WO2011040508A1 - Support d'enregistrement pour jet d'encre - Google Patents

Support d'enregistrement pour jet d'encre Download PDF

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Publication number
WO2011040508A1
WO2011040508A1 PCT/JP2010/067038 JP2010067038W WO2011040508A1 WO 2011040508 A1 WO2011040508 A1 WO 2011040508A1 JP 2010067038 W JP2010067038 W JP 2010067038W WO 2011040508 A1 WO2011040508 A1 WO 2011040508A1
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Prior art keywords
ink
receiving layer
ink receiving
colloidal silica
support
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PCT/JP2010/067038
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English (en)
Japanese (ja)
Inventor
義雄 吉田
貴之 佐藤
昌也 登坂
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日本製紙株式会社
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Publication of WO2011040508A1 publication Critical patent/WO2011040508A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
    • B41M5/52—Macromolecular coatings
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
    • B41M5/52—Macromolecular coatings
    • B41M5/5218—Macromolecular coatings characterised by inorganic additives, e.g. pigments, clays
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
    • B41M5/52—Macromolecular coatings
    • B41M5/5245—Macromolecular coatings characterised by the use of polymers containing cationic or anionic groups, e.g. mordants

Definitions

  • An ink jet recording medium has a structure in which an ink receiving layer containing a porous pigment such as silica or alumina and a binder is provided on the surface of a support such as paper, and an ink liquid is provided on the ink receiving layer. Drops are fixed. With the remarkable progress of ink jet printers in recent years and the remarkable spread of digital cameras, the quality required for ink jet recording media is increasing year by year. In particular, in an inkjet recording medium having a gloss comparable to that of a conventional silver salt photograph, quality requirements are strict and technological development is actively being carried out.
  • the above-mentioned glossy inkjet recording medium is generally produced by a cast coating method using a cast coater from the viewpoint of production cost.
  • a coating liquid mainly composed of a pigment and a binder is coated on a support to provide a coating layer, and the coating layer is pressed against a heated cast drum to give a gloss finish.
  • This glossy coating layer is the ink receiving layer.
  • the cast coating method includes (1) a wet casting method (direct method) in which a coating layer is pressed onto a mirror-finished heating drum while the coating layer is wet, and (2) a wet coating layer is once dried.
  • Patent Document 5 A glossy paper having a thickness of / m 2 has been reported (for example, Patent Document 5). Further, the ink-receiving layer containing a pigment and a binder is laminated on both surfaces of the gas-permeable substrate, and a plurality of coating layers are formed by laminating the gloss-expressing layer on the ink-receiving layer. A double-sided ink jet recording sheet having a thickness of 1/10 or less of the thickness of the ink receiving layer has been reported (for example, Patent Document 6).
  • the present invention provides an inkjet recording medium having excellent glossiness, high printing density when ink jet recording is performed using a dye ink, excellent ink absorption and water resistance, and uniform glossiness on both sides.
  • the purpose is to provide.
  • the present inventors have found that the above-mentioned problems can be solved by allowing the cationic colloidal silica to stably exist in the vicinity of the surface of the ink receiving layer.
  • the surface on which the ink receiving layer is first formed by the coagulation cast coating method is the surface side of the support
  • the surface of the ink receiving layer on the front side and the back side of the support is respectively
  • the amount of the cationic colloidal silica present is preferably in the range of 1.4 to 7.5 in the ratio of (the front surface side / the back surface side).
  • the support preferably contains 3 to 25% by mass of light calcium carbonate as ash as defined in JIS-P 8251.
  • an ink jet recording medium having a high printing density when ink jet recording is performed using a dye ink, excellent ink absorbability and water resistance, and uniform glossiness on both sides.
  • the ink jet recording medium of the present invention comprises an ink-receiving layer provided on both surfaces of a gas-permeable support by a coagulation cast coating method.
  • any support may be used as long as it has a gas permeability sufficient to allow water vapor generated on the cast drum during the cast coating.
  • paper such as coated paper and uncoated paper is preferably used.
  • the raw material pulp of the support includes chemical pulp (coniferous bleached or unbleached kraft pulp, hardwood bleached or unbleached kraft pulp, etc.), mechanical pulp (ground pulp, thermomechanical pulp, chemithermomechanical pulp, etc.), deinking Pulp or the like can be used alone or mixed at an arbitrary ratio.
  • softwood pulp is contained as raw material pulp.
  • the strength of the base paper is improved and the glossiness of the ink receiving layer tends to be improved.
  • the surface property of the support tends to decrease as the content of softwood pulp increases, the content of softwood pulp is preferably 30% by mass or less in the total pulp.
  • the pH of the support may be acidic, neutral or alkaline.
  • the support preferably contains rosette-type light calcium carbonate as a filler.
  • Rosetta-type light calcium carbonate is obtained by agglomerating primary particles of spindle-shaped light calcium carbonate in a radial manner to form Rosetta-type secondary particles.
  • Specialty Minerals Inc. Products such as Albuquer HO, Albuquer 5970, Albuquer LO, etc. can be preferably mentioned.
