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WO2001089853A1 - Moyen de reproduction a jet d'encre - Google Patents

Moyen de reproduction a jet d'encre Download PDF

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Publication number
WO2001089853A1
WO2001089853A1 PCT/JP2001/004218 JP0104218W WO0189853A1 WO 2001089853 A1 WO2001089853 A1 WO 2001089853A1 JP 0104218 W JP0104218 W JP 0104218W WO 0189853 A1 WO0189853 A1 WO 0189853A1
Authority
WO
WIPO (PCT)
Prior art keywords
ink
pigment
recording medium
absorbing layer
water
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2001/004218
Other languages
English (en)
Japanese (ja)
Inventor
Hidetsugu Oda
Suguru Kashima
Hiroyuki Onishi
Masaya Shibatani
Jun Sugiyama
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Seiko Epson Corp
Mitsubishi Paper Mills Ltd
Original Assignee
Seiko Epson Corp
Mitsubishi Paper Mills Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP2000150331A external-priority patent/JP2001328344A/ja
Priority claimed from JP2000296146A external-priority patent/JP2002103793A/ja
Application filed by Seiko Epson Corp, Mitsubishi Paper Mills Ltd filed Critical Seiko Epson Corp
Publication of WO2001089853A1 publication Critical patent/WO2001089853A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
    • B41M5/52—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

