereinafter also referred to simply as recording paper
  • a void-type inkjet recording paper that has a porous layer with a fine void structure formed on it as inorganic ink and hydrophilic polymer as an ink absorbing layer has high gloss, vivid color, and absorbs ink. It is becoming one of the closest to photographic image quality because of its excellent properties and dryness.
  • such a void-type recording paper has a problem that the coating transparency is low due to the refractive index of the inorganic fine particles, and as a result, the color developability is low.
  • Ink jet recording is generally divided into a case where a water-soluble dye ink is used and a case where a pigment ink is used.
  • Pigment inks have high image durability, but as the image changes in gloss, it is difficult to obtain prints that are close to photographic quality.
  • Water-soluble dye inks on the other hand, have color clarity comparable to that of photographic images with high image clarity and uniform surface gloss. One print is obtained. However, this water-soluble dye has a weak point that bleeding occurs under high humidity due to its high hydrophilicity.
  • a cationic substance is mainly added to the porous layer. In general, a method of strongly immobilizing a dye by combining it with a ergonal dye is generally used. As a typical cationic substance,
  • Examples include polymers of quaternary ammonia salts, for example, “Inkjet printer materials and technology” (issued by CMC Co., Ltd. July 1998) or Japanese Patent Application Laid-Open No. 10-217601. Has been. However, in the method in which a cationic substance is simply added to the porous layer, since the cationic polymer is present in the entire ink absorbing layer, it is difficult to fix the dye at the top, and until satisfactory color development is obtained. The current situation has not yet reached.
  • Japanese Patent Application Laid-Open No. 2001-1632 discloses a method of applying a solution containing a mordant on an ink absorbing layer after applying an ink absorbing layer coating solution containing silica fine particles and polybulal alcohol. Is disclosed. This method is intended to increase the print density obtained by fixing the dye in the landed ink droplets on the upper part of the ink absorbing layer by allowing the mordant to be present in the upper region of the ink absorbing layer. It was insufficient to obtain a higher print density.
  • boric acid is used as a crosslinking agent for polyvinyl alcohol, which is a hydrophilic binder, and boric acid is applied at the same time as the mordant, but from the time when the mordant and boric acid are applied, Since crosslinking with boric acid is initiated, it is assumed that the mordant penetrates significantly into the ink absorption layer, resulting in insufficient print concentration.
  • Japanese Patent Application Laid-Open No. 2002-144700 discloses a method of impregnating a water-soluble organic substance more in the vicinity of the surface of the ink absorption layer.
  • the organic substance used in the method swells when absorbing the ink, thereby inhibiting the ink absorption rate.
  • JP-A-2001-287451 discloses a method in which a water-soluble metal salt such as an aluminum salt is contained in the outermost ink absorbing layer.
  • Japanese Patent Publication No. 3-24907 discloses a method for incorporating a basic polyhydric acid-aluminum compound in an ink absorbing layer.
  • Japanese Patent Application Laid-Open No. 2004-122520 discloses an inorganic material in an ink absorbing layer.
  • methods for incorporating a mordant and a betaine surfactant are disclosed, In this method, the single layer ink absorbing layer has a basic polyhydric acid-aluminum compound! /, And an inorganic mordant is applied as an overcoat.
  • JP-A-2002-160442 discloses a method of distributing a large amount of water-soluble polyvalent metal compound in a region away from the support!
  • the dye in the ink on the outermost layer is disclosed. Is insufficient to fix the color, and the color developability is still insufficient.
  • Patent Document 1 Japanese Patent Laid-Open No. 10-217601
  • Patent Document 2 Japanese Patent Laid-Open No. 2001-1632
  • Patent Document 3 Japanese Patent Laid-Open No. 2002-144700
  • Patent Document 4 JP 2001-287451 A
  • Patent Document 5 Japanese Patent Publication No. 3-24907
  • Patent Document 6 Japanese Patent Application Laid-Open No. 2004-122520
  • Patent Document 7 Japanese Unexamined Patent Application Publication No. 2002-160442
  • Patent Document 8 Special Table 2002-526564
  • Patent Document 9 Japanese Patent Laid-Open No. 2002-320842
  • Patent Document 10 Japanese Patent Application Laid-Open No. 2004-202964
  • Non-Patent Document 1 "Inkjet Printer Materials and Technologies” (issued by CME Co., Ltd. July 1998)
  • An object of the present invention is to stabilize the ink absorbing layer coating liquid to suppress cracks on the surface of the ink absorbing layer and to obtain a high gloss inkjet recording paper having a high print density.
  • Silica fine particles having a weight average molecular weight of 60-: a water-soluble compound having an aliphatic hydroxyl group of LOOO and a water-soluble polyvalent metal compound. Cationic fine particle dispersion of 45 mV or more.
  • Two or more ink absorption layers are laminated on the support, and the outermost ink absorption layer located at the farthest position of the support force is the cationic fine particle dispersion of any one of (1) to (7) Inkjet recording paper containing a hydrophilic binder.
  • Mass ratio A (the oxide mass Z of the water-soluble polyvalent metal compound) when the water-soluble polyvalent metal compound and silica fine particles contained in the outermost ink absorbing layer are converted into their respective oxides Silica fine particles (amount of acid and soot substance) force included in all ink absorbing layers except the outermost ink absorbing layer
  • Total mass ratio B of water-soluble polyvalent metal compound and silica fine particles converted to their respective oxides (total mass of water-soluble polyvalent metal compound acid Z (8) Inkjet recording paper larger than (total mass).
  • the maximum secondary ion intensity derived from a water-soluble polyvalent metal compound obtained by time-of-flight secondary ion mass spectrometry (TOF-SIMS) in the depth direction of the laminated ink absorption layer group is (9) Inkjet recording paper, whose outermost surface force is within 10 ⁇ m in the depth direction.
  • the condition defined by the following formula (1) is the mass ratio when the ratio between the water-soluble polyvalent metal compound and the silica fine particles contained in the outermost ink absorbing layer is converted into each oxide: Fill (9) or (10) inkjet recording paper.
  • M represents a divalent or higher valent metal atom
  • X represents a divalent or higher valent metal atom M.
  • FIG. 1 is a graph showing an example of a profile of secondary ion intensity derived from a water-soluble polyvalent metal compound measured by time-of-flight secondary ion mass spectrometry (TOF-SIMS).
  • FIG. 2 is a distribution measurement chart in the depth direction of an ink absorption layer of aluminum ions obtained by TOF-SIMS measurement of recording paper 2 as a comparative example.
  • FIG. 3 is a distribution measurement chart in the depth direction of an ink absorption layer of aluminum ions obtained by TOF-SIMS measurement of the recording paper 4 of the present invention.
  • the present inventor adds a water-soluble polyvalent metal compound adsorbed on silica fine particles by a dispersion method to the outermost ink absorbing layer located at the farthest support force, thereby allowing the polyvalent metal compound to diffuse.
  • a silica fine particle dispersion in the presence of a water-soluble polyvalent metal compound, by changing the pH during the dispersion, a highly concentrated water-soluble polyvalent metal compound is obtained. Obtaining the knowledge that the dispersion liquid contained can be prepared, the inventors have reached the first embodiment of the present invention.
  • the dispersion liquid is stabilized by dispersing silica fine particles in the presence of a water-soluble cationic polymer having a weight average molecular weight of 50000 or less and a water-soluble polyvalent metal compound, and setting the zeta potential of the dispersion liquid to +45 mV or more.
  • a water-soluble polyvalent metal compound in the dispersed state of the cationic silica composite fine particles with a zeta potential of +45 mV or higher alone is highly cationic, so inorganic salts, binders, etc.
  • the compound having an aliphatic hydroxyl group is bonded via a hydrogen bond by dispersing the water-soluble polyvalent metal compound and the silica fine particles in the presence of the compound.
  • Silica fine particles and water-soluble polyvalent metal compound power Cationic silica composite fine particles Cover the surface moderately and maintain the cationic property with inorganic salts, binders, etc.
  • silica fine particles are roughly classified into wet method silica fine particles and gas phase method silica fine particles according to the production method.
  • the former wet method silica fine particles are mainly produced by producing active silica by acid decomposition of the silicate, and then polymerizing it appropriately and aggregating and precipitating to obtain hydrous silica.
  • NIPGEL manufactured by Nippon Silica Industry Co., Ltd., manufactured by Tokuyama Co., Ltd. using the gel method.
  • Precipitated silica is roughly 10-60 nm
  • gel silica is roughly 3-: LOnm primary particles are characterized as sili- force particles with secondary aggregates formed.
  • gas phase method silica fine particles are synthesized by a combustion method using tetrasalt silicate and hydrogen as raw materials.
  • Aerosil series manufactured by Nippon Aerosil Co., Ltd., Tokuma Corporation The Leo Mouth Seal Series is commercially available.