  • radial means, for example, that the longitudinal direction of each primary particle extends radially from the vicinity of the center of the secondary particle.
  • Light calcium carbonate is excellent in terms of production cost and operability, and high opacity can be obtained even when the amount added is small, and Rosetta-type light calcium carbonate has a special shape, so it is contained in the support. When blended at a high ratio, the opacity is greatly improved, and the back-through during ink jet recording is effectively prevented. Furthermore, since Rosetta-type light calcium carbonate has a larger specific surface area than conventional light calcium carbonate, a support excellent in ink absorbability can be obtained. In particular, when the amount of ink-receiving layer applied is small, the effect of increasing the ink absorbability can be obtained by using rosetta-type light calcium carbonate.
  • the average particle size of the rosetta type light calcium carbonate is preferably 1.0 to 5.0 ⁇ m.
  • the average particle diameter is measured by a laser diffraction / scattering method, and can be measured by, for example, “Mastersizer 2000” manufactured by Sysmex Corporation.
  • the average particle size of Rosetta-type light calcium carbonate is less than 1.0 ⁇ m, the transparency of the support is lowered due to the improved light transmission, and as a result, the printed image can be seen through from the back side of the recording paper. , There may be strike-through.
  • the oil absorption of Rosetta-type light calcium carbonate is preferably 90 to 300 ml / 100 g, particularly preferably 90 to 140 ml / 100 g.
  • the oil absorption of Rosetta-type light calcium carbonate is less than 90 ml / 100 g, the ink absorbability of the obtained inkjet recording medium tends to decrease.
  • the oil absorption of Rosetta-type light calcium carbonate exceeds 300 ml / 100 g, the support absorbs too much, and only the binder component penetrates into the paper when the ink receiving layer coating liquid is applied. Cheap. As a result, the surface strength of the ink receiving layer decreases, and problems such as powder falling off during cutting may occur.
  • FIG. 1 is an electron microscopic image showing an example of the form of Rosetta-type light calcium carbonate (secondary particles) in a state dispersed in a liquid.
  • the bases of the respective primary particles are aggregated, and each primary particle extends radially toward the tip.
  • each primary particle has a slightly larger width (diameter) at the base and narrows toward the tip.
  • micron in a figure shows micrometer.
  • the density of the support is lowered and the paper becomes bulky, and the cushioning property is improved.
  • the ink receiving layer coating layer is pressed against the cast drum at the time of cast coating, the ink receiving layer easily adheres to the surface of the cast drum, and as a result, the glossiness of the obtained ink receiving layer is improved.
  • Conceivable The higher the 20 degree gloss value, the better the glossiness.
  • the 20 degree gloss is preferably 20% or more.
  • the higher the value of image clarity the better the glossiness.
  • the image clarity is preferably 50% or more, and particularly preferably 70% or more.
  • the image clarity is measured on the surface of the ink receiving layer of the obtained inkjet recording medium using a image clarity measuring instrument (for example, model number: ICM-1DP, manufactured by Suga Test Instruments Co., Ltd.) according to JIS-K 7105. Can be measured. If the image clarity is 50% or more, the reflected image is clearly visible and the glossiness is excellent. When the image clarity is less than 50%, the reflected image appears unclear and the glossiness is inferior.
  • the density of the support is preferably 0.8 g / cm 3 or less.
  • the content of light calcium carbonate in the support is preferably 3 to 25% by mass, more preferably 10 to 20% by mass as ash as defined in JIS-P 8251.
  • the ash content of the rosetta-type light calcium carbonate in the support increases, the glossiness of the surface of the ink receiving layer provided by the cast coating method is greatly improved, and the effect of improving the ink absorbency when printing is increased.
  • the light calcium carbonate include other light calcium carbonates (for example, calcite type light calcium carbonate) in addition to the above-mentioned Rosetta type light calcium carbonate.
  • the content (ash content) of the light calcium carbonate in the support indicates the total content (ash content) of these multiple types of light calcium carbonate.
  • the light calcium carbonate ash content preferably does not exceed 25 mass%.
  • the ash content specified in JIS-P 8251 represents the amount of ash residue after burning the sample (paper) at a temperature of 525 ⁇ 25 ° C. as a percentage of the absolute dry weight of the sample.
  • fillers such as hydrated silicic acid, white carbon, talc, kaolin, clay, calcium carbonate (other than rosetta-type light calcium carbonate), titanium oxide, and synthetic resin fine particles. It can be appropriately selected and used in combination with the above-mentioned rosetta-type calcium carbonate.
  • the filler other than the rosetta-type calcium carbonate is preferably 30% by mass or less of the entire filler in the support, and more preferably contains no filler other than the rosetta-type calcium carbonate.
  • the air permeability of the support is preferably 1000 seconds or less from the viewpoint of the production efficiency of the ink jet recording medium, and the sticky size of the support is preferably 10 seconds or more from the viewpoint of coating properties. desirable.