Definitions

  • the present invention relates to an ink jet recording medium for recording using a pigment ink. More specifically, the present invention relates to an ink jet recording medium having high ink absorbency and good color reproduction range. Further, the present invention also relates to an ink jet recording medium capable of printing on both sides.
  • the ink jet recording system uses a variety of operating principles to fly fine ink droplets and attach them to recording media such as paper to record images, characters, etc.
  • High-speed, low-noise, multi-color recording It is easy to use, has great flexibility in recording patterns, and does not require uniform development. It is rapidly spreading in various applications as a recording device for various graphics including kanji and color images.
  • images formed by the multi-color ink jet method can obtain recorded images comparable to multi-color printing by the plate making method and printing by the color photographic method. Also, in applications where the number of copies required is small, it is being widely applied to the field of full-power image recording because it is cheaper than photographic technology and printing technology.
  • the density of the print dots is high, the color tone is bright and vivid, the ink is quickly absorbed, and the ink does not flow or bleed even when the print dots overlap,
  • the diffusion in the horizontal direction is uniform and not excessively large, and the periphery is smooth and not blurred.
  • the image quality does not change with time or environment.For example, it has excellent light resistance, water resistance, and ozone resistance. Is required.
  • Several proposals have been made in response to such demands.
  • a method of providing an ink absorbing layer on a support has been disclosed in JP-A-52-9744 and JP-A-58-72495.
  • Japanese Patent Application Laid-Open No. 55-144172 discloses a method using a specific additive that adsorbs a dye component in an ink absorbing layer.
  • Japanese Patent Application Laid-Open No. 60-113389 discloses that a basic oligomer is contained.
  • No. 5 discloses the use of a polybulamine copolymer for a coating layer in or on a substrate.
  • inkjet recording devices With the availability of inkjet recording devices, inkjet recording devices have changed from special recording devices used by specific people to general-purpose recording devices. In addition, since images can easily be obtained in quality comparable to printed matter and photographs, they are also being used as printers for self-made postcards and digital photographs. In this case, the texture and feel of postcards and photographic prints were required. In addition, in such applications, the amount of ink to be ejected is large, and the ink solvent reaching the base paper causes the printed sheet to undulate, thereby causing a problem of poor appearance.
  • the form of the ink jet recording medium is a so-called plain paper type typified by so-called high-quality paper and pond paper, and a paper such as high-quality paper; It is roughly classified into a coating type provided with an ink absorbing layer.
  • various characteristics of the coated ink absorbing layer directly affect the printing quality.Therefore, regarding the absorptivity, the selection of the specific surface area and shape of the pigment, color saturation, color density, etc.
  • Investigating the transparency and refractive index of pigments examining the coating layer structure and surface shape for image quality, and examining the improvement of paper undulations, such as elongation in water and blending of synthetic and glass fibers.
  • Various studies have been made on coating methods and the like.
  • ink jet recording media In addition to conventional plain paper or matte paper, it has no gloss or low gloss! A glossy appearance similar to paper, cast paper, photographic paper, etc. may be required. This is because there is a demand for the appearance to be similar because the ink jet recorded image can reproduce image quality comparable to printing and photography.
  • an ink jet recording medium having improved surface gloss a medium in which an ink absorbing layer made of a resin is provided on a support has been proposed.
  • resins used in such applications include polyvinylpyrrolidone, vinylpyrrolidone-vinyl acetate copolymer, as disclosed in JP-A-57-38185 and JP-A-62-184879.
  • JP-A-60-234879, JP-A-60-171143 and JP-A-61-134290 disclose resinous compositions mainly composed of polyvinyl alcohol disclosed in JP-A-60-234879.
  • Runime Takuriruami de-grafted polymers, in JP 62-220383 An acryl-based polymer having a carboxyl group as disclosed, a polyvinyl acetal-based polymer as disclosed in JP-A-4-1214382, and the like, and disclosed in JP-A-4-282282 and JP-A-285285.
  • Japanese Patent Application Laid-Open Nos. 4-282282 and 4-285650 disclose an ink jet recording medium using a polymer matrix composed of a crosslinkable polymer and an absorbent polymer in combination.
  • the ink absorption layer made of these resins has a lower surface gloss but has a lower absorption rate and a lower absorption capacity. It has the disadvantage of being small.
  • a medium using alumina hydrate cationic alumina hydrate
  • JP-A 60-245588, JP-B 3-24906, JP-A 6-199035, JP-A 7-82694, and the like support fine quasi-boehmite-type alumina hydrate together with a water-soluble binder.
  • An ink jet recording medium coated on the body surface is disclosed.
  • an ink jet recording medium using pseudo-boehmite alumina hydrate has very high surface gloss, but has a small pore volume, and is described in, for example, JP-A-5-24335.
  • the ink absorption capacity is small, and thick film coating is necessary to obtain a sufficient ink absorption capacity.
  • Japanese Patent Application Laid-Open No. 10-203006 discloses an ink jet recording medium having a primary particle diameter of 3 nm to 3 Onm and using synthetic silica mainly by a gas phase method. In this case, a film thickness of 30 Aim or more is required to obtain a sufficient absorption capacity.
  • JP-A-9-195042, JP-B-3-26665, and JP-A-10-297079 disclose specific examples of coating pigments.
  • an ink jet recording medium or a filler for a recording medium which defines a surface area, a particle diameter, and a uniform number n of rosin-lamellar distribution.