  • a high porosity can be obtained and a cationic fine particle dispersion can be produced. It is preferable to use vapor-phase silica particles because coarse aggregates are hardly formed. Also
  • vapor phase silica secondary agglomerates are formed by relatively weak interaction with wet silica, and therefore have low characteristics when compared to wet silica with low energy! is doing.
  • the vapor phase silica fine particles have a particularly large specific surface area, so that the ink absorbency and retention ratio are high, and the refractive index is low. There is an advantage that a high color development density and a good hue can be obtained.
  • the silica fine particles preferably have an average primary particle size of 3 to 50 nm. If the average particle size of the primary particles is 50 nm or less, high glossiness of the recording paper can be achieved, and a clear image can be obtained by preventing the decrease in the maximum density due to irregular reflection on the surface.
  • the average particle size of the silica fine particles is obtained by observing the cross section or surface of the particle itself or the porous ink absorption layer with an electron microscope, and determining the particle size of a large number of arbitrary particles. ). Each particle size is expressed as a diameter assuming a circle equal to the projected area.
  • the average particle size is 20 to 200 nm, which provides high ink absorption and high gloss. If you get the record paper you have achieved, you are very much fond of it.
  • the amount of silica fine particles added depends largely on the required ink absorption capacity, the porosity of the porous ink absorption layer, and the type of the hydrophilic binder, but generally 5 to 2 per lm 2 of recording paper. 30g, preferably 10-25g.
  • the ratio of the silica fine particles used in the ink absorbing layer to the hydrophilic binder is approximately 2: 1 to 20: 1 by mass ratio, and preferably 3: 1 to LO: 1.
  • the ability to increase the ink absorption capacity as the amount of silica fine particles added increases There is also a break-up such as curling and cracking, so the capacity is increased by the porosity! ] Is preferable.
  • the preferred porosity is 40-75%. Porosity depends on the type of silica particles selected, the type of hydrophilic binder, or their mixing ratio, or the amount of other additives. Can be adjusted by.
  • the porosity here refers to the ratio of the total volume of the voids to the volume of the ink absorbing layer, and is calculated from the total volume of the constituents of the layer and the thickness of the layer. Further, the total volume of the voids can be easily obtained by measuring the amount of water absorption.
  • water-soluble polyvalent metal compound examples include aluminum, calcium, magnesium, zinc, iron, strontium, norium, nickel, copper, scandium, gallium, indium, titanium, zirconium, tin, and lead. And metal hydrochlorides, sulfates, nitrates, acetates, formates, succinates, malonates, black acetates, and the like.
  • water-soluble salts composed of aluminum, calcium, magnesium, zinc and zirconium are preferred because their metal ions are colorless.
  • a water-soluble aluminum compound and a water-soluble zirconium compound are particularly preferable.
  • the water-soluble aluminum compound examples include polyaluminum chloride (basic aluminum chloride), aluminum sulfate, basic aluminum sulfate, potassium aluminum sulfate (miyoban), and ammonium sulfate (ammonium sulfate).
  • polyaluminum chloride basic aluminum chloride
  • aluminum sulfate basic aluminum sulfate
  • potassium aluminum sulfate potassium aluminum sulfate
  • ammonium sulfate ammonium sulfate
  • ammonium sulfate ammonium sulfate
  • -Ummyoban sodium sulfate, aluminum nitrate, aluminum phosphate, aluminum carbonate, polysulfate aluminum silicate, aluminum acetate, basic aluminum lactate and the like.
  • the water solubility in the water-soluble polyvalent metal compound means that it dissolves in water at 20 ° C. in an amount of 1% by mass or more, more preferably 3% by mass or more.
  • the most preferable water-soluble aluminum compound is basic aluminum chloride having a basicity of 80% or more from the viewpoint of ink absorbability, and can be represented by the following molecular formula.
  • the basicity is expressed as nZ6 X 100 (%).
  • the water-soluble zirconium compound are preferably zirconyl carbonate, zirconyl carbonate, zirconium acetate, zirconium nitrate, zirconium oxychloride, zirconium lactate, and zirconium citrate.
  • zirconium carbonate and zirconium acetate are particularly preferred.
  • acid salt and zirconium acetate are resistant to bleeding during long-term storage. The viewpoint power is also preferable.
  • the cationic fine particle dispersion of the first embodiment of the present invention is dispersed by adding gas phase method silica fine particles having an anionic surface to an aqueous solution containing a water-soluble polyvalent metal compound ( Primary dispersion), a pH adjuster is added to the obtained primary dispersion, and the mixture is dispersed (secondary dispersion).
  • the cationic fine particle dispersion of the second embodiment of the present invention comprises silica fine particles in an aqueous solution containing a water-soluble polyvalent metal compound in the presence of a water-soluble cationic polymer having a weight average molecular weight of 50000 or less. It is added and dispersed (primary dispersion), and a pH adjuster is added to the obtained primary dispersion, and the mixture is dispersed (secondary dispersion).
  • the cationic fine particle dispersion of the second embodiment of the present invention is an aqueous solution containing a water-soluble polyvalent metal compound in the presence of a compound having an aliphatic hydroxyl group having a weight average molecular weight of 1,000 or less. Then, dispersion is performed by adding silica fine particles (primary dispersion), a pH adjuster is added to the obtained primary dispersion, and the mixture is dispersed (secondary dispersion).
  • the primary dispersion method a known method can be used.
  • a dispersion medium mainly composed of a water-soluble polyvalent metal compound and water using a jet stream inductor mixer manufactured by Mitamura Riken Kogyo Co., Ltd.
  • a primary dispersion can be obtained by sucking and dispersing the vapor phase silica fine particles therein.
  • Examples of the secondary dispersion method include conventionally known high-speed rotary dispersers, medium agitating dispersers (ball mill, sand mill, etc.), ultrasonic dispersers, colloid mill dispersers, roll mill dispersers, and high pressure dispersers.
  • Various dispersers can be used, but in the present invention, an ultrasonic disperser or a high-pressure disperser is preferable from the viewpoint of efficiently dispersing the aggregated vapor phase method silica fine particles formed. Used.
  • Ultrasonic dispersers are usually dispersed by energizing 20-25kHz ultrasonic waves into the solid-liquid interface so that they can be dispersed very efficiently. Particularly suitable when preparing dispersions.
  • high-pressure dispersers are equipped with one or two homogenous valves at the outlet of a high-pressure pump with three or five pistons, the gap of which can be adjusted by screws or hydraulic pressure. And by high pressure pump The liquid medium that has been fed is squeezed by the homogenous valve and pressure is applied, and at the moment when the liquid medium passes through the homogenous valve, the fine lumps are crushed. Since this method can disperse a large amount of liquid continuously, it is particularly preferred when preparing a large amount of dispersion.
  • the pressure applied to the homogeneous valve is usually 5 to: LOOMPa, and the dispersion can be done in one pass or repeated many times.
  • the surface of the silica fine particles is completely replaced with cationic to stabilize.
  • the mixing ratio of the water-soluble polyvalent metal compound to the silica fine particles is expressed as 0. 0 as the mass ratio (the oxide mass of the water-soluble polyvalent metal compound z the amount of the oxidized substance of the silica fine particles). It is preferably 10 or more and 1.0 or less, more preferably 0.15 or more and 0.80 or less.
  • the silica fine particles are almost completely covered with the cationic component, so This is preferable because it does not cause the formation of coarse particles due to ionic bonds with the valent metal compound.
  • the coating solution is prepared as the ratio of the water-soluble polyvalent metal compound decreases, it tends to gel when mixed with a hydrophilic binder.
  • the ratio of the water-soluble polyvalent metal compound increases, There may be problems with stagnation stability.
  • the cationic fine particle dispersion of the first embodiment it is necessary to add and disperse the vapor phase silica fine particles in the presence of a water-soluble polyvalent metal compound.
  • the cationic fine particle dispersion obtained by adding the water-soluble polyvalent metal compound to the silica slurry obtained by adding the vapor phase method silica fine particles to the aqueous medium and mixing and stirring the dispersion is later made hydrophilic.
  • the ink absorption layer coating solution is prepared by adding a binder or the like, if the viscosity increases, gelation occurs and the desired coating solution cannot be obtained!
  • the cationic fine particle dispersion of the first embodiment is obtained by changing the pH with a pH adjuster from the primary dispersion state.
  • a uniform dispersion of cation-converted silica fine particles can be obtained, and a stable coating liquid without turbidity change or viscosity change can be obtained in the subsequent process of preparing the ink absorbing layer coating liquid.
  • the pH is raised at the time of dispersion to obtain a cationic fine particle dispersion, and as a result, ink absorbability and ink fixability can be improved.
  • the pH change range is preferably from 0.20 to 1.0. If the change width is 0.20 or less, the effect of the present invention is hardly obtained. If the change width is 1.0 or more, gelation or aggregation of the dispersion may occur.
  • the time of dispersion means the time of primary dispersion, that is, the period from the end of primary dispersion to the end of secondary dispersion.