  • a liquid containing various additives such as a water-soluble polymer additive is coated on the support by an on-machine or off-machine using a tab size, size press, gate roll coater, film transfer coater, or the like. It is possible to work.
  • water-soluble polymer additive examples include starch derivatives such as starch, cationized starch, oxidized starch, etherified starch, and phosphate esterified starch; polyvinyl alcohol derivatives such as polyvinyl alcohol and carboxy-modified polyvinyl alcohol; carboxymethylcellulose Cellulose derivatives such as hydroxymethyl cellulose, hydroxyethyl cellulose, cellulose sulfate; water-soluble natural polymers such as gelatin, casein, soybean protein; sodium polyacrylate, sodium styrene-maleic anhydride copolymer, sodium polystyrene sulfonate, etc. Water-soluble polymers such as maleic anhydride resins; aqueous polymer adhesives such as thermosetting synthetic resins such as melamine resins and urea resins are used.
  • starch derivatives such as starch, cationized starch, oxidized starch, etherified starch, and phosphate esterified starch
  • additives include petroleum resin emulsion as sizing agent, ammonium salt of styrene-maleic anhydride copolymer alkyl ester, alkyl ketene dimer, alkenyl succinic anhydride, styrene-butadiene copolymer, ethylene-vinyl acetate copolymer Examples thereof include dispersions such as coalescence, polyethylene, and polyvinylidene chloride. Examples of other additives include sodium chloride, calcium chloride, and bow glass, which are antistatic agents and inorganic electrolytes. Moreover, glycerin, polyethylene glycol, etc. are mentioned as a hygroscopic substance.
  • additives examples include pigments such as clay, kaolin, talc, barium sulfate, titanium oxide, calcium carbonate, hydrated silicic acid, white carbon, and synthetic resin fine particles.
  • pigments such as clay, kaolin, talc, barium sulfate, titanium oxide, calcium carbonate, hydrated silicic acid, white carbon, and synthetic resin fine particles.
  • hydrochloric acid, caustic soda, sodium carbonate, etc. which are pH regulators, are used, and other additives such as dyes, fluorescent brighteners, antioxidants, ultraviolet absorbers can be used in combination. is there.
  • the pigment of the ink receiving layer As the pigment of the ink receiving layer (the coating layer is made into an ink receiving layer by a coagulation cast coating method, but for convenience, the coating layer and the ink receiving layer are used without distinction), the pigment is colloidal particularly from the viewpoint of color development and gloss It is preferable to use silica. From the viewpoint of ink absorbability, it is preferable to use synthetic amorphous silica in combination with colloidal silica.
  • the colloidal silica used in the ink receiving layer is preferably anionic. This is because the colloidal silica in the coagulant described later is cationic, and therefore it is preferable to use an anionic colloidal silica that causes an agglomeration reaction effective in improving the coagulability in the ink receiving layer.
  • the primary particle size of the anionic colloidal silica is preferably 5 to 100 nm, more preferably 20 to 70 nm. When the primary particle diameter of the anionic colloidal silica is less than 5 nm, ink colorability may be lowered when printing is performed with an ink jet printer using pigment ink.
  • the primary particle diameter of anionic colloidal silica exceeds 100 nm, the voids between the particles increase and the ink absorption of the ink receiving layer is improved. However, since the opacity increases, color development when ink-jet recording with a dye ink is performed. May decrease.
  • synthetic amorphous silica may be used in combination as the pigment in the ink receiving layer.
  • Synthetic amorphous silica can be roughly classified into wet process silica and gas phase process silica depending on the production method.
  • Synthetic amorphous silica produced by a wet method (hereinafter referred to as “wet method synthetic amorphous silica”) is inferior to gas phase method silica in pigment transparency, but polyvinyl alcohol is bound to the ink receiving layer. Excellent paint stability when contained as an agent.
  • the wet method synthetic amorphous silica has better dispersibility than the gas phase method silica having no internal voids, and can increase the coating concentration.
  • the ratio of the pigment (to the binder) in the ink receiving layer can be increased, and the absorbability of the ink receiving layer can be increased, so that the ink absorbability can be improved and the color developability of the dye ink can be improved.
  • the secondary particle diameter of the wet-process synthesized amorphous silica is preferably 1 to 5 ⁇ m, and the BET specific surface area is preferably 100 to 300 m 2 / g.
  • the secondary particle diameter is smaller than 1 ⁇ m, the ink absorbability is inferior, and when it exceeds 4 ⁇ m, the glossiness tends to decrease.
  • the primary particle diameter of the vapor phase silica is preferably 4 to 30 nm, and the BET specific surface area is preferably 100 to 400 m 2 / g.
  • the mass blending ratio of colloidal silica and synthetic amorphous silica is preferably 10:90 to 60:40.
  • the blending ratio of the colloidal silica is less than 10% by mass, the color developability and glossiness are inferior, and when the blending ratio of the colloidal silica exceeds 60% by mass, the ink absorbability tends to be inferior.
  • inorganic fine particles and organic fine particles can be used in combination as other pigments in the ink receiving layer.