  • pigment inks have excellent light resistance and water resistance as described above, but they are weaker in abrasion resistance than inks that use dyes as coloring agents, and are used to prevent stains on printed matter. Need to be fixed on a recording medium.
  • Examples of fixing means include a case in which a water-soluble resin is mixed with the ink (Japanese Patent Application Laid-Open Nos. Hei 6-108010 and Hei 6-128486) and the inside of a recording medium.
  • Examples of adding a penetrant for the purpose of penetrating pigment into pigments JP-A-6-116522, JP-A-4-159072
  • Examples Japanese Unexamined Patent Publication No. Hei 6-135006
  • Examples Japanese Unexamined Patent Publication No. Hei 6-135006
  • a pigment ink composition for an ink jet is disclosed in WO99Z0530. That is, the cyan ink composition, as a colorant pigment, CI Pigment Blue 15: contains 3 from 2 4 wt 0/0, the magenta ink yarn ⁇ comprises a I. Pigment Red 122 as a colorant pigment 3-5 weight includes 0/0, Ieroinku composition comprises CI pigment Yellow 128. 3 to 5 wt% as a coloring material ⁇ , Purakkui ink composition comprises carbon black 2-5% by weight as the color material pigment, orange Inku composition, the I. Pigment Orange 43 or I. Pigment Orange 36, good Mashiku comprises 2-5 wt 0/0, green ink composition, a CI Pigment green 7 also properly CI Pigment green 36, preferably Comprises 2-5% by weight.
  • the cyan ink composition as a colorant pigment, CI Pigment Blue 15: contains 3 from 2 4 wt 0/0
  • these ink compositions an acetylene glycol compound as a penetrant from 0.1 to 5 weight 0 /.
  • Glycerin and ethylene glycol monobutyl ether as high boiling organic solvents in an amount of 2 to 15% by weight
  • the water-soluble dispersant is a styrene- (meth) acrylic acid-based water-soluble resin
  • Method An acrylic acid-based water-soluble resin in a ratio of 0.1 to 1% by weight in terms of solid content is exemplified.
  • the ink composition technology of the ink jet recording medium is adapted to the ink jet recording technology which has been highly developed in recent years, particularly the ink composition using a coloring material pigment in order to improve light resistance and storage stability. It was not enough to satisfy the requirements for ink absorption, color, and color density.
  • the present inventors have intensively pursued an inkjet recording medium that has high ink absorption, colorant / material adhesion, and excellent color reproduction range when recording with pigment ink. It has been found that when recording is performed using a pigment ink containing a specific composition on an ink jet recording medium provided with an ink absorbing layer using a pigment, the above-described problem is satisfied, and it was found that the ink jet recording medium of the present invention was completed. Reached. That is, according to the present invention, the following ink jet recording medium and its use are provided.
  • An ink jet recording medium for pigment ink comprising: a support; and an ink absorbing layer provided on one surface of the support, wherein a colorant pigment and a high boiling organic solvent are provided on the ink absorbing layer.
  • the ink absorbing layer contains an inorganic pigment and a polymer adhesive, and the inorganic pigment is A recording medium having an oil absorption specified in JISK5101 of at least 150 ml / 100 g and an average secondary particle diameter of at least 3.0 ⁇ m and at most 15 ⁇ m.
  • the ink absorbing layer is provided in an amount of 7 g / m 2 or more and 20 g / m 2 or less, The recording medium of (2).
  • An ink jet recording medium for a pigment ink comprising a support and an ink absorbing layer, wherein the ink absorbing layer contains an inorganic pigment and a polymer adhesive, and the inorganic pigment is 150 ml / 100. g or more of the oil absorption specified in JISK 5101 and an average secondary particle diameter of 3.0 ⁇ m or more and 15 ⁇ m or less. Use for recording by ejecting droplets of pigment ink containing solvent, dispersant, penetrant and water.
  • Examples of the support that can be used in the present invention include resin films such as polyester films, polyolefin films, polyvinyl chloride, paper such as plain paper, coated paper, and tracing paper, resin-coated paper, synthetic paper, and adhesive paper.
  • An adhesive film or the like is used.
  • the support on which the ink-absorbing layer can be provided such as glass, ethanol foil, vapor-deposited paper, vapor-deposited film, non-woven fabric, leather products, and ceramic products.
  • the body is most preferred.
  • the inorganic pigment used in the ink absorbing layer in the present invention has an oil absorption of at least 150 ml Zl 00 g and a mean secondary particle diameter of 3.0 determined based on the pigment test method JIS-K5109.
  • the oil absorption is 200 ml / 100 g or more.
  • the inorganic pigment synthetic amorphous silica fine particles, synthetic magnesium carbonate fine particles and the like are preferable, and synthetic amorphous silica fine particles are particularly preferable.
  • the coloring material pigment, a high-boiling organic solvent, a dispersant, a penetrant and water in combination with a liquid medium in the pigment ink containing at least water, absorbability, Desired performance such as color saturation and color density can be obtained.
  • the average secondary particle diameter is less than 3.0 // m, the fixability of the pigment ink is reduced, and a bronzing phenomenon of the black ink occurs.
  • Bronze-dani means that the black color appears brownish, reducing the color density and deteriorating the quality. Also, the average particle size
  • the color density will decrease. This is thought to be because the coloring material in the ink wraps around the backside of the inorganic pigment particles, concealing the coloring material pigment seen from the surface. In particular, when a penetrant is contained in the ink, the particle size has a significant effect. It is not clear why the oil absorption affects the color reproduction range, etc., but it is presumed to have some effect on the absorption state of the high-boiling organic solvent and penetrant contained in the ink. It is presumed that the combination of the high-boiling organic solvent and the penetrant in the ink used in the present invention favors the oil absorption of the pigment in the ink absorption layer, under conditions.
