JP2013202791A - Ink medium set and recording method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an ink medium set for forming an image having excellent glitter and including a recording ink and a recording medium, and to provide a recording method using the ink medium set.SOLUTION: An ink medium set includes a recording ink and a recording medium 100. The recording ink contains a glittering pigment. The recording medium has a receiving layer 12 formed at least on one surface of a base material 10, and at least one inorganic particle containing layer 14 formed above the receiving layer. The inorganic containing layer is formed on a recorded surface.

Description

  The present invention relates to an ink media set, in particular, an ink media set capable of forming an image excellent in glitter, and a recording method using the ink media set.

  As a technique for forming an image having glitter (hereinafter referred to as “brilliant image”) on a printed material, gold powder produced from brass, aluminum particles, silver particles, etc., printing ink or metal foil using silver powder as a pigment Foil stamping printing using heat transfer, thermal transfer using metal foil, and the like have been used.

  In recent years, there have been many examples of application to an ink jet system in printing, and one of them is metallic printing. For example, Patent Document 1 discloses an inkjet ink containing a glitter pigment capable of forming a glitter image.

  On the other hand, as a conventional recording medium in the case of using pigment ink, a recording medium provided with a receiving layer having a gap for taking up ink on a substrate and further provided with a porous gloss layer as required is mainly used. Various types of recording media have been proposed. For example, Patent Document 2 proposes an ink jet recording medium in which an ink receiving layer made of a pigment, a binder resin, and a light resistance improver is provided on at least one surface of a substrate.

JP 2008-174712 A Japanese Patent No. 3594838

  However, when an image is recorded using an ink containing a glitter pigment on a conventional recording medium, there is a problem that it is difficult to obtain sufficient glitter.

  Some aspects of the present invention provide an ink media set comprising a recording ink and a recording medium capable of forming an image having excellent glitter by solving at least a part of the above-described problems, and the A recording method using an ink media set is provided.

  SUMMARY An advantage of some aspects of the invention is to solve at least a part of the problems described above, and the invention can be implemented as the following aspects or application examples.

[Application Example 1]
One aspect of the ink media set according to the present invention is:
A set of recording ink and recording media,
The recording ink contains a glitter pigment,
The recording medium has a receiving layer on at least one surface of a substrate, further has at least one inorganic particle-containing layer above the receiving layer, and has the inorganic particle-containing layer on the recording surface. It is characterized by being.

  According to the ink media set of Application Example 1, since it is possible to easily arrange the glitter pigment on the inorganic particle-containing layer that is the recording surface of the recording medium, a glitter image with reduced unevenness is formed. It becomes possible. This makes it possible to form an image with excellent glitter on the recording medium. Moreover, since it has a receiving layer, it is excellent in the surface drying property of the ink.

[Application Example 2]
In the ink media set of Application Example 1,
The average thickness of the inorganic particle-containing layer may be 0.1 μm or more and 3 μm or less.

[Application Example 3]
In the ink media set of Application Example 1 or Application Example 2,
The receiving layer may have an average thickness of 3 μm to 50 μm.

[Application Example 4]
In the ink media set of any one of application examples 1 to 3,
The average thickness of the inorganic particle-containing layer may be 0.01 times or more and 0.1 times or less with respect to the average thickness of the receiving layer.

[Application Example 5]
In the ink media set of any one of Application Examples 1 to 4,
The inorganic particles contained in the inorganic particle-containing layer can be alumina particles.

[Application Example 6]
In the ink media set of any one of Application Examples 1 to 5,
The recording medium may have a parallel transmittance of 84% or more and a haze of 5% or less.

[Application Example 7]
In the ink media set of any one of application examples 1 to 6,
The glitter pigment may be particles containing silver or aluminum.

[Application Example 8]
One aspect of the recording method according to the present invention is:
A recording medium having a receiving layer on at least one surface of the base material, further having at least one inorganic particle-containing layer above the receiving layer, and having the inorganic particle-containing layer on the recording surface. Recording is performed using a recording ink containing a pigment.

FIG. 3 is a cross-sectional view schematically showing an example of a recording medium that constitutes the ink media set according to the embodiment.

  Hereinafter, preferred embodiments of the present invention will be described. The embodiment described below describes an example of the present invention. In addition, the present invention is not limited to the following embodiments, and includes various modifications that are implemented within a range that does not change the gist of the present invention.