  • Other pigments include, for example, alumina hydrate (alumina sol, colloidal alumina, pseudo boehmite, etc.), alumina ( ⁇ type crystal alumina, ⁇ type crystal alumina, ⁇ type crystal alumina, etc.), calcium carbonate, titanium dioxide Etc. can be used.
  • alumina hydrate alumina sol, colloidal alumina, pseudo boehmite, etc.
  • alumina ⁇ type crystal alumina, ⁇ type crystal alumina, ⁇ type crystal alumina, etc.
  • calcium carbonate titanium dioxide Etc.
  • the primary particle size of the pigment of the ink receiving layer and the cationic colloidal silica in the coagulant solution described later can be measured by the BET method particle size (measured by a nitrogen adsorption method), and the secondary particle size is determined by dynamic light.
  • Each can be measured by a scattering particle size (measurement by laser diffraction / scattering method).
  • the binder for the ink receiving layer preferably contains polyvinyl alcohol which is a water-based binder resin having a coagulating action.
  • polyvinyl alcohol which is a water-based binder resin having a coagulating action.
  • Other water-based binder resins may be used in combination with polyvinyl alcohol as necessary in order to ensure the strength of the ink receiving layer.
  • aqueous means that the resin is dissolved or dispersed and stabilized (water-soluble and / or water-dispersible resin emulsion) in water or a medium composed of water and a small amount of an organic solvent.
  • the water-based binder resin means a water-soluble resin or a water-dispersible resin.
  • the aqueous binder resin is dissolved or dispersed in the coating liquid to be coated on the support, but after coating and drying, it becomes a binder for the pigment and forms an ink receiving layer.
  • aqueous binder resins include, for example, polyvinyl pyrrolidone; urethane resin derived from urethane resin emulsion; starches such as oxidized starch and esterified starch; cellulose derivatives such as carboxymethyl cellulose and hydroxyethyl cellulose; casein; gelatin; soy protein; -Acrylic resin and derivatives thereof; styrene-butadiene resin latex; acrylic resin emulsion, vinyl acetate resin emulsion, vinyl chloride resin emulsion, urea resin emulsion, alkyd resin emulsion, and derivatives thereof. These aqueous binder resins can be used by mixing with polyvinyl alcohol.
  • the polyvinyl alcohol is preferably partially saponified polyvinyl alcohol.
  • the addition amount of polyvinyl alcohol is preferably 5 to 30 parts by mass with respect to 100 parts by mass of the total pigment in the ink receiving layer.
  • the type of the binder is not particularly limited as long as the necessary ink receiving layer strength can be obtained.
  • the ink receiving layer contains the above-described pigment and binder, but other components such as a thickener, an antifoaming agent, an antifoaming agent, a pigment dispersant, a release agent, a foaming agent, a pH adjusting agent, and a surface.
  • Sizing agent, coloring dye, coloring pigment, fluorescent dye, ultraviolet absorber, antioxidant, light stabilizer, preservative, water resistance agent, dye fixing agent, surfactant, wet paper strength enhancer, water retention agent, cation In the range which does not impair the effect of this invention, a conductive polymer electrolyte etc. can be suitably added to the coating layer used as the precursor of an ink receiving layer.
  • a known coating machine such as a coater or a short dwell coater can be appropriately selected from the coating methods used on-machine or off-machine.
  • the coating amount of the ink receiving layer can be arbitrarily adjusted as long as the surface of the support is covered and sufficient ink absorbability is obtained.
  • the coating amount of the ink receiving layer is preferably 3 to 25 g / m 2 in terms of solid content per one side of the support, and in particular, taking productivity into consideration. Then, it is preferably 5 to 20 g / m 2 . If the coating amount of the ink receiving layer exceeds 25 g / m 2 , the peelability from the mirror finish surface of the cast drum will be reduced, and problems such as adhesion of the coating layer to the mirror finish surface of the cast drum may occur. .
  • the ink receiving layer when a large coating amount of the ink receiving layer (coating layer) is required, the ink receiving layer can be multilayered. Further, an undercoat layer having various functions such as ink absorptivity, adhesiveness and the like may be provided between the support and the ink receiving layer. Further, a back coat layer having various functions such as ink absorbability, writing property, printer printability and the like may be further provided on the side opposite to the surface on which the ink receiving layer is provided.
  • gloss is imparted by forming the outermost ink receiving layer by a solidified cast coating method.
  • the coagulation cast coating method is performed as follows, for example. First, an ink receiving layer coating solution is applied to a support to provide a coating layer. Next, a coagulant solution having the action of coagulating the binder (particularly the aqueous binder) in the coating layer is applied to the wet coating layer and gelled, and then applied to the heated mirror-finished surface. Crimp and dry.
  • the coagulation cast coating method can provide the ink receiving layer with a surface feel and gloss comparable to silver salt photography.
  • the coating layer is in a dry state when applying the coagulant solution, it is difficult to copy the surface of the mirror drum, and the surface of the resulting ink-receiving layer will have many fine irregularities, giving it the same glossiness as a silver salt photograph. Hateful.