  • the amorphous silica force particles preferably used in the present invention S i O 29 3% or more on a dry basis, A 1 2 0 3 to about 5% or less, with microparticles containing N a 2 0 to about 5% Yes, there are so-called white carbon, silica gel and amorphous fine powder silica.
  • the method for producing amorphous silica fine particles is roughly classified into a dry method and a wet method.
  • the dry method includes a combustion method and a heating method.
  • the wet method includes a production method called a precipitation method and a gel method.
  • the dry combustion method is a method in which a mixture of hydrogenated silicon tetrachloride and hydrogen is burned in air at 1600 to 2000 ° C., which is also called a gas phase method.
  • Wet precipitation method usually a silicofluoride sodium and sulfate are reacted in an aqueous solution, S i 0 2 in a method of precipitating a specific surface area of the silica according to the conditions of the addition rate of the reaction temperature and the acid (40 to 400 2 / g) and the primary particle size (5-80 nm) can be adjusted.
  • the secondary particle size ⁇ silica physical properties change subtly under drying and milling conditions.
  • the wet gel method is generally produced by reacting sodium silicate and sulfuric acid at the same time, for example.
  • the polymerization of silica particles such as dehydration condensation of silanol groups, progresses to a three-dimensional hydrogel structure. It is a natural thing. The feature is that since the primary particles have a relatively small hydrogel structure, secondary particles with a large specific surface area can be produced.
  • amorphous silica fine particles of the above, silica fine particles synthesized by a wet method are preferable, the oil absorption is 150 ml or more, and the average secondary particle diameter is 3. Amorphous silica fine particles of 0 ⁇ m or more and 15 ⁇ m or less. ,
  • the polymer adhesive used in the present invention is a water-soluble or water-insoluble polymer compound, and is a compound having an affinity for ink as a component of the ink absorbing layer.
  • the water-soluble polymer compound include starch derivatives such as starch, oxidized starch, cationized starch, etherified starch, phosphorylated ester starch, carboxymethylcellulose, hydroxymethylinoresenolerose, and hydroxyxe.
  • Cellulose derivatives such as chinoresenolose, cellulose sulfate, etc., various derivatives such as polyvinyl alcohol or silanol-modified products thereof, carboxylated products, force-thione products, etc., casein, gelatin, denatured gelatin, soy protein, etc.
  • Water-soluble synthetic polymers such as natural polymers, polyvinylpyrrolidone, sodium polyacrylate, sodium salt of styrene-maleic anhydride copolymer, and sodium polystyrenesulfonate are used.
  • conjugated copolymer latexes such as styrene-butadiene copolymer and methyl methacrylate-butadiene copolymer
  • acrylic polymer latex such as polymers or copolymers of atarylate and methacrylate esters.
  • Vinyl-based polymer latex such as ethylene-vinyl acetate-copolymer, vinyl chloride mono-vinyl acetate copolymer, or a functional group-modified polymer latex with a functional group-containing monomer such as a carboxy group of these various polymers
  • thermosetting synthetic resins such as polyurethane resin latex, melamine resin and urea resin.
  • it is polyvinyl alcohol or a derivative thereof.
  • water-insoluble polymer compound examples include alcohols such as ethanol and 2-propanol, and water-insoluble binders that are dissolved in a mixed solvent of these alcohols and water.
  • non-water-soluble binder Byurupiro Li Dong // vinyl acetate copolymer, polyvinyl butyral, can be cited Asetaru resin such as polyvinyl formal, especially Asetaru degree is 5 mole 0/0 or 2 0
  • the acetal resin in the range of mol% or less is particularly preferable because it can contain water to some extent and can facilitate dispersion of the amorphous silica fine particles.
  • These polymer adhesives may be used alone or in combination of two or more, and are used in an amount of 2 to 60% by weight with respect to the inorganic pigment. /. Is added. Preferably, 10 to 50% by weight is added. If the amount is less than the above range, the strength of the coating film becomes weak. The color density decreases.
  • the ink absorption layer contains a cationic water-soluble resin.
  • the cationic water-soluble resin used in the present invention include secondary amine, tertiary amine, and quaternary ammonium salts such as polyethyleneimine salts, dimethylamineephalohydrin condensates, polybieramine salts, polyallylamine salts, and polydimethyl salts. Examples include a quaternary ammonium salt methacrylate, a polydiaryldimethylammonium salt, a diarylamineatarylamide copolymer salt, and a quaternary ammonium salt of polystyrene.
  • quaternary cyclic amines can be cited as ones that lead to more favorable color and color density. There is no problem in blending and using two or more of these cationic resins. Rather, they may be blended aggressively in order to maximize each characteristic.
  • the coloring material in the pigment ink is dispersed in the liquid medium by the dispersing agent, and the surface thereof is negatively charged. is there. Therefore, it is considered that the dispersed colorant pigment in the ink is trapped near the surface, and the color reproduction range becomes wider. Further, the smaller the difference in the refractive index from other materials (inorganic pigments and adhesives) used in the ink absorbing layer, the more the light scattering in the ink absorbing layer is reduced. It is thought that the presence of color has improved color saturation and color density, and has helped to broaden the color reproduction range.
  • the method of applying the coating liquid for forming the ink absorption layer in the present invention includes various coating methods such as E-par coating, curtain coating, strado hopper coating, eta-strusion coating, roll coating, air knife coating, gravure coating, and rod bar coating. Can be adopted.
  • the layer constitution of the ink absorbing layer may be a single layer or a laminated constitution.