  • Acids of the pH adjusting agent used in both embodiments include, for example, formic acid, acetic acid, dallic acid, oxalic acid, propionic acid, malonic acid, conocuccinic acid, adipic acid, maleic acid, and lingo Organic acids such as acid, tartaric acid, citrate, benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, glutaric acid, darconic acid, lactic acid, aspartic acid, glutamic acid, pimelic acid and suberic acid, hydrochloric acid, nitric acid, boric acid and Examples thereof include inorganic acids such as phosphoric acid.
  • alkali examples include sodium hydroxide, potassium hydroxide, calcium hydroxide, aqueous ammonia, potassium carbonate, sodium carbonate, trisodium phosphate, and triethanolamine.
  • the present invention is not limited to these.
  • the amount of these various acids or alkalis to be added must be determined in consideration of the acidity or alkalinity of the various acids depending on the progress of dispersion and the stability of the dispersion.
  • a boron compound is preferable.
  • Boron compound means boric acid and its salts, such as borax, boric acid, borate (for example, orthoborate, InBO, ScB
  • metaborate eg, LiBO, Ca (BO), NaBO, KBO
  • tetraborate eg,
  • Two or more boron compound aqueous solutions can be used alone.
  • a mixture of borax and boric acid is particularly preferred.
  • Each of the aqueous solutions of boric acid and borax can be added only in a relatively dilute aqueous solution, but by mixing them both can be made into a concentrated aqueous solution and the dispersion can be concentrated.
  • the dispersion described above can be used in combination with a cationic polymer having a quaternary ammonium base from the viewpoint of ink absorbability, film strength, and the like.
  • various additives can be added.
  • nonionic or cationic surfactants for example, various nonionic or cationic surfactants, antifoaming agents, nonionic hydrophilic polymers (polybulal alcohol, polybutylpyrrolidone, polyethylene oxide, polyacrylamide, various sugars, gelatin, Pullulan, etc.), non-ionic or cationic latex dispersions, water-miscible organic solvents (such as ethyl acetate, methanol, ethanol, isopropanol, n-propanol, acetone), inorganic salts, etc. as needed Can be used.
  • nonionic or cationic surfactants for example, various nonionic or cationic surfactants, antifoaming agents, nonionic hydrophilic polymers (polybulal alcohol, polybutylpyrrolidone, polyethylene oxide, polyacrylamide, various sugars, gelatin, Pullulan, etc.), non-ionic or cationic latex dispersions, water-misc
  • a water-miscible organic solvent when a water-miscible organic solvent is mixed with an aqueous solution containing vapor-phase silica fine particles having a surface-on property and a water-soluble polyvalent metal compound, formation of fine lumps is suppressed. Is preferable.
  • Such water-miscible organic solvents are used in the dispersion in the range of 0.1 to 20% by weight, particularly preferably in the range of 0.5 to 10% by weight.
  • a cationic polymer having a weight average molecular weight of 50000 or less is used in combination when the silica fine particles and the water-soluble polyvalent metal compound are dispersed.
  • the cationic polymer is a polymer having a primary to tertiary amine, a quaternary ammonium base, or a quaternary phosphonium base in the polymer main chain or side chain, and is used for ink jet recording paper.
  • substantially water-soluble compounds are preferred as polyethyleneimine, polyallylamine, polyvinylamine, dicyandiamide polyalkylenepolyamine.
  • Burylpyrrolidone / Burimidazole copolymer Polyburpyridine, Polyamidine, Chitosan, Cationized starch, Bulbendil trimethylammonum chloride polymer, (2-Metachloroxychetyl) trimethylammonum chloride polymer, Examples thereof include dimethylaminoethyl methacrylate polymer.
  • the weight average molecular weight of the cationic polymer needs to be 50000 or less, and is preferably in the range of 2000 to 30000. If the weight average molecular weight exceeds 50000, the molecular weight is large, and the cationic silica composite fine particles are completely wrapped, so that the adhesive strength with the binder is weakened, and film surface failure is likely to occur.
  • the weight average molecular weight is 60 to L000 for the purpose of improving dispersion stability together with the water-soluble polyvalent metal compound and the silica fine particles.
  • a water-soluble compound having an aliphatic hydroxyl group is used, and a compound containing a sulfur atom is preferable.
  • the weight average molecular weight of the aliphatic hydroxyl group is preferably 60 to 500 from the viewpoint of obtaining better dispersion stability.
  • the water-soluble compound as used in the present invention means a compound that dissolves in water at 20 ° C in an amount of 1% by mass or more, preferably 3% by mass or more.
  • water-soluble compound having an aliphatic hydroxyl group examples include compounds represented by formulas (1-1, 1-2, 1-3, JP-A-2002-187345, as compounds containing sulfur. 1-4, 1-9, 1-10, 1-12), glycols such as ethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, diethylene glycol monobutyl ether, glycerin, diglycerin Powers including butanediol, butanetriol, trimethylolpropane, triethanolamine, sorbitol, etc.
  • a compound containing sulfur is more preferable than the viewpoint of the dispersion stability of the cationic fine particle dispersion.
  • silica fine particles are added to a solution containing a water-soluble polyvalent metal compound in the presence of a water-soluble compound having an aliphatic hydroxyl group having a weight average molecular weight of 60 to LOOO. It is preferable to add and disperse, but the water-soluble polyvalent metal compound or the weight-average molecular weight of 60 to:
  • the water-soluble compound having an aliphatic hydroxyl group of LOOO is not dispersed before the start of secondary dispersion, that is, primary dispersion. It is preferable to add it before or during the primary dispersion or during the secondary dispersion. (Zeta potential)
  • the zeta potential at 25 ° C. of the cationic fine particle dispersion of the second embodiment or the average zeta potential of the cationic silica composite fine particles contained in the dispersion is set to +45 mV or more.
  • the zeta potential was measured using a concentrated zeta potential measuring machine (Matec Applied Sciences: ESA-9800), and the dispersion was diluted to 3% by mass in terms of SiO solid content.
  • the zeta potential measured in the dispersion is the average value of each particle, and the power that should be the average zeta potential even in the case of the dispersion is simply the zeta potential here.
  • the zeta potential or the zeta potential of the cationic silica composite fine particles is +45 mV or higher as the dispersion, a high printing density can be obtained. More preferably +50 mV or more
  • Means for adjusting the zeta potential of the dispersion to this range can be achieved by cationizing silica based on the high thione concentration of the cationic polymer or the amount of metal salt.
  • the method for realizing the average zeta potential of the cationic silica composite fine particles defined in the present invention is not particularly limited, but the compound having an aliphatic hydroxyl group having a weight average molecular weight of 1000 or less according to the present invention. A method of appropriately selecting the type and amount added is effective. (Inkjet recording paper)
  • the ink jet recording paper of the present invention comprises two or more ink absorption layers laminated on a support, and the cationic fine particle dispersion of the present invention and a hydrophilic binder on the ink absorption layer (outermost layer) having the farthest support force. It contains.
  • the mass ratio A (the oxide mass Z of the water-soluble polyvalent metal compound) Oxide mass of Licca fine particles) Force Total mass ratio B when water-soluble polyvalent metal compound and silica fine particles contained in all ink absorption layers except the outermost ink absorption layer are converted into their respective acid compounds B It is preferable that the total mass of the acid compound of the water-soluble polyvalent metal compound is larger than the total mass of the acid compound of the silica fine particles. At this time, the total mass ratio B includes no case of an oxide of a water-soluble polyvalent metal compound. [0055] Further, it is preferable that two or more ink absorbing layers are applied simultaneously.
  • hydrophilic binder that can be used in the present invention, conventionally known various hydrophilic binders are used, and when mixed with the cationic silica composite fine particle dispersion of the present invention, aggregation or marked thickening action is achieved. Do not show! /, Hydrophilic binders are preferred. Examples of such hydrophilic binders include polyvinyl alcohol, gelatin (preferably acid-treated gelatin), polyethylene glycol (preferably an average molecular weight of 100,000 or more), polyethylene oxide, and polybutylpyrrolidone (preferably an average molecular weight of 200,000).
  • hydrophilic refers to being soluble in a mixed solvent of water and a water miscible organic solvent such as methanol, isopropyl alcohol, acetone, and ethyl acetate in addition to being soluble in water.
  • a water miscible organic solvent such as methanol, isopropyl alcohol, acetone, and ethyl acetate
  • the ratio of the water-miscible organic solvent is usually 50% by mass or less based on the total amount of the solvent.
  • a hydrophilic binder those which dissolve usually 1 mass% or more at room temperature in the solvent, preferably from , is to dissolve 3 weight 0/0 above.
  • the hydrophilic binder particularly preferably used in the present invention is polybulal alcohol, and in addition to the usual polyvinyl alcohol obtained by hydrolyzing polyvinyl acetate, the terminal is cationically modified polyvinyl alcohol. Also included are modified polyvinyl alcohols such as ion-modified polyvinyl alcohol having a functional group and ultraviolet-crosslinked modified polyvinyl alcohol.