  • polyvinyl alcohol is used as the water-based binder of the ink receiving layer
  • borate is used as the coagulant, so that it is easy to make the hardness at the time of solidification moderate, and the ink receiving layer Good glossiness can be imparted and operability is also improved.
  • cationic colloidal silica is added to the coagulant solution in the present invention, when borate is used in the coagulant solution, it aggregates with the cationic colloidal silica. For this reason, when a borate is used, it may be difficult to prepare a coagulant solution.
  • anionic colloidal silica is included in the ink-receiving layer coating solution, the coagulation reaction between the anionic coating solution and the cationic coagulant solution further improves print quality and provides high gloss. It is possible to provide an ink receiving layer having a stable operation.
  • the coagulant solution used in the present invention contains a boron compound, a cationic resin, and cationic colloidal silica.
  • the coagulant solution contains boric acid but does not contain borate.
  • (Cationic colloidal silica) When cationic colloidal silica is added to the coagulant solution, the cationic colloidal silica adheres to (is present on) the surface of the ink receiving layer due to the cast coat.
  • fine cationic colloidal silica having a primary particle size of 10 to 50 nm is present on the surface of the ink receiving layer, the printing density when printing with dye ink is improved.
  • fine cationic colloidal silica having a primary particle diameter of 10 to 50 nm is present on the outermost surface of the ink receiving layer, the surface of the ink receiving layer becomes smooth and gloss is improved.
  • Cationic colloidal silica is colloidal silica whose particle surface is highly positively charged.
  • Cationic colloidal silica is, for example, aluminum ion, magnesium ion, calcium ion, zirconium ion, etc., compared to colloidal silica obtained by heating and aging silica sol obtained through metathesis or acid exchange resin layer of sodium silicate, etc. It can be obtained by reacting multivalent metal ions.
  • Japanese Patent Publication No. 47-26959 discloses cationic colloidal silica by aluminum treatment.
  • Examples of the commercially available cationic colloidal silica include LUDOX CL and LUDOX CL-P manufactured by Grace, SNOWTEX AK and SNOWTEX AK-L manufactured by Nissan Chemical Co., Ltd.
  • two or more kinds of cationic colloidal silica may be mixed and used.
  • the primary particle size of the cationic colloidal silica is preferably 10 to 50 nm.
  • the primary particle size of the cationic colloidal silica is smaller than 10 nm, the glossiness of the ink receiving layer is excellent, but the absorbability of the dye ink may be inferior.
  • the primary particle size of the cationic colloidal silica is larger than 50 nm, the transparency of the ink receiving layer is lowered, and the printing density when printing with a dye ink may be lowered.
  • the primary particle diameter may exceed 50 nm, or the shapes such as tufts and rods may be different (various forms of agglomerated forms), and cationic colloidal silica may be used in combination. .
  • the primary particle diameter of the cationic colloidal silica is preferably smaller than the primary particle diameter of the pigment of the ink receiving layer. In this way, the finest cationic colloidal silica covers the outermost surface of the ink receiving layer, so that the glossiness is improved.
  • the “primary particle diameter of cationic colloidal silica” means the primary particle diameter of each cationic colloidal silica and the content ratio of each cationic colloidal silica. The weighted average value.
  • the “primary particle diameter of the pigment” is a value obtained by weighted averaging the primary particle diameter of each pigment by the content ratio of each pigment.
  • boric acid is preferably added to the coagulant solution to control coagulation, but boric acid is more solid (harder than borate). It is difficult to control. Therefore, an anionic colloidal silica is contained in the ink receiving layer coating solution so that the pH of the coating solution is 7 to 10 (30 ° C.), while the pH of the (cationic) coagulant solution is set to 1. By adjusting to ⁇ 4 (30 ° C.), solidification can be easily controlled even when boric acid is used, and stable operation is possible.
  • the piping of the coating apparatus or the like may melt.
  • the pH of the ink receiving layer coating solution is less than 7 or the pH of the coagulant solution is more than 4
  • the coagulation reaction becomes insufficient and stable operation tends to be difficult.
  • the cationic colloidal silica is preferably contained in an amount of 2 to 15% by mass in the coagulant solution.
  • the content of the cationic colloidal silica is less than 2% by mass, the glossiness is lowered, and the printing density when printing with a dye ink may be lowered.
  • the content rate of cationic colloidal silica exceeds 15 mass%, an aggregate (precipitate) will generate
  • pigments other than cationic colloidal silica hydrated alumina (alumina sol, colloidal alumina, pseudoboehmite, etc.), alumina ( ⁇ type crystal alumina, ⁇ type crystal alumina, ⁇ type crystal alumina, etc.), etc. are cationic. Although it may be used by mixing with colloidal silica, the mixing ratio of the other pigment to the cationic colloidal silica is preferably 50% by mass or less.