  • all layers may be layers having the same composition, or may be a laminated structure with a layer composed of other components.
  • the coating amount of the ink absorbing layer when an ink absorbing layer is provided on one side of the support, the coating amount of the ink absorbing layer must be 0.5 g or more per unit square meter in terms of solid content. Is preferably not less than 1. O g and not more than 4 ° g per square meter.
  • the coating amount of the ink absorbing layer When an ink absorbing layer is provided on both sides of the support, the coating amount of the ink absorbing layer must be 7 g or more per unit square meter in terms of solid content. 7 g or more and 20 g or less. If the coating amount is less than 7 g Zm 2 , the penetrant-containing ink used in the present invention penetrates the base paper layer to reach the back surface, and a phenomenon of strike-through occurs.
  • the coating layer contains an inorganic pigment with an oil absorption of 15 Om1 / 100 g or more, and
  • a coating amount of 7 g / m 2 or more is required. Further possible coating amount is large although for these problems is effective, even when applied 2 0 g / m 2 or more effects never change much, lowering the difficulty and the coating layer strength of the coating Therefore, it is not very desirable.
  • a general known method can be used, and is not limited. For example, there are a method in which heated air generated by a heat source is conveyed into a heated heater, and a method in which the air is passed near a heat source such as a heater.
  • the inorganic pigment and the polymer adhesive used in the present invention preferably further, a coating liquid for forming an ink absorption layer containing a cationic water-soluble polymer, if necessary, a surfactant, Color dyes, color pigments, UV absorbers, antioxidants, pigment dispersants, defoamers, leveling agents, preservatives, fluorescent whitening agents, viscosity stabilizers, pH regulators, hardeners, etc
  • the pigment ink referred to in the present invention refers to one that uses a pigment as a coloring material, contains a dispersant and a penetrant, and also contains water, a high-boiling organic solvent, and the like.
  • a pigment ink disclosed in W099 / 05230.
  • a low-boiling organic solvent may be used as needed for the pigment ink.
  • the ink containing the penetrant and, if necessary, a low-boiling organic solvent has a strong penetrating power into the recording medium, and is said to be a quick-penetrating ink.
  • the pigment ink is an ink using a pigment as a coloring material, and any pigment may be used, and any of an inorganic pigment and an organic pigment may be used, and there is no particular limitation. For example, the following are mentioned.
  • organic pigments include azo dyes (including azo lakes, insoluble azo pigments, condensed azo pigments, chelate azo pigments, etc.), polycyclic pigments (for example, phthalocyanine).
  • carbon black used as black ink for example, Mitsubishi Chemical No.2300, No.900, MCF88, No.33, No.40, No.45, No.52, MA7, MA8, MA100, NO.220QB, etc., Colombian: t
  • R Raven5750, Raven5250, Raven3500, Ravenl255, Raven700, etc. are Cabotnet clay made Regal400R, Regal330R, Regal660R, Mogul L, Monarch 700, Monarch 800, Monarch 880, Monarch 900, Monarch 1000, Monarch 1100, Monarch 1300, Monarch 1400, etc.
  • Examples of the pigment used in the yellow ink include CI Pigment Yellow 1, CI Pigment Yellow 2, CI Pigment Yellow 3, CI Pigment Yellow 12, CI Pigment Yellow 13, CI Pigment Yellow 14C, CI Pigment Yellow 16, and CI Pigment Yellow 16. 17, CI Pigment Yellow 73, CIPigment Yellow 74, CI Pigment Yellow 75, CI Pigment Yellow 83, CIPigment Yellow 93, CIPigment Yellow 95, CI Pigment Yellow 97, CIPigment Yellow 98, CIPigment Yellow 114, CI Pigment Yellow 128, CI Pigment Yellow 129, CI Pigment Yellow 151, CI Pigment Yellow 154 and the like.
  • pigments used in magenta ink include CI Pigment Red 5, CI Pigment Red 7, CI Pigment Red 12, CI Pigment Red 48 (Ca), CI Pigment Red 48 (Mn), and CI Pigment Red 57 (Ca).
  • CI Pigment Red 57 1, CI Pigment Red 112, CI Pigment Red 122, CI Pigment Red 123, CI Pigment Red 168, CI Pigment Red 184, CI Pigment Red 202 and the like.
  • pigments used for cyan ink CIPigment Blue 1, CI Pigment Blue 2, CI Pigment Blue 3, CI Pigment Blue 15: 3, CI Pigment Blue 15:34, CI Pigment Blue 16, CI Pigment Blue 22, CI Pigment Blue 60, CI Vat Blue 4, CI Vat Blue 60, etc. Is mentioned.
  • a dispersant is used to disperse the pigment.
  • dispersant examples include styrene-acrylic acid copolymer, styrene-methacrylic acid copolymer, styrene-methacrylic acid-acrylic acid alkyl ester copolymer, styrene-CK-methylstyrene-acrylic acid copolymer, styrene-acrylic acid copolymer.
  • a-Methylstyrene-acrylic acid-acrylic acid alkyl ester copolymer sodium polyacrylate, styreneacrylic acid copolymer-ammonium salt, polymer dispersant such as sodium hexamethaphosphate or surfactant Can be mentioned.
  • Preferred is a styrene mono (meth) acrylic acid-based water-soluble resin.
  • a penetrant is added to control the permeability of the ink into the recording medium.
  • Adione surfactants sodium dodecylbenzenesulfonate, sodium laurate, ammonium polyoxyethylene alkyl ether sulfate) Salt, etc.
  • non-ionic surfactants polyoxyethylene alkyl ether, polyoxyethylene alkyl ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene alkylphenyl ether ether, polyoxyethylene alkylamine, polyoxyethylene alkyl Amide
  • acetylene glycol Olfine Y, Surfynol 82.10.44.40.465.48.55 (all manufactured by Air products and Chemicals Inc.)
  • Preferred is an acetylene glycol-based penetrant.
  • High-boiling organic solvents are added to prevent ink clogging and to aid ink permeability. They are water-miscible and water-retaining, and have a low vapor pressure (a vapor pressure of 0.0
  • the boiling point is preferably from 120 to 250 ° C, the viscosity is from 2 mPa ⁇ s to 15 OmPa ⁇ s, and the surface tension is 0. .01 to 0.IN Zm are preferably used.
  • Examples thereof include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, polypropylene glycol, and propylene glycol, butylene glycol, 1.2.6—hexanetriol, thioglycol, and so on.