  • a polybulal alcohol obtained by subjecting butyl acetate to brine decomposition is preferably one having an average degree of polymerization of 1000 or more. Particularly, those having an average degree of polymerization of 1500 to 5000 have good film brittleness. Power is preferable. Furthermore, the degree of kenning of polybulal alcohol is preferably 70 to 100%, particularly preferably 80 to 99.5%.
  • Examples of the cation-modified polybutyl alcohol include those described in JP-A-61-10483.
  • Examples of the ethylenically unsaturated monomer having a cationic group include trimethyl (2 acrylamide-1,2,2 dimethylethyl) ammonium chloride, trimethyl-1- (3-acrylamide-3,3-dimethylpropyl) ammonium chloride, N-bule.
  • the ratio of the cationically modified poly Bulle alcohol cation-modified group containing monomer is 0. respect acetate Bulle 10 mol 0/0, preferably from 0.2 to 5 mol 0/0.
  • Examples of the arion-modified polybulal alcohol include polybulal alcohols having a terionic group as described in JP-A-1 206088, JP-A-61-27681, and JP-A-63768. — Copolymers of bur alcohol and bully compounds having water-soluble groups as described in 307979 and modified polyvinyl alcohols having water-soluble groups as described in JP-A-7-285265 Is mentioned.
  • non-one-modified polybulal alcohol examples include, for example, a polyvinyl alcohol derivative in which a polyalkylene oxide group as described in JP-A No. 7-9758 is attached to a part of the bull alcohol.
  • examples thereof include a block copolymer of a bur compound having a hydrophobic group and bur alcohol described in Kaihei 8-25795.
  • UV-crosslinking modified polyvinyl alcohol examples include a modified polybulal alcohol having a photoreactive side chain as described in JP-A-2004-262236.
  • polyvinyl alcohol may be used in combination of two or more types having different degrees of polymerization or modification.
  • the ink jet recording paper of the present invention is excellent in glossiness and has a high porosity and a coating brittleness. In order to obtain it without deteriorating, it is preferable that it is hardened with a hardener when polybulal alcohol is used.
  • the hardener is generally a compound having a group capable of reacting with polybulal alcohol, or a compound that promotes the reaction between different groups of polyvinyl alcohol.
  • Filming agents eg, diglycidyl ethyl ether, ethylene glycol diglycidyl ether, 1,4 butanediol diglycidyl ether, 1,6-diglycidinolecyclohexane, N, N diglycidinole 4-glycidinole xylaniline, sorbi Tall polyglycidyl ether, glycerol polyglycidyl ether, etc.), aldehyde hardeners (eg formaldehyde, darioxal, etc.), active halogen hardeners (2, 4 dichloro-4 hydroxy-1, 3, 5 s triazine, etc.) ), Active bulle compounds (eg 1, 3, 5 trisacryloyl Hydro one s Toriajin, Bisubinirusu s
  • boric acid and salts thereof oxygen acids having boron atom as a central atom and salts thereof are shown. Specifically, orthoboric acid, diboric acid, metaboric acid, tetraboric acid, pentaboric acid, Octaboric acid and salts thereof are included.
  • the amount of the hardening agent used varies depending on the type of polyvinyl alcohol, the type of hardening agent, the type of silica fine particles, the ratio to polyvinyl alcohol, etc. Usually 5 to 500 mg per lg of polyvinyl alcohol, preferably 10 to 300 mg.
  • the hardener may be added to the water-soluble coating solution for forming the ink absorbing layer, or may be added to the coating solution, or the water-soluble coating solution for forming the ink absorbing layer (hardening film). After coating and drying, a solution containing a hardener can be supplied by overcoating.
  • the ink absorbing layer containing the cationic fine particle dispersion of the present invention has the farthest support strength and the ink absorbing layer (the outermost layer). ).
  • an ink absorbing layer with a high concentration of water-soluble polyvalent metal compound It is preferable to localize near the surface.
  • the maximum secondary ion intensity derived from a water-soluble polyvalent metal compound obtained by time-of-flight secondary ion mass spectrometry (TOF-SIMS) in the depth direction of the laminated ink absorption layer group It is preferable that the maximum surface force is within 10 m in the depth direction.
  • the water-soluble polyvalent metal compound contained in the outermost layer is 0.1 to 1. Og / m 2 as the mass of the polyvalent metal compound in terms of oxide. It is preferable that Below 0. lg / m 2, there is a difference in performance in terms of image density, and above 1. Og / m 2, there is a difference in performance in terms of ink absorption.
  • a water-soluble polyvalent metal can be contained in the ink absorbing layer other than the outermost layer as long as the conditions specified in the present invention are satisfied.
  • the mass when the water-soluble polyvalent metal compound contained in the ink absorbing layer located at the outermost portion is converted to an oxide is defined as O, and the mass ratio of the total water-soluble polyvalent metal compound converted into oxides [ ⁇ ( ⁇ +
  • FIG. 1 is a graph showing an example of a profile of secondary ion intensity derived from a water-soluble polyvalent metal compound measured by time-of-flight secondary ion mass spectrometry (TOF-SIMS).
  • time-of-flight secondary ion mass spectrometry (TOF-SIMS) is shown with the maximum surface force on the horizontal axis and the measurement distance m in the depth direction on the horizontal axis and the respective depth positions on the vertical axis.
  • the secondary ionic strength values derived from the polyvalent metal compound measured in (1) were plotted.
  • Profile B is a typical example showing a state with a clear maximum ionic strength within 10 m.
  • the maximum value of the secondary ion intensity derived from the polyvalent metal compound is Since the ink is present inside the ink absorption layer (in Fig. 1, the depth is approximately 15 / zm), the ink that has landed on the outermost surface is more fixed inside the ink absorption layer. As a result, a high image density cannot be obtained.
  • the ink absorbing layer profile according to the present invention which is composed of two or more ink absorbing layers and is configured by adding a high-concentration polyvalent metal compound to the outermost layer, is shown. Since the maximum value of secondary ionic strength derived from the polyvalent metal compound exists within 10 / zm depth from the outermost surface (in Fig. 1, at a position of about 6 m depth), The ink landed on the outermost surface is fixed in the surface area of the ink absorbing layer, and as a result, a high image density can be obtained.
  • the ratio of the water-soluble polyvalent metal compound and the silica fine particles contained in the ink absorbing layer located on the outermost part of the two or more laminated ink absorbing layers is the same. It is better than SiO / MO ⁇ 10 when converted to each oxide.
  • M is divalent or higher contained in water-soluble polyvalent metal compounds
  • X represents the valence of a metal atom M having a valence of 2 or more.
  • the content of the water-soluble polyvalent metal compound in the depth direction of the ink absorption layer can be measured by using an electron probe microanalyzer (EPMA) or a flight of a sample obtained by trimming the side surface of an ink jet recording paper with a microtome or the like.
  • EPMA electron probe microanalyzer
  • TOF SIMS time-type secondary ion mass spectrometer
  • the distribution of secondary ion fragments peculiar to polyvalent metal compounds is measured using a time-of-flight secondary ion mass spectrometer capable of obtaining chemical structure information, and the thickness of the existing portion of the polyvalent metal atom is determined.
  • the method to obtain is preferable.
  • a smooth ink absorption layer cross section is exposed with a microtome or the like, and TOF-SIMS measurement is performed on the ink absorption layer.
  • the ion species preferable as the primary ion at the time of TOF—SIMS measurement are In and Ga + among the forces that are metal ion species such as Au +, In +, Cs +, and Ga +.
  • a secondary ion to be detected a secondary ion mass spectral force of a polyvalent metal measured in advance is selected.
  • the beam diameter measured by the knife edge method in which the acceleration voltage of primary ions is preferably 20 kV to 30 kV, is 0.25 / zm or less.
  • Irradiation conditions such as beam current and irradiation time are arbitrary. A typical example is the primary ion A preferable measurement condition is a beam current of 0.9 nA, an irradiation time of 20 minutes, and the like. Note that the ink jet recording paper or the ink absorbing layer is poor in conductivity, and therefore, it is preferable to appropriately perform charge neutralization such as using a neutralizing electron gun.
  • the primary ion beam is scanned within a range in which the entire area of the ink absorption layer can be measured.
  • a 40 m square area is scanned. It is possible to obtain an image of chemical species present in the ink absorption layer from the scanning position of the primary ion beam and the detected secondary ions.
  • a secondary ion mass spectrum at 256 ⁇ 256 points is obtained within the scanning region, and the intensity of the target secondary ion peak is recorded from the mass spectrum, thereby obtaining an image of the chemical species.
  • a profile in the thickness direction of a specific secondary ion can be obtained.
  • Creating a secondary ion image and creating a profile are usually functions attached to data processing software of a secondary ion mass spectrometer, and this function can also be used in the present invention.
  • a portion of 1.5 times or more the minimum value of the secondary ion intensity derived from the polyvalent metal in the ink absorption layer It is defined as the metal existence part.
  • the position of the ink absorption layer and the thickness of the ink absorption layer are the regions where metal ions contained in the silica fine particles present in the ink absorption layer are detected, as in the case of polyvalent metals.