  • boric acid As the boron compound in the coagulant solution, boric acid is preferably used. It is preferable that 1 to 10% by mass of boric acid is contained in the coagulant solution. If the boric acid content is less than 1% by mass, the coagulation action may be insufficient. Moreover, when the content rate of boric acid exceeds 10 mass%, it cannot melt
  • the cationic resin By including the cationic resin in the coagulant solution, the cationic resin adheres (exists) to the surface of the ink receiving layer by the coagulation cast coat.
  • the cationic resin fixes the ink, improves the printing density when using the water-soluble dye ink, and further improves the water resistance.
  • the electrically positive cationic resin and the cationic colloidal silica coexist so that they do not aggregate.
  • the cationic resin examples include polyamine sulfone, polyalkylene polyamine, polyamine condensate, polyallylamine, polydiallylamine, polyvinylamine, polyethyleneimine, dicyandiamide condensate, cationic acrylic resin, and cationic urethane resin. Species or multiple species can be selected and used.
  • the content of the cationic resin in the coagulant solution is not particularly limited, but it is preferably 0.5 to 10% by mass. When the content ratio of the cationic compound is less than 0.5% by mass, the ink fixing function is lowered, and the print density of the printed image may be lowered. When the content ratio of the cationic compound exceeds 10% by mass, the viscosity of the coagulant increases and the coatability may be deteriorated.
  • the compounding quantity of the cationic colloidal silica in the coagulant solution applied to the front side is increased as compared with the back side so that the glossiness of the ink receiving layer on the front side becomes high.
  • the surface of the support on which the ink receiving layer is first formed by the coagulation cast coating method (the surface on which cast coating is first performed) is referred to as “the surface side of the support”. Since the casting method cannot give gloss to both sides simultaneously, the first cast coated surface comes into contact with the roll and anticipates that the gloss will decrease, and the coagulating liquid is applied a second time to match this glossiness. Reduce the amount of colloidal silica in the coagulation liquid on the surface to match the gloss after casting on both sides.
  • the 20 degree gloss of the ink receiving layer on the front side and the back side is adjusted.
  • the degree of gloss becomes 20% or more, and the difference in glossiness between 20 degrees is within 5%, so that a double-sided glossy paper having the same glossiness on the front side and back side of the support can be obtained.
  • the blending amount of the cationic colloidal silica in the coagulant solution applied to the coating layer on the surface side of the support is 10 to 15% by mass.
  • the amount of the cationic colloidal silica can be 2 to 7% by mass. More preferably, the amount of the cationic colloidal silica in the coagulant solution applied to the coating layer on the surface side of the support is 13 to 15% by mass, and the coagulant applied to the coating layer on the back side of the support.
  • the amount of the cationic colloidal silica in the solution is 5 to 7% by mass.
  • the amount of cationic colloidal silica contained in the coagulant solution applied to the coating layer on the front side and the back side is in the range of 1.4 to 7.5 in terms of the ratio of (front side / back side).
  • the amount of cationic colloidal silica present on the surface of the ink receiving layer after cast coating is similarly 1.4 to 7.5 in terms of (surface side / back side).
  • the amount of the cationic colloidal silica contained in the coagulant solution applied to the coating layer on the front surface side and the back surface side is in the range of 2.5 to 3 in the ratio of (front surface side / back surface side).
  • the amount of the cationic colloidal silica described above is less than 1.4 in the ratio of (front side / back side), the glossiness of the ink receiving layer on the front side tends to be lower than that on the back side. For this reason, the difference in glossiness between the ink-receiving layer on the front side and the back side of the support becomes large, resulting in images with different glossiness when printed on both sides. In the case of the spread state, the left and right glossiness is different.
  • the amount of the above-described cationic colloidal silica is larger than 7.5 in the ratio of (front side / back side), the glossiness of the ink receiving layer on the back side tends to be lower than that on the front side. . For this reason, the difference in the glossiness of the ink receiving layer between the front surface side and the back surface side of the support increases.
  • the method for applying the coagulant solution is not particularly limited as long as it can be applied to the coating layer, and can be appropriately selected from known methods (for example, roll method, spray method, curtain method, etc.).
  • the adhesion amount of the coagulant (solution) is preferably 1 to 10 g / m 2 in terms of solid content.
  • the adhesion amount of the coagulant is less than 1 g / m 2 , the coagulation effect is insufficient, and glossiness may not be sufficiently imparted to the ink receiving layer.
  • Even when the adhesion amount of the coagulant exceeds 10 g / m 2 the effect of improving the glossiness of the ink receiving layer is saturated and the solid content concentration of the coagulant solution must be increased. There is.
  • the concentration of the coagulant solution is preferably 3% by mass or more and less than 30% by mass. If the concentration of the coagulant solution is less than 3% by mass, the adhesion amount of the coagulant to the coating layer (below 1 g / m 2 in solid content) may be insufficient, and the coagulation action may be insufficient. Moreover, when the density
  • a release agent can be added to the coating layer and / or the coagulant as necessary.
  • the melting point of the release agent is preferably 90 to 150 ° C., and particularly preferably 95 to 120 ° C. In the above temperature range, since the melting point of the release agent is substantially equal to the temperature of the mirror finish surface, the ability as a release agent is maximized.