  • Xylene glycol, glycerin, Polyhydric alcohols such as trimethylolmethane and trimethylolpropane, ethylene glycolone monoethylene ether, ethylene glycol monobutylinoleatenoethylene, methylenglyconele monomethinoleatenole, and methylene glycol monoethylene Alkyl ethers of polyhydric alcohols such as ter, triethylene glycol monoethyl ether, triethylene glycol monomethyl ether, urea, 2-pyrrolidone, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidino And triethanolamine are examples.
  • Polyhydric alcohols such as trimethylolmethane and trimethylolpropane, ethylene glycolone monoethylene ether, ethylene glycol monobutylinoleatenoethylene, methylenglyconele monomethinoleatenole, and methylene glycol monoethylene Alkyl ethers of polyhydric alcohols
  • the low-boiling organic solvents used as necessary include methanol, ethanol, n-propanol, iso-propanol, n-butanol, sec-butanol, tert-butanol, iso-butanol, n-propanol. Pentanol and the like.
  • resin emulsion and sugar can be added to the pigment ink.
  • the resin emulsion include (meth) atallylic acid-based water-soluble resin, butyl acetate-based resin, styrene-butadiene-based resin, butyl chloride-based resin, ataryl-styrene-based resin, butadiene-based resin, styrene-based resin, and crosslinked acrylic-based resin Resin, cross-linked styrene resin, benzoguanamine resin, phenol resin, silicon resin, urethane resin, epoxy resin, etc., and these resins have a structure that has both a hydrophilic part and a hydrophobic part It is desirable that
  • Sugars include monosaccharides, disaccharides, oligosaccharides, polysaccharides and the like. Specific examples include gnorecose, mannose, funolectose, xylose, arabinose, galactose, aldonic acid, glycissile, sorbitol, maltose, cellobiose, ratatose, sucrose, trenulose, maltotriose, and polysaccharides. , Alginic acid, ⁇ -cyclodextrin, cellulose and the like. In addition to the above, ⁇ adjusters, preservatives, fungicides, antioxidants, and the like can be included.
  • the feature of the pigment ink used in the present invention is that it contains at least a colorant pigment, a high-boiling organic solvent, a dispersant, a penetrant and water.
  • a dispersant a styrene- (meth) acrylic acid-based water-soluble resin is preferable, and as the penetrant, an acetylene glycol compound is preferable.
  • the color reproduction range is particularly improved.
  • the oil absorption in the recording medium is at least 150 m1Z100 g, and the average particle size is 3 It is considered that there is some influence on the absorption behavior of dispersants and penetrants between pigments with a size of 0 ⁇ m or more and 15 ⁇ m or less, and that the penetration of colorant pigments is controlled.
  • the color reproduction range is C (cyan), M (magenta), Y (yellow), R (red, M + Y), G (green, C + Y), B (blue, C + M) depending on the inkjet color printer. ) Is printed in solid color, and the color is measured with a colorimeter (spectrophotometer) to determine the L * a * b * value.
  • the a *, 1> * values are plotted with the & * value on the axis and the b * value on the y axis, and a hexagonal figure can be obtained by connecting adjacent points. This is called the color reproduction range (also called the color gamut or color rendering range).
  • the sum of the densities of Y, M, C, and Bk (black) is simply used as a numerical value representing the color reproduction range.
  • the coating composition of the ink absorbing layer is composed of amorphous fine particles (Mizukasil P78A: oil absorption 245 m1 Z100 g, average secondary particle diameter 3.5 ⁇ m: manufactured by Mizusawa Chemical Co., Ltd.) 10 0 parts, Polyvier alcohol (PVA 117: Kurarene earth) 25 parts, Cationic dye fixing agent (Sumirezuzu resin 101: Sumitomo Chemical Co., Ltd.) 20 parts, mixed, ink absorption layer coating liquid A
  • the coating composition of the ink absorbing layer was composed of amorphous silica fine particles (fine seal X-60: oil absorption 24 Oml / 100 g, average secondary particle diameter 6.2 ⁇ : manufactured by Tokuyama Corporation) 100 parts, Silanol-modified polyvinyl alcohol (Rl 130: made of Kuraray clay) 20 parts, 20 parts of a cationic dye fixing agent (Violet Resin 1001: manufactured by Sumitomo Chemical Co., Ltd.) were mixed to prepare an ink absorbing layer coating solution B.
  • amorphous silica fine particles fine seal X-60: oil absorption 24 Oml / 100 g, average secondary particle diameter 6.2 ⁇ : manufactured by Tokuyama Corporation
  • Silanol-modified polyvinyl alcohol Rl 130: made of Kuraray clay
  • a cationic dye fixing agent Violet Resin 1001: manufactured by Sumitomo Chemical Co., Ltd.
  • the coating composition of the ink absorbing layer was composed of amorphous silica fine particles (Mizukasil P 78 F: oil absorption 22 Oml / 100 g, average secondary particle diameter 12.0 ⁇ : manufactured by Mizusawa Chemical Co., Ltd.) 100 parts, Polyvinyl alcohol (PVA 117: Kuraray Co., Ltd.) 15 parts, Silanol-modified Polyvinyl alcohol (Rl 130: Kurarene earth) 15 parts, Cationic dye fixing agent (Violet Resin 1001: Sumitomo Chemical Co., Ltd.) 20 parts were mixed to prepare the ink absorbing layer coating solution C.
  • amorphous silica fine particles Mizukasil P 78 F: oil absorption 22 Oml / 100 g, average secondary particle diameter 12.0 ⁇ : manufactured by Mizusawa Chemical Co., Ltd.
  • Polyvinyl alcohol PVA 117: Kuraray Co., Ltd.
  • Silanol-modified Polyvinyl alcohol Rl
  • the coating composition of the ink absorbing layer was composed of 100 parts of amorphous silica fine particles (Mizukasil 5—50: oil absorption amount: 17 Oml / 100 g, average secondary particle size: 9.5: manufactured by Mizusawa Chemical Co., Ltd.) Livinyl alcohol (PVA117: Kuraray clay) 15 parts, Silanol-modified polybutyl alcohol (R110: Kuraray) 15 parts, cationic dye fixing agent (Violets resin 1001: Sumitomo Chemical) Co., Ltd.) (20 parts) was mixed to prepare an ink absorbing layer coating solution D.
  • amorphous silica fine particles Livinyl alcohol (PVA117: Kuraray clay) 15 parts, Silanol-modified polybutyl alcohol (R110: Kuraray) 15 parts, cationic dye fixing agent (Violets resin 1001: Sumitomo Chemical) Co., Ltd.) (20 parts) was mixed to prepare an ink absorbing layer coating solution D.
  • the coating composition of the ink absorption layer was composed of 100 parts amorphous fine particles (Fine Seal X-37: oil absorption: 275 ml / 100 g, average secondary particle diameter: 2.7 ⁇ m: manufactured by Tokuyama Corporation), 25 parts of polyvinyl alcohol (PVA117: manufactured by Kuraray Co., Ltd.) and 20 parts of a cationic dye fixing agent (Sumitetsu Resin 1001: manufactured by Sumitomo Chemical Co., Ltd.) were mixed to prepare a coating solution E for an ink absorbing layer.