  • the position of each layer is 50% of the integrated ion intensity in the profile in the thickness direction.
  • the distribution amount of the polyvalent metal compound in the depth direction was measured under the conditions of ion species: In and acceleration voltage: 25 kV using TRIFT-II manufactured by Pysical Electronics.
  • the dry film thickness of the outermost layer according to the present invention is 2 to 20% of the total dry film thickness of the total ink absorbing layer, more preferably 5 to 1. 5%. That is, by laminating two or more ink absorbing layers and containing the above water-soluble polyvalent metal compound in a high concentration in the outermost layer of the thin layer, the surface area as shown in FIG. In addition, it is possible to realize an ink absorbing layer in which the maximum secondary ion intensity derived from the polyvalent metal compound appears.
  • the outermost layer of the ink absorbing layer according to the present invention preferably contains a surfactant.
  • a surfactant that can be used in the ink absorption layer, any of cationic, betaine, and nonionic hydrocarbon, fluorine, and silicon surfactants can be used. Among them, from the viewpoint of coating quality such as coating failure resistance and suitability for simultaneous multi-layer coating
  • the cationic and betaine surfactants described in JP-A-2003-312134 are preferred.
  • the amount of surfactant 0. 0001-1. More preferably Og / m 2 is preferred instrument 0. 00 1 ⁇ 0. 5gZ m (? Mel.
  • These ultraviolet absorbers, antioxidants, and anti-smudge agents include alkylated phenol compounds (including hindered phenol compounds), alkylthiomethyl phenol compounds, hydroquinone compounds, alkylated hydroquinone compounds, Tocopherol compounds, thiodiphenyl-ether ether compounds, compounds having two or more thioether linkages, bisphenol compounds, ⁇ -, N-, S benzyl compounds, hydroxybenzyl compounds, triazine compounds, phosphonate compounds, acyl acylamines ⁇ nol compounds, ester compounds, amido compounds, ascorbic acid, amine-based antioxidants, 2- (2-hydroxyphenol) benzotriazole compounds, 2-hydroxybenzophenone compounds, attalylate, water-soluble or Hydrophobic metal salts, organometallic compounds, metal complexes, Hinderdamine compounds (including so-called TEMPO compounds), 2- (2 hydroxyphenol) 1, 3, 5, triazine compounds, metal inert agents, phosphite compounds,
  • alkylated phenol compounds having two or more thioether bonds
  • Compounds, bisphenol compounds, ascorbic acid, amine-based antioxidants, water-soluble or hydrophobic metal salts, organometallic compounds, metal complexes, hindered amine compounds, hydroxyamine compounds, polyamine compounds, thiourea Compounds, urea compounds, hydrazide compounds, hydroxybenzoic acid compounds, dihydroxybenzoic acid compounds, trihydroxybenzoic acid compounds, and the like are preferable.
  • polystyrene polyacrylic acid esters, polymethacrylic acid esters, polyacrylamides, polyethylene, polypropylene, polychlorinated butyl, polysalt vinylidene, or a copolymer thereof, urea resin, melamine resin, etc.
  • Organic latex fine particles liquid paraffin, dioctyl phthalate, tricresyl phosphate, silicone oil and other oil droplets, various cationic and non-ionic surfactants, JP-A 57-74193, 57-87988 No. 62-261476, JP-A 57-74192, 57-87989, 60-72785, 61-146591, JP-A-1-95091 No.
  • pH adjusters such as sulfuric acid, phosphoric acid, citrate, sodium hydroxide, potassium hydroxide, potassium carbonate, etc.
  • defoaming as described in Japanese Patent No. 242871 and JP-A-4-219266
  • Various known additives such as an agent, a preservative, a thickener, an antistatic agent, and a matting agent can be contained.
  • a non-water-absorbing support that does not generate cockling during printing is preferred.
  • the non-water-absorbing support is a plastic resin film support or a support in which both sides of paper are coated with a plastic resin film.
  • the body is mentioned.
  • the plastic resin film support include a polyester film, a polychlorinated bull film, a polypropylene film, a cellulose triacetate film, a polystyrene film, and a film support in which these are laminated. These plastic resin films can be transparent or translucent. Most preferred is a support having both sides of paper coated with polyolefin resin.
  • each constituent layer including an ink absorbing layer can be produced by individually or simultaneously selecting a known coating method force and coating and drying on a support. Simultaneous multilayer coating is preferred.
  • the application method include roll coating method, rod bar coating method, air knife coating method, spray coating method, curtain coating method, or U.S. Pat.Nos. 2,761,419 and 2,761,791.
  • a slide bead coating method using the described hopper, an extrusion one-coat method, or the like is preferably used.
  • the viscosity of each coating solution when two or more constituent layers are applied simultaneously is preferably in the range of 5 to: LOOmPa's when the slide bead coating method is used. Is in the range of 10-50mPa's. Further, when the curtain coating method is used, the range of 5 to 120 OmPa's is preferable, and the range of 25 to 500 mPa's is more preferable.
  • the viscosity at 15 ° C of the coating solution is preferably lOOmPa's or more, more preferably 100-30, OOOmPa's force S, and more preferably ⁇ to 3,000-30, OOOmPa's. And most preferred is 10,000 to 30, OOOmPa, s.
  • the coating liquid was heated to 30 ° C or higher, and after simultaneous multi-layer coating, the temperature of the formed coating film was cooled to 1 to 15 ° C and cooled. It is preferable to dry at a temperature of ° C or higher. Preparation, application, and drying of the coating liquid at a temperature not higher than Tg of the thermoplastic resin so that the thermoplastic resin contained in the surface layer does not form a film during preparation of the coating liquid, during application, and during drying. Is preferred. More preferably, the drying conditions are a wet bulb temperature of 5 to 50 ° C and a film surface temperature of 10 to 50 ° C. Also, as a cooling method immediately after coating, it is preferable to use a horizontal setting method from the viewpoint of the uniformity of the formed coating film.
  • the heating condition is not particularly limited as long as it is stored under conditions of 35 ° C or higher and 70 ° C or lower for 24 hours or longer and 60 days or shorter.
  • a preferable example is, for example, 36 ° C. 3 days to 4 weeks, 2 days to 2 weeks at 40 ° C, or 1 to 7 days at 55 ° C.
  • the above water-based ink is a recording liquid having the following colorant, solvent, and other additives.
  • the colorant include water-soluble dyes such as direct dyes, acid dyes, basic dyes, reactive dyes, and food-use dyes known in ink jet, or water-dispersible pigments.
  • water and various water-soluble organic solvents can be used.
  • Polyhydric alcohols such as diethylene glycol and triethanolamine and glycerin, and lower alkyl of polyhydric alcohol such as triethylene glycol monobutyl ether. Ether etc. are preferred.
  • water-based ink additives examples include pH adjusters, metal sequestering agents, fungicides, viscosity modifiers, surface tension modifiers, wetting agents, surfactants and antifungal agents.
  • the water-based ink liquid usually has a surface tension within a range of 0.025 to 0.06 NZm, preferably 0.03 to 0.05 NZm, at 20 ° C. It is preferable to have.
  • the pH of the ink is preferably 5 to 10, particularly preferably 6 to 9.
  • Fine particle dispersion A-1 was prepared.
  • a cationic fine particle dispersion A-2 was prepared in the same manner as the cationic fine particle dispersion A-1, except that the aqueous solution containing boric acid and borax was removed. At this time, the respective pH values after the primary dispersion and the secondary dispersion were 3.48.
  • Aqueous solution containing 2% ethanol (31.5 L) with 7.89 kg of basic salt-aluminum aqueous solution (Taki Chemical: Takibine # 1500, 23.75% AlO, basicity 83.5%)
  • a uniform dispersion medium was prepared by stirring.
  • gas phase method silica (Aerosil 300 manufactured by Nippon Aerosil Co., Ltd.) with an average primary particle size of about 0.007 ⁇ m, and Jetstream 'Inductor Mixer TDS manufactured by Mitamura Riken Kogyo Co., Ltd. Used, and suction-dispersed (primary dispersion) in the previously prepared dispersion medium, and the gas phase silica concentration is 18.5% (A1 O
  • the type of water-soluble polyvalent metal compound, the mass ratio of the water-soluble polyvalent metal compound to the silica vapor phase method, and the pH adjusting agent during secondary dispersion Cationic fine particle dispersions A-4 to A-10 were prepared in the same manner except that the dispersion, pH after the primary dispersion and after the secondary dispersion were changed as shown in Table 1.
  • the cationic fine particle dispersions A-1 to A-10 prepared above were filtered using a TCP-30 type filter manufactured by Advantech Toyo Co., Ltd. having a filtration accuracy of 30 ⁇ m. went.
  • the dispersion state of each dispersion liquid was confirmed according to the method described in JP-A-11-321079. As a result, extremely stable cation-converted fine particles were obtained. Confirmed that.