  • the release agent is not particularly limited as long as it has the above characteristics, but it is preferable to use a polyethylene wax emulsion.
  • the content of the release agent in the coagulant solution is not particularly limited, but is preferably 0.1 to 5% by mass.
  • Example 1 Rosetta-type light calcium carbonate (Albuquer 5970) as a filler for a 350 ml Canadian standard freeness (CSF) pulp slurry consisting of 90 parts hardwood bleached kraft pulp (L-BKP) and 10 parts softwood bleached kraft pulp (N-BKP) : SMI) was added so that the ash content was 20%, and 1.0 part of aluminum sulfate, 0.20 part of alkyl ketene dimer (AKD), and 0.05 part of a yield improver were added. The slurry was used for paper making with a paper machine.
  • CSF Canadian standard freeness
  • the coating liquid A was coated on the surface of the support with a roll coater so that the coating amount was 12 g / m 2 in terms of solid content. While this coating layer is in a wet state, the coagulant solution B1 is solidified so that the amount of adhesion is 3.0 g / m 2 , solidified, and then heated through a press roll to a mirror finish The mirror surface was copied by pressure bonding to the surface to obtain a 195 g / m 2 single-sided glossy paper. Subsequently, the coating liquid A was coated on the back surface by a roll coater so that the coating amount was 12 g / m 2 in terms of solid content.
  • the coagulant solution B2 is solidified so as to have an adhesion amount of 3.0 g / m 2 and solidified, and then heated through a press roll to a mirror finish.
  • the mirror surface was copied by pressure bonding to the surface to obtain a recording medium for double-sided ink jet of 210 g / m 2 .
  • ⁇ Coating liquid A> As a pigment, 20 parts of anionic colloidal silica (Quarton PL-3: manufactured by Fuso Chemical Industry Co., Ltd., average primary particle size 30 m), gas phase synthetic amorphous silica (Aerosil 200V: Nippon Aerosil) 10 parts manufactured by Co., Ltd., average primary particle diameter 12 nm) and 70 parts wet-process synthetic amorphous silica (Fine Seal X-37: manufactured by Tokuyama Co., Ltd., average secondary particle diameter 2.3 ⁇ m), polyvinyl as a binder 12 parts of alcohol (PVA217: manufactured by Kuraray Co., Ltd.), 1.5 parts of fluorescent dye (BLANKOPHORP liquid01: manufactured by LANXESS), 0.5 part of mold release agent (Maycatex HP68: manufactured by Meisei Chemical Co., Ltd.) 0.1 parts of a foaming agent (SN deformer 480: manufactured by San Nopco) was blended to prepare a coating solution having a
  • ⁇ Coagulant solution B1> boric acid 4%, cationic resin (Saftomer ST3300: manufactured by Mitsubishi Chemical Corporation) 1%, cationic colloidal silica (LUDOX CL-P: manufactured by Grace, average primary particle size 22 nm) 15%
  • a coagulant solution having a pH of 3 was prepared by blending 0.5 part of a release agent (Maycatex HP68: manufactured by Meisei Chemical Co., Ltd.) and 0.1% of an antifoaming agent (SN deformer 480: manufactured by San Nopco).
  • ⁇ Coagulant solution B2> boric acid 4%, cationic resin (Saftomer ST3300: manufactured by Mitsubishi Chemical Corporation) 1%, cationic colloidal silica (LUDOX CL-P: manufactured by Grace, average primary particle size 22 nm) 2%
  • a coagulant solution having a pH of 3 was prepared by blending 0.5 part of a release agent (Maycatex HP68: manufactured by Meisei Chemical Co., Ltd.) and 0.1% of an antifoaming agent (SN deformer 480: manufactured by San Nopco).
  • Example 2 An inkjet recording medium was obtained in the same manner as in Example 1 except that the amount of the cationic colloidal silica (LUDOX CL-P: manufactured by Grace) in the coagulant solution B2 was changed to 5%.
  • the amount of the cationic colloidal silica (LUDOX CL-P: manufactured by Grace) in the coagulant solution B2 was changed to 5%.
  • Example 3 An ink jet recording medium was obtained in the same manner as in Example 1 except that the amount of the cationic colloidal silica (LUDOX CL-P: manufactured by Grace) in the coagulant solution B2 was changed to 7%.
  • the amount of the cationic colloidal silica (LUDOX CL-P: manufactured by Grace) in the coagulant solution B2 was changed to 7%.
  • Example 4 The blending amount of the cationic colloidal silica (LUDOX CL-P Grace, average primary particle size 22 nm) in the coagulant solution B1 was changed to 12.5%, and the cationic colloidal silica (LUDOX in the coagulant solution B2) An inkjet recording medium was obtained in the same manner as in Example 1 except that the blending amount of CL-P Grace, average primary particle size 22 nm) was changed to 5%.
  • Example 5 The amount of the cationic colloidal silica (LUDOX CL-P, manufactured by Grace Co., Ltd., average primary particle size 22 nm) in the coagulant solution B1 was changed to 10%, and the cationic colloidal silica (LUDOX CL- in the coagulant solution B2) was changed.