  • amorphous fine particles Fine Seal X-37: oil absorption: 275 ml / 100 g, average secondary particle diameter: 2.7 ⁇ m: manufactured by Tokuyama Corporation
  • PVA117 manufactured by Kuraray Co., Ltd.
  • a cationic dye fixing agent Suditetsu Resin 1001: manufactured by Sumitomo Chemical Co., Ltd.
  • the coating and composition of the ink absorbing layer are made of amorphous silica fine particles (Nipseal VN3: oil absorption: 180-200 ml / 100g, average secondary particle diameter: 18. 8. ⁇ : manufactured by Nippon Siri Riki Co., Ltd.) 100 parts, Polyvinyl alcohol (PVA 117: manufactured by Kuraray Co., Ltd.) 25 parts, Cationic dye fixing agent (Sumiretzu Resin 1001: manufactured by Sumitomo Chemical Co., Ltd.) 20 parts were mixed, and the ink absorbing layer coating solution was mixed.
  • amorphous silica fine particles Niseal VN3: oil absorption: 180-200 ml / 100g, average secondary particle diameter: 18. 8. ⁇ : manufactured by Nippon Siri Riki Co., Ltd.
  • Polyvinyl alcohol PVA 117: manufactured by Kuraray Co., Ltd.
  • Cationic dye fixing agent Sumiretzu Resin 1001: manufactured by Sumitomo Chemical Co., Ltd
  • ⁇ Ink absorbing layer coating liquid G > 100 parts of amorphous silica fine particles (Mizukasil P832: oil absorption 145 ml / 100 g, average secondary particle diameter 2.5: manufactured by Mizusawa Chemical Co., Ltd.) 25 parts of PVA117: made of Kurarene earth) and 20 parts of a cationic dye fixing agent (Violets resin 1001: manufactured by Sumitomo Chemical Co., Ltd.) were mixed to prepare a coating solution G for the ink absorbing layer.
  • amorphous silica fine particles Mizukasil P832: oil absorption 145 ml / 100 g, average secondary particle diameter 2.5: manufactured by Mizusawa Chemical Co., Ltd.
  • PVA117 made of Kurarene earth
  • Violets resin 1001 manufactured by Sumitomo Chemical Co., Ltd.
  • Coating is performed using coated base paper (basis weight 1 57
  • the above coating liquids A to E were applied to a talc filler content of 6%, a cop size of 9 g / m 2 , and acidic paper) using a wire bar so as to have a dry coating amount of 10 g / m 2 .
  • the ink jet recording medium was left standing at 90 ° C. for 10 minutes and dried to prepare an ink jet recording medium for the examples and comparative examples shown in Table 1.
  • the following pigments were respectively dispersed in the following liquid media to obtain an ink set composed of four color ink compositions.
  • Styrene-methacrylic acid copolymer 1.5% by weight Grandul PP-1000
  • Acetylene glycol compound (Surfinol 465: penetrant)
  • Viscosity 3.0 to 3.8 mPa's, Surface tension: 3 ° to 40 NZm, H: 8.0 to 8.8.
  • Ink set 2 was obtained in the same manner as in ink set 1, except that the styrene-methacrylic acid copolymer as a dispersant was replaced with sodium polyacrylate.
  • Ink set 3 was obtained in the same manner as in ink set 1 except that the penetrant (Surfinol 465) was omitted.
  • the ink absorbability was evaluated by using these ink sets, printing a heavy-color rectangular pattern with cyan ink and magenta ink, and visually evaluating the boundary between this print pattern and the unprinted area according to the following criteria. .
  • the friction resistance was evaluated by using a black ink of these ink sets, printing a solid rectangular pattern, and rubbing with a nail or finger to evaluate the ink peeling.
  • the color reproduction range is preferably 5.3 or more.
  • Example 1 A 1 ⁇ ⁇ 1.37 1.28 1.36 1.56 5.57
  • Example 2 B 1 ⁇ ⁇ 1.40 1.32 1.40 1.60 5.72
  • Example 3 C 1 ⁇ ⁇ 1.36 1.27 1.34 1.52 5.49
  • Example 4 D 1 ⁇ 2 1.32 1.25 1.32 1.48 5.37
  • Example 5 A 2 ⁇ ⁇ 1.35 1.27 1.34 1.55 5.51
  • Example 6 B 2 ⁇ ⁇ 1.37 1.30 1.38 1.56 5.61
  • Example 8 D 2 ⁇ ⁇ 1.31 1.26 1.30 1.47 5.34 Comparative example 1 A 3 o X 1.25 1.18 1.28 1.37 5.08 Comparative Example 2 B 3 ⁇ X 1.23 1.20 1.27 1.39 5.09 Comparative Example 3 C 3 ⁇ X 1.27 1.20 1.31 1.40 5.18 Comparative Example 4 D 3 ⁇ X 1.25 1.19 1.28 1.36 5.08 Comparative Example 5 E 1 ⁇ ⁇ 1.26 1.21 1.27 1.36 5.
  • Comparative Examples 1, 2, 3, and 4 using ink set 3 containing no penetrant had a narrower color reproduction range and abrasion resistance even with the same recording medium than Examples 1, 2, 3, and 4. Was not possible.
  • Examples 1, 2, and 3 having an oil absorption of 20 Om 1/100 g or more were slightly superior in the color reproduction range as compared with Example 4 having an oil absorption of 170 ml / 100 g. The same can be said between Examples 5, 6, 7 and 8.
  • the coating was performed by coating the above coating liquids A to E on a coated base paper (basic weight: 157 g Zm 2 , talc filler content: 6%, cob size: 9 g Zm acidic paper) using a wire par as a support. Apply to the indicated surface dry coating amount, leave it at 90 ° C for 10 minutes, dry, and apply to the opposite surface also the back surface dry coating amount shown in Table 2. After drying in the same manner, ink jet recording media for Examples and Comparative Examples shown in Table 2 were produced.
  • the color reproduction range is preferably 5.3 or more.
  • the strike-through was evaluated by visually observing the extent to which the image printed on both sides was seen through the back. ⁇ No strikethrough is observed
  • the abrasion resistance and the color reproduction range were slightly lower than those of, 11, 12, 13 and 14.
  • Comparative Examples 15, 16, 17, and 18 using the ink set 3 containing no penetrant the color reproduction range was narrower than that of Examples 9, 11, 13, and 14, even with the same recording medium.
  • an ink jet recording medium having good absorbability, excellent ink pigment fixing property (abrasion resistance), and a wide color reproduction range.
  • an ink jet recording medium useful as a recording medium when a pigment ink containing a styrene- (meth) atalylic acid-based water-soluble resin dispersant and an acetylene glycol compound penetrant is used can be supplied.
  • a double-sided ink jet recording medium excellent in these various properties can be supplied.
  • a double-sided ink jet recording medium capable of obtaining good printed matter without strikethrough can be supplied.