  • coating solution A-1 The following additives were sequentially added and mixed to prepare coating solution A-1.
  • the total volume was made up to 1000 ml with pure water.
  • the coating liquid A-1 In the preparation of the coating liquid A-1, the coating liquid was similarly used except that the cationic fine particle dispersions A-2 to A-10 prepared above were used instead of the cationic fine particle dispersion A-1. A-2 to A-9 were prepared.
  • the coating liquid A-1 For coating liquids A-2 and A-4 using cationic fine particle dispersions A-2 and A-4 that do not contain boric acid and borax, the coating liquid A-1 is used when preparing the ink absorbing layer coating liquid. The same amounts of boric acid and borax as A-3 were added.
  • ⁇ per hour is 1.
  • OmPa's is acceptable, preferably within 0.5mPa's
  • the cationic fine particles of the present invention prepared by dispersing vapor phase method silica fine particles in the presence of a water-soluble polyvalent metal compound and changing the pH at the time of dispersion.
  • the coating liquid prepared using the particle dispersion liquid does not increase the viscosity of the coating liquid or generate aggregates, and has good viscosity stability even after the coating liquid has been stagnated for a long time.
  • high transparency was maintained, that is, no agglomerates were generated at the time of stagnation.
  • a fluorescent fluorescent whitening agent (Ciba 400L of si
  • a silica dispersion D-2 was prepared in the same manner as in the preparation of the silica dispersion D-1, except that the light-on fluorescent whitening agent was removed.
  • silica dispersions Dl and D-2 prepared above were filtered using a TCP-30 type filter manufactured by Advantec Toyo Co., Ltd. having a filtration accuracy of 30 m.
  • each ink absorption layer coating solution for the porous layer was prepared using the silica dispersions prepared above.
  • each addition amount was indicated by the amount per liter of coating solution.
  • the whole volume was made up to 1000ml with pure water.
  • Acrylic copolymerized emulsion made by Daido Kasei Kogyo; Bisol 1083)
  • the whole volume was made up to 1000ml with pure water.
  • the whole volume was made up to 1000ml with pure water.
  • the whole volume was made up to 1000ml with pure water.
  • Each ink absorbing layer coating solution prepared as described above was filtered with a TCPD-30 filter manufactured by Advantech Toyo Co., Ltd. having a filtration accuracy of 20 m, and then filtered with a TCPD-10 filter.
  • each of the ink absorbing layer coating solutions prepared above is placed on a paper support (RC paper) coated with polyethylene on both sides at 40 ° C. so that the wet film thickness described below is obtained. 4 layers were simultaneously applied using a coating machine.
  • 3rd layer 44 / ⁇ ⁇ (3) Amount: 4. 40 g / m 2 )
  • the RC paper is in the form of a roll with a width of about 1.5m and a length of about 4000m, the moisture content is 8%, the basis weight is 170g, and the surface of the photographic paper is 170%.
  • the contained polyethylene was extruded and melt coated at a thickness of 35 ⁇ m, and polyethylene on the back was extruded and melt coated at a thickness of 35 / zm.
  • a polybum alcohol Karl's PVA235
  • Tg was about 80 ° C.
  • a back layer containing about 0.4 g of a styrene-acrylic ester latex donor, 0.1 lg of an antistatic agent (cationic polymer) and 0. lg of silica of about 2 ⁇ m as a matting agent was applied. .
  • Drying after applying the ink absorbing layer coating liquid is performed by passing the cooling zone maintained at 5 ° C for 15 seconds to reduce the film surface temperature to 13 ° C, and then the temperature of the multiple drying zones.
  • the total dry film thickness of the ink absorbing layer thus formed was 42.5 m, and the dry film thickness of the fourth layer (outermost layer) was 11.5 m. Further, the recording paper 1 does not contain a water-soluble polyvalent metal compound in all layers.
  • Recording paper 2 was produced by overcoating so that the amount of 2 3 2 3 was 0.5 g / m 2 .
  • the silica dispersion D-2 in the fourth layer was changed to the cationic fine particle dispersion A-3 prepared in Example 1, and the SiO amount of the fourth layer was 2.0 g. / m 2 , Al O
  • the silica dispersion D-2 in the third layer was changed to the cationic fine particle dispersion A-3 prepared in Example 1, and the SiO coating amount of the third layer was 2. Og. / m 2 , Al O
  • Recording paper 4 was prepared in the same manner except that the amount of 2 2 3 was changed to 0.5 gZm 2 and the dry film thickness was changed to 4. O / zm (9.4% of the total dry film thickness). The silica fine particles of 2.40 g / m 2 min were equally distributed to the first layer, the second layer, and the fourth layer, and the total amount of SiO was the same. ⁇ 4 ( ⁇ + j8) of recording paper 4 is 0
  • Recording paper 5 was produced in the same manner except that 2 3 2 3 was added to 0.05 g / m 2 .
  • the recording paper 5 has ⁇ Z ( ⁇ + j8) of 0.9.
  • the basic layer-aluminium aqueous solution (Taki Chemical: Takibine # 1500, 23.75% Al O, contained in base 4)
  • Recording paper 9 was prepared in the same manner except that the dry film thickness was 4.0 m (9.4% of the total dry film thickness). In addition, 2.40g / m 2 minute silica fine particles were equally distributed to the 1st to 3rd layers, and the total amount of SiO was the same.
  • the recording paper 6 has ⁇ Z ( ⁇ + j8) of 1.0.
  • the fourth layer has an SiO coating weight of 2.0 g / m 2 and a dry film thickness of 4.0 ⁇ m.
  • the recording paper 7 has ⁇ Z ( ⁇ + j8) of 1.0.
  • Recording paper 8 was produced in the same manner except that in was added.
  • the recording paper 8 has ⁇ ⁇ ( ⁇ + ⁇ ) of 0.86.
  • the cross section of the ink absorption layer is TRIFT-II manufactured by Pysical Electronics, and the ion species is In and the acceleration voltage is 25 kV.
  • the distribution in the depth direction of the ink absorption layer of aluminum ions was determined by TOF-SIMS measurement. As a result, it was confirmed that the recording paper of the present invention had a maximum value force and a maximum surface force of secondary ion intensity derived from aluminum within 10 m in the depth direction.
  • FIGS. 2 and 3 show distribution measurement charts of the polyvalent metal compound on the comparative recording sheet 2 and the recording sheet 3 of the present invention.
  • Fig. 2 shows a distribution measurement chart in the depth direction of the ink absorption layer of aluminum ions obtained by TOF-SIMS measurement of recording paper 2 as a comparative example.
  • the outermost layer is the right end of the chart, and LengthO m) represents the support surface.
  • LengthO m represents the support surface.
  • Fig. 3 shows a distribution measurement chart in the depth direction of an aluminum ink absorption layer obtained by TOF-SIMS measurement of the recording paper 4 of the present invention. Similarly in FIG. 3, the outermost layer is the right end of the chart, and LengthO ( ⁇ m) represents the support surface.
  • the maximum surface force is very large in the region up to 10 m deep, and that basic aluminum chloride is distributed in the surface region.
  • the image quality determined by the absolute value of the surface reflection component dominates the surface quality.
  • the image quality measuring device ICM-1DP manufactured by Suga Test Instruments Co., Ltd. was used to measure the C value at 60 degrees reflection.
  • Line width change rate (Line width of the black line after saving Z Line width of the black line before saving) X 100
  • Inkjet printer PM manufactured by Seiko Epson in an environment of 23 ° C and 80% RH -A blue solid image was printed at 950C, and the surface of the solid image immediately after printing was rubbed with a finger to visually observe the disorder of the image, and ink absorbency was evaluated according to the following criteria.
  • Table 2 shows the evaluation results except the measurement of polyvalent metal compound distribution in the ink absorption layer obtained as described above.
  • Vapor phase silica (manufactured by Nippon Aerosil: Aerosil 200) lOOOg
  • silica fine particle dispersion 1 The above was added, dispersed with a high-pressure homogenizer manufactured by Sanwa Co., Ltd., and then finished to 5500 ml to prepare silica fine particle dispersion 1.
  • Silica composite fine particle dispersion liquid 1 was dispersed by adding 200 g of zirconyl acetate (manufactured by Daiichi Rare Element Chemicals Co., Ltd .: Zircosol ZA-30) as a ZrO equivalent amount to obtain silica composite fine particle dispersion liquid 3.
  • silica composite fine particle dispersion 3 Same as for silica composite fine particle dispersion 3, except that 200 g of zirconium acetate was used as Al 2 O equivalent using basic salt ⁇ aluminum (manufactured by Taki Chemical: Takibine # 1500)
  • a silica composite fine particle dispersion 4 was prepared.
  • a silica composite fine particle dispersion 5 was prepared in the same manner as in the silica composite fine particle dispersion 4, except that the basic salt of aluminum was changed to 10 g.
  • Silica composite fine particle dispersion 6 was prepared in the same manner except that the basic salt-aluminum was changed to salt-magnesium and 200 g was used as the MgO equivalent in silica composite fine particle dispersion 4.