  • An ink jet recording medium was obtained in the same manner as in Example 1 except that the blending amount of P Grace (average primary particle size 22 nm) was changed to 5%.
  • Example 6 The amount of the cationic colloidal silica (LUDOX CL-P, manufactured by Grace Co., Ltd., average primary particle size 22 nm) in the coagulant solution B1 was changed to 10%, and the cationic colloidal silica (LUDOX CL- in the coagulant solution B2) was changed.
  • An ink jet recording medium was obtained in the same manner as in Example 1 except that the blending amount of P Grace Co., Ltd. (average primary particle size 22 nm) was changed to 7%.
  • Example 7 An ink jet recording medium was obtained in the same manner as in Example 1 except that the cationic colloidal silica in each of the coagulant solutions B1 and B2 was changed to LUDOX CL (manufactured by Grace, average primary particle diameter: 12 nm).
  • Example 8 An ink jet recording medium was obtained in the same manner as in Example 1 except that the cationic colloidal silica in each of the coagulant solutions B1 and B2 was changed to Snowtex AK (manufactured by Nissan Chemical Co., Ltd., average primary particle size: 12 nm).
  • Example 11 Rosetta type light calcium carbonate (Albuquer 5970: manufactured by SMI Co.) as an ash content 15%, calcite type light calcium carbonate (PC: manufactured by Shiroishi Kogyo Co., Ltd.) as a filler in the paper support to have an ash content of 5%, and An ink jet recording medium was obtained in the same manner as in Example 1, except that the total amount of ash was 20%.
  • Example 1 An inkjet recording medium was obtained in the same manner as in Example 11 except that no cationic colloidal silica was added to the coagulant solution B2.
  • Example 6 Inkjet recording as in Example 1 except that the cationic colloidal silica in each of the coagulant solutions B1 and B2 was changed to colloidal silica having a primary particle size of 60 nm (Snowtex AK-YL: manufactured by Nissan Chemical Industries). A medium was obtained.
  • Example 7 An ink jet recording medium was obtained in the same manner as in Example 1 except that boric acid was not blended in each of the coagulant solutions B1 and B2.
  • the 20 ° glossiness of the unprinted portions of the surface of the ink-receiving layer on the front side and the back side of the obtained inkjet recording medium is determined according to JIS Z 8741. (Manufactured by True GLOSS GM-26PRO). If the 20 degree glossiness is 20% or more, there is no practical problem.
  • Comparative Example 6 In the case of Comparative Example 6 in which the primary particle size of the cationic colloidal silica in the coagulant solution exceeded 50 nm, the 20-degree glossiness of the surface of the ink receiving layer on the front side and the back side was significantly reduced, and the print density was also reduced. . In the case of Comparative Example 7 in which boric acid was not blended in the coagulant solution, the coating layer was insufficiently solidified to deteriorate the cast coating property, and the glossiness could not be imparted to the ink receiving layer.

Landscapes

  • Ink Jet Recording Methods And Recording Media Thereof (AREA)

Abstract

L'invention concerne un support d'enregistrement pour jet d'encre doté d'un aspect brillant uniforme sur les deux faces, tout en présentant un excellent aspect brillant, une densité d'impression élevée lors d'un enregistrement par jet d'encre mettant en œuvre une encre à base de colorants, et d'excellentes propriétés d'absorption de l'encre et de résistance à l'eau. Le support d'enregistrement pour jet d'encre est obtenu par agencement d'une couche de revêtement contenant un pigment et un liant sur chacune des faces, recto et verso, d'une base perméable à l'air; puis une solution d'agent coagulant, qui coagule le liant, est appliquée sur la face recto de la couche de revêtement, afin de former une couche de réception d'encre par un procédé de couverture par coulée coagulée. Un composé de bore, une résine cationique et une silice colloïdale cationique contenus dans la solution d'agent de coagulation sont présents sur la face recto avec couche de réception d'encre. La face recto avec couche de réception d'encre sur les côtés faces recto et verso de la base a un degré de brillance de 20 degrés d'au moins 20% sur chaque côté, et une différence pour chaque degré de brillance de 20 degrés de moins de 5%.
PCT/JP2010/067038 2009-09-30 2010-09-30 Support d'enregistrement pour jet d'encre WO2011040508A1 (fr)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003101746A1 (fr) * 2002-06-04 2003-12-11 Canon Kabushiki Kaisha Support d'enregistrement dote d'une couche amoureuse d'encre et procede de production associe
JP2008062599A (ja) * 2006-09-11 2008-03-21 Oji Paper Co Ltd 両面インクジェット記録用シート

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003101746A1 (fr) * 2002-06-04 2003-12-11 Canon Kabushiki Kaisha Support d'enregistrement dote d'une couche amoureuse d'encre et procede de production associe
JP2008062599A (ja) * 2006-09-11 2008-03-21 Oji Paper Co Ltd 両面インクジェット記録用シート

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