Landscapes

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

Abstract

L'invention concerne un moyen de reproduction à jet d'encre à utiliser dans la reproduction par la production de gouttelettes d'une encre pigmentaire contenant un pigment coloré, un solvant organique possédant un point d'ébullition élevé, un dispersant, un agent de suppression de perméation et de l'eau, ledit moyen comprenant un support et une couche absorbant l'encre. La couche absorbant l'encre comporte un pigment inorganique et un adhésif polymère, ledit pigment organique présentant une caractéristique d'absorption de l'huile spécifiée dans JIS K5101 d'au moins 150 ml/100 g et un diamètre de particule secondaire moyen de 3,0 νm à 15 νm. Le moyen de reproduction à jet d'encre peut comporter une couche absorbant l'encre supplémentaire sur l'autre surface du support. Ledit moyen de reproduction par jet d'encre possède des caractéristiques d'absorption de l'encre élevées et une bonne zone de reproduction de couleurs.
PCT/JP2001/004218 2000-05-22 2001-05-21 Moyen de reproduction a jet d'encre Ceased WO2001089853A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2000150331A JP2001328344A (ja) 2000-05-22 2000-05-22 顔料インク用インクジェット被記録媒体
JP2000-150331 2000-05-22
JP2000-296146 2000-09-28
JP2000296146A JP2002103793A (ja) 2000-09-28 2000-09-28 顔料インク用両面インクジェット被記録媒体

Publications (1)

Publication Number Publication Date
WO2001089853A1 true WO2001089853A1 (fr) 2001-11-29

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2001/004218 Ceased WO2001089853A1 (fr) 2000-05-22 2001-05-21 Moyen de reproduction a jet d'encre

Country Status (1)

Country Link
WO (1) WO2001089853A1 (fr)

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0811422A (ja) * 1994-07-05 1996-01-16 Mitsubishi Paper Mills Ltd 両面インクジェット記録シート
WO1999005230A1 (fr) * 1997-07-28 1999-02-04 Seiko Epson Corporation Composition d'encre
JPH1158934A (ja) * 1997-08-18 1999-03-02 Mitsubishi Paper Mills Ltd インクジェット記録シート
JPH11268400A (ja) * 1998-03-19 1999-10-05 Oji Paper Co Ltd インクジェット記録用シート
JP2000079752A (ja) * 1998-06-30 2000-03-21 Oji Paper Co Ltd インクジェット記録体及び記録方法
JP2000203152A (ja) * 1999-01-13 2000-07-25 Mitsubishi Paper Mills Ltd インクジェット記録用シ―ト及び画像形成方法
JP2000238420A (ja) * 1999-02-23 2000-09-05 Hokuetsu Paper Mills Ltd インクジェット記録シート及びその製造方法
JP2001010213A (ja) * 1999-06-29 2001-01-16 Oji Paper Co Ltd インクジェット記録体及び記録方法

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0811422A (ja) * 1994-07-05 1996-01-16 Mitsubishi Paper Mills Ltd 両面インクジェット記録シート
WO1999005230A1 (fr) * 1997-07-28 1999-02-04 Seiko Epson Corporation Composition d'encre
JPH1158934A (ja) * 1997-08-18 1999-03-02 Mitsubishi Paper Mills Ltd インクジェット記録シート
JPH11268400A (ja) * 1998-03-19 1999-10-05 Oji Paper Co Ltd インクジェット記録用シート
JP2000079752A (ja) * 1998-06-30 2000-03-21 Oji Paper Co Ltd インクジェット記録体及び記録方法
JP2000203152A (ja) * 1999-01-13 2000-07-25 Mitsubishi Paper Mills Ltd インクジェット記録用シ―ト及び画像形成方法
JP2000238420A (ja) * 1999-02-23 2000-09-05 Hokuetsu Paper Mills Ltd インクジェット記録シート及びその製造方法
JP2001010213A (ja) * 1999-06-29 2001-01-16 Oji Paper Co Ltd インクジェット記録体及び記録方法

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