  • a silica composite fine particle dispersion 7 was prepared in the same manner except that the basic salt / aluminum of the silica composite fine particle dispersion 4 was changed to 66 g.
  • the weight average molecular weight of the cationic polymer of silica composite fine particle dispersion 4 is about 200,000.
  • a silica composite fine particle dispersion 8 was prepared in the same manner except that the cationic polymer (manufactured by Nittobo: PAS-H-10L) was used.
  • Table 3 shows the zeta potential of the dispersion, the mass ratio in terms of oxide of the silica Z water-soluble polyvalent metal compound as the outermost layer, and the degree of stabilization as a dispersion, depending on the stability of the dispersion. Evaluation based on the criteria.
  • the zeta potential of the dispersion was measured using a concentrated zeta potential measuring machine (manufactured by Matec Applied Sciences: ESA-9800), and the dispersion was adjusted to 3% by mass in terms of SiO solid content.
  • the silica Z water-soluble polyvalent metal compound ratio in the outermost layer is calculated by calculating the composition of the outermost layer coating liquid composition in terms of acid oxide, and the dispersion stability is determined by passing through the dispersion.
  • the viscosity was determined as follows by increasing the viscosity after storage. Viscosity was measured at a temperature of 25 ° C using a Brooksfield digital viscometer PV-II + (B-type rotational viscometer). (Dispersion stability)
  • the silica composite fine particle dispersion of the present invention has good dispersion stability.
  • the following coating solutions 1, 2, 3, and 4 are applied to the recording surface of a photographic paper support (thickness 220 / zm) coated on both sides of a base paper weighing 200gZm 2 with a wet film thickness of 50, 55. , 60, and 15 m, cooled at 5 ° C for 10 seconds, and then dried with 40 ° C air to prepare Recording Paper 1.
  • a coating solution was prepared by adding pure water so that the total solution was 1000 ml.
  • Recording paper 2 was prepared in the same manner as recording paper 1 except that silica composite fine particle dispersion 2 was used as the outermost layer.
  • a recording paper 3 was prepared in the same manner as the recording paper 1 except that the silica composite fine particle dispersion 3 was used as the outermost layer.
  • Recording paper 4 was prepared in the same manner as recording paper 1 except that silica composite fine particle dispersion 4 was used as the outermost layer.
  • a recording paper 5 was prepared in the same manner as the recording paper 1 except that the silica composite fine particle dispersion 5 was used as the outermost layer.
  • a recording paper 6 was prepared in the same manner as the recording paper 1 except that the silica composite fine particle dispersion 6 was used as the outermost layer. “Preparation of Recording Paper 7: (Invention)”
  • Recording paper 7 was prepared in the same manner as recording paper 1 except that silica composite fine particle dispersion 7 was used as the outermost layer.
  • a recording paper 8 was prepared in the same manner as the recording paper 1 except that the silica composite fine particle dispersion 8 was used as the outermost layer.
  • Recording paper 9 was prepared in the same manner except that the wet film thickness of the first, second, third, and fourth layers of recording paper 4 was changed to 40, 40, 50, m.
  • the thickness of the outermost layer of the produced recording paper was measured. For the measurement, tomographic photographs were taken for each recording sheet using a scanning electron microscope, and the ratio (%) of the thickness of the outermost layer to the thickness of the outermost layer and the entire thickness of the ink absorbing layer was measured.
  • Recording sheets 1 to 8 had a surface layer thickness in the range of 3.6 to 3.9 m, and the ratio of the surface layer thickness to the entire ink absorbing layer was 8.0 to 8.7%.
  • the outermost layer thickness of the recording paper 9 was 12.3 m, and the ratio of the outermost layer thickness to the entire ink absorbing layer was 27.3%.
  • the recording sheets 1 to 9 produced above were evaluated as follows. The results are shown in Table 4. For each recording paper, in the profile of the secondary ion fragment derived from the water-soluble polyvalent metal compound obtained by T OF-SIMS of the water-soluble polyvalent metal compound in the direction of the ink absorption layer thickness, The force that has the maximum value of the ionic strength peak within m. The results confirmed by using the TRIFT-II manufactured by Pysical Electronics Co., Ltd. according to the above method are the values of the zeta potential of the silica composite fine particle dispersion used. The results are shown in Table 4.
  • a black solid print was made using an Epson inkjet printer PMG800, and the reflection density was measured.
  • the reflection density was measured with a spectrocolorimeter densitometer X-Rite938 (manufactured by X Rite).
  • the image clarity C value was measured at 60 degrees reflection using a image clarity measuring instrument (ICM 1DP) manufactured by Suga Test Instruments Co., Ltd.
  • the viscosity changing power of the coating solution over time was also determined as follows.
  • the viscometer was measured at 25 ° C using a digital viscometer PV-II + (B-type rotational viscometer) manufactured by Brooksfield. Measurement was performed using a spherical turbidimeter SEP-PT-706D (25 ° C).
  • the ink jet recording paper of the invention may have a film surface failure due to the stability of the coating liquid. It can be seen that there is little glossiness and the printing density is high and good.
  • the above additives were sequentially mixed, dispersed with a high pressure homogenizer manufactured by Sanwa Co., Ltd., and finished to 5500 ml to prepare silica fine particle dispersion B.
  • the zeta potential of the silica fine particles contained in the silica fine particle dispersion B prepared above was 3% by mass in terms of Si 2 O solid content using a concentrated zeta potential measuring instrument (Matec Applied Sciences: ESA-9800). The dispersion was diluted so that the average zeta potential was measured.
  • silica fine particle dispersion A instead of the compound having an aliphatic hydroxyl group, zirconyl acetate (Dilcosol ZA-30, manufactured by Daiichi Rare Element Chemical Industry) was converted into ZrO amount.
  • zirconyl acetate (Dilcosol ZA-30, manufactured by Daiichi Rare Element Chemical Industry) was converted into ZrO amount.
  • Cationic silica composite fine particle dispersion B-1 was prepared in the same manner except that 200 g was added as 2.
  • the average zeta potential of the silica composite fine particles contained in the above-prepared cationic silica composite fine particle dispersion B-1 was measured in the same manner as described above, and was found to be +50 mV.
  • the silica fine particle dispersion A was prepared in the same manner except that 200 g of zirconium acetate (Zircozole ZA-30, manufactured by Daiichi Rare Element Chemical Co., Ltd.) was added in terms of ZrO.
  • Cationic silica composite fine particle dispersion B-2 was prepared.
  • the average zeta potential of the silica composite fine particles contained in the above-prepared cationic silica composite fine particle dispersion B-2 was measured in the same manner as described above, and was found to be +50 mV.
  • Cationic silica composite fine particle dispersion B-3 was prepared in the same manner except that 200 g was used in an amount of 2 3.
  • the average zeta potential of the silica composite fine particles contained in the cationic silica composite fine particle dispersion B-3 prepared above was measured in the same manner as described above, and was found to be +55 mV.
  • the cationic silica composite fine particle dispersion B-3 was prepared in the same manner except that a 25% aqueous solution of trimethylolpropane was used instead of the compound having an aliphatic hydroxyl group (compound A). Silica composite fine particle dispersion B-4 was prepared.
  • the average zeta potential of the silica composite fine particles contained in the above-prepared cationic silica composite fine particle dispersion B-4 was measured in the same manner as described above, and was found to be +55 mV.
  • Cationic silica composite fine particle dispersion B-5 was prepared in the same manner as in the preparation of the above-mentioned cationic silica composite fine particle dispersion B-3 except that the amount of basic aluminum chloride added was changed to lOg. Prepared.
  • the average zeta potential of the silica composite fine particles contained in the above-prepared cationic silica composite fine particle dispersion B-5 was measured in the same manner as described above, and was found to be +43 mV.
  • cationic silica composite fine particle dispersion B-3 basic aluminum chloride was used.
  • Cationic silica composite fine particle dispersion B-6 was prepared in the same manner except that -um was changed to magnesium chloride and 200 g in terms of MgO was used.
  • the average zeta potential of the silica composite fine particles contained in the prepared cationic silica composite fine particle dispersion B-6 was measured in the same manner as described above, and was found to be +50 mV.
  • Cationic silica composite fine particle dispersion B-7 was prepared in the same manner as in the preparation of the above-mentioned cationic silica composite fine particle dispersion B-3 except that the amount of basic aluminum chloride added was changed to 66 g. Prepared.
  • the average zeta potential of the silica composite fine particles contained in the prepared cationic silica composite fine particle dispersion B-7 was measured in the same manner as described above, and was found to be +47 mV.
  • cationic silica composite fine particle dispersion B-3 the compound having an aliphatic hydroxyl group (Compound A) was changed to polyvinyl alcohol (Kuraray: PVA203) having a low polymerization degree. Similarly, cationic silica composite fine particle dispersion B-8 was prepared.
  • the average zeta potential of the silica composite fine particles contained in the above-prepared cationic silica composite fine particle dispersion B-8 was measured in the same manner as described above, and was found to be +50 mV.
  • a cationic silica composite fine particle dispersion B-9 was prepared in the same manner except that 200 g of a 20% aqueous solution of the following cationic polymer was added. .
  • the average zeta potential of the silica composite fine particles contained in the above-prepared cationic silica composite fine particle dispersion B-9 was measured in the same manner as described above, and was found to be +57 mV.
  • the average zeta potential of the silica composite fine particles contained in the above-prepared cationic silica composite fine particle dispersion B-10 was measured in the same manner as described above, and was found to be +53 mV.
  • silica fine particle dispersion B and the cationic fine particle dispersion B-1 prepared above were prepared.
  • the viscosity of each dispersion after stirring for 12 hours at 40 ° C. was measured by Tokyo Keiki Co., Ltd. Measurement was made using a B-type viscometer BL, and the dispersion stability was evaluated according to the following criteria.
  • Dispersion viscosity after 12 hours is 50 mPa's or more and less than 200 mPa's
  • X Dispersion viscosity after 12 hours is 200 mPa's or more and less than 500 mPa's
  • XX After 12 hours Dispersion viscosity is 500mPa's or more
  • Table 5 shows the results obtained as described above.
  • each ink absorption layer coating solution for the porous layer was prepared using the silica fine particle dispersion B prepared above.
  • each addition amount was displayed by the amount per 1L of coating solution.
  • Silica fine particle dispersion B (prepared and stagnated at 40 ° C for 12 hours) 550 g Poly280% 6.0% aqueous solution of polybulal alcohol (Kuraren clay PVA235)
  • Silica fine particle dispersion B (prepared and stagnated at 40 ° C for 12 hours) 660 g 6.0% aqueous solution of polybulal alcohol (PVA235 made of KURARENE) 250 g
  • the total volume was made up to 1000 ml with pure water.
  • Each ink absorption layer coating solution prepared as described above was filtered through a TCPD-30 filter manufactured by Advantech Toyo with a filtration accuracy of 20 ⁇ m, and then filtered through a TCPD-10 filter.
  • each of the ink absorbing layer coating solutions prepared above is placed on a paper support (RC paper) coated with polyethylene on both sides at 40 ° C. so that the wet film thickness described below is obtained. 4 layers were simultaneously applied using a coating machine. ⁇ Wet film thickness>
  • Second layer 55 ⁇
  • the RC paper is the same as in Example 2.
  • the recording paper b-1 was prepared in the same manner as the recording paper b-1, except that the silica fine particle dispersion B of the fourth layer was changed to the cationic fine particle dispersions B-1 to B-10 prepared in Example 4.
  • b-2 to b-10 and b-12 were prepared.
  • the total dry film thickness of each ink absorbing layer of recording papers b-2 to b-10 and b-12 was 45 ⁇ m, and the dry film thickness of the fourth layer was 3.75 m.
  • the recording paper b-11 was prepared in the same manner except that the wet film thicknesses of the first to fourth layers were changed to 40 m, 40 ⁇ m, 50 ⁇ m, and 50 m, respectively.
  • the total dry film thickness of the ink absorbing layer of recording paper b-11 was 45 / ⁇ ⁇ , and the dry film thickness of the fourth layer was 12.5 m.
  • the cross section of the ink absorbing layer was measured by TOF-SIMS measurement using TRIFT-II manufactured by Pysical Electronics.
  • the distribution of polyvalent metal ions in the depth direction of the ink absorption layer as shown in Fig. 1 was measured, and the position where the maximum value of the secondary ion intensity derived from the polyvalent metal ions was measured was measured.
  • the film surface failure resistance was evaluated according to the following criteria.
  • ⁇ The number of crack failures is less than 5, and the occurrence of streak failures is not recognized.
  • a black solid image was printed with genuine ink using an ink jet printer PM-950C manufactured by Seiko I Epson, and after natural drying for 3 hours, the resulting black density was measured using a reflection densitometer manufactured by X-rite. This was used as a measure of color developability.
  • the image quality determined by the absolute value of the surface reflection component dominates the surface quality.
  • the image quality measuring device ICM-1DP manufactured by Suga Test Instruments Co., Ltd. was used to measure the C value at 60 degrees reflection.
  • the viscosity of the coating solution was measured using a B-type viscometer BL manufactured by Tokyo Keiki Co., Ltd.
  • the turbidity measurement of the coating solution was performed using an integrating sphere turbidimeter SEP- Measurements were taken using a PT-706D.
  • ⁇ The increase in the viscosity of the coating solution after 3 hours is less than lOmPa's, or the increase in the turbidity is less than ⁇ pm
  • ⁇ The increase in viscosity of the coating solution after 3 hours is lOmPa's or more and less than 20mPa's, or the increase in turbidity is lOppm or more and less than 20ppm
  • X The increase in the viscosity of the coating solution after 3 hours is 20 mPa's or more, or the increase in turbidity is 2 Oppm or more.
  • Table 6 shows the evaluation results obtained as described above.
  • the recording paper of the present invention used in the present invention is superior in coating solution stability to the comparative example, has a polyvalent metal compound in the surface area, and has high film surface resistance, glossiness, and color development of printed images. I understand that.
  • a high-quality ink jet recording paper that is excellent in glossiness and ink absorbability that are free from defects such as cracks during production and that can obtain a high image density, and excellent in dispersion stability that can be achieved.
  • a cationic fine particle dispersion can be provided.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Ink Jet Recording Methods And Recording Media Thereof (AREA)
  • Ink Jet (AREA)
  • Silicon Compounds (AREA)

Abstract

L’invention concerne des dispersions de fines particules cationiques que l’on obtient soit en dispersant de fines particules de silice en phase vapeur en présence d’un composé de métal polyvalent soluble dans l’eau et en modifiant l’acidité pH dans la phase de dispersion ou bien en dispersant de fines particules de silice en phase vapeur en présence d’un composé de métal polyvalent soluble dans l’eau et en augmentant l’acidité pH dans la phase de dispersion ; elle concerne également des dispersions de fines particules cationiques contenant chacune un polymère cationique soluble dans l’eau d’un poids moléculaire moyen en poids inférieur ou égal à 50000 et un composé de métal polyvalent soluble dans l’eau aux potentiels zêta supérieurs ou égaux à +45mV à 25°C; et des dispersions de fines particules cationiques contenant chacune de fines particules de silice, un composé hydroxyle aliphatique soluble dans l’eau d’un poids moléculaire moyen en poids de 60 à 1000, et un composé de métal polyvalent soluble dans l’eau et susceptible de former de fines particules composites de silice cationiques aux potentiels zêta supérieurs ou égaux à +45mV.
PCT/JP2005/019296 2004-10-28 2005-10-20 Dispersions de fines particules cationiques et papiers d’enregistrement à jet d’encre WO2006046463A1 (fr)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007301890A (ja) * 2006-05-12 2007-11-22 Tokuyama Corp インクジェット記録材
JP2009214324A (ja) * 2008-03-07 2009-09-24 Fujifilm Corp インクジェット記録媒体及びその製造方法
JP2013519802A (ja) * 2010-02-11 2013-05-30 ストラ エンソ オサケ ユキチュア ユルキネン 表面処理組成物

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Publication number Priority date Publication date Assignee Title
JP2000239536A (ja) * 1998-12-24 2000-09-05 Tokuyama Corp カチオン性樹脂変性シリカ分散液及びその製造方法
JP2002201385A (ja) * 1999-11-12 2002-07-19 Canon Inc 液体組成物、及び、それを用いたインクセット、画像形成方法、画像形成装置、画像及びブリード緩和方法
JP2002526564A (ja) * 1998-10-02 2002-08-20 キャボット コーポレイション シリカ分散体、コーティング組成物、及び記録媒体
WO2004018359A1 (fr) * 2002-08-22 2004-03-04 Degussa Ag Dispersion de dioxyde silicium aqueuse stabilisee

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002526564A (ja) * 1998-10-02 2002-08-20 キャボット コーポレイション シリカ分散体、コーティング組成物、及び記録媒体
JP2000239536A (ja) * 1998-12-24 2000-09-05 Tokuyama Corp カチオン性樹脂変性シリカ分散液及びその製造方法
JP2002201385A (ja) * 1999-11-12 2002-07-19 Canon Inc 液体組成物、及び、それを用いたインクセット、画像形成方法、画像形成装置、画像及びブリード緩和方法
WO2004018359A1 (fr) * 2002-08-22 2004-03-04 Degussa Ag Dispersion de dioxyde silicium aqueuse stabilisee

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007301890A (ja) * 2006-05-12 2007-11-22 Tokuyama Corp インクジェット記録材
JP2009214324A (ja) * 2008-03-07 2009-09-24 Fujifilm Corp インクジェット記録媒体及びその製造方法
JP2013519802A (ja) * 2010-02-11 2013-05-30 ストラ エンソ オサケ ユキチュア ユルキネン 表面処理組成物

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