1. Ink Media Set The ink media set according to the present embodiment is a set of a recording ink and a recording medium, wherein the recording ink contains a glitter pigment, and the recording medium is It has a receiving layer on at least one surface of a substrate, further has at least one inorganic particle-containing layer above the receiving layer, and has the inorganic particle-containing layer on the recording surface. To do. Hereinafter, the recording ink and the recording medium constituting the ink media set according to the present embodiment will be described in detail in this order.

1.1. Recording ink 1.1.1. Bright pigment The recording ink constituting the ink media set according to the present embodiment is not particularly limited as long as it contains a bright pigment, and may be a water-based ink or a non-water-based ink. Also good. A water-based ink is one in which the main solvent contained in the ink is water. The water content in the water-based ink is preferably 50% by mass or more, more preferably 70% by mass or more. Non-aqueous ink refers to an ink in which the main solvent contained in the ink is an organic solvent. The content of the organic solvent in the non-aqueous ink is preferably 50% by mass or more, more preferably 70% by mass or more.

  In the present invention, the glitter refers to a property characterized by, for example, the specular gloss of an obtained image (see Japanese Industrial Standard (JIS) Z8741). For example, the types of glitter include glitter that reflects light in a specular manner and so-called matte glitter, and can be characterized by, for example, high or low specular gloss.

  The glitter pigment is not particularly limited as long as it can exhibit glitter when attached to a medium. For example, aluminum, silver, gold, platinum, nickel, chromium, tin, zinc, indium, titanium, and Examples thereof include one or two or more alloys selected from the group consisting of copper (also referred to as metal pigments) and pearl pigments having pearly luster. Representative examples of pearl pigments include pigments having pearly luster and interference gloss such as titanium dioxide-coated mica, fish scale foil, and bismuth oxychloride. Further, the glitter pigment may be subjected to a surface treatment for suppressing reaction with water. By including a glitter pigment in the ink, an image having glitter can be recorded.

  The glitter pigment is preferably a metal particle from the viewpoint of ensuring good glitter. Moreover, among the metal particles exemplified above, particles containing silver or aluminum are preferable, and particles containing silver are more preferable.

  The silver-containing particles may have any shape such as spherical particles or tabular (leaf-like) particles, but spherical particles are preferable from the viewpoint of having high glitter. In the case of an ink media set in which ink containing silver-containing spherical particles and a recording medium to be described later are combined, spherical particles can be smoothly arranged on the recording medium, so that it is particularly bright. An excellent image can be recorded.

  The average particle diameter of the silver-containing particles is not particularly limited, but is preferably 5 to 500 nm, more preferably 10 to 200 nm, and particularly preferably 10 to 80 nm. When the average particle diameter of the silver-containing particles is in the above range, a smooth glitter image can be recorded in which the granularity of the individual particles is not noticeable. In addition, since the dispersion stability of the particles in the ink becomes good, nozzle clogging and the like can be prevented when the ink is used for ink jet recording.

  The average particle diameter of the silver-containing particles can be measured by a “laser method” in which laser light having a constant wavelength is applied to the particles and the particle diameter and particle size distribution are analyzed from the scattered light intensity pattern. An example of an apparatus based on this laser method is “Microtrac UPA” manufactured by Nikkiso Co., Ltd.

  On the other hand, the particles containing aluminum may have any shape such as spherical particles or tabular (leaf-like) particles, but are preferably tabular (leaf-like) particles from the viewpoint of having high glitter. The tabular grains containing aluminum can be produced, for example, by the method described in JP-A-2008-174712. Specifically, the aluminum or aluminum alloy layer and the release resin layer of the composite pigment base material having a structure in which a release resin layer and an aluminum or aluminum alloy layer are sequentially laminated on the sheet-like substrate surface Separating from the sheet-like base material with the interface as a boundary, pulverizing and refining to obtain tabular grains. And when the major axis on the plane of the obtained tabular grains is X, the minor axis is Y, and the thickness is Z, 50% average grains of the equivalent circle diameter determined from the area of the XY plane of the tabular grains A material having a diameter R50 of 0.5 to 3 μm and a condition satisfying R50 / Z> 5 is collected.

  The major axis X, minor axis Y, and equivalent circle diameter on the plane of the aluminum pigment (tabular grains) can be measured using a particle image analyzer. As the particle image analyzer, for example, flow type particle image analyzers FPIA-2100, FPIA-3000, and FPIA-3000S manufactured by Sysmex Corporation can be used.

  The aluminum or aluminum alloy layer is preferably formed by vacuum deposition, ion plating or sputtering.

  The thickness of the aluminum or aluminum alloy layer is preferably 20 nm or more and 100 nm or less. Thereby, an aluminum pigment having an average thickness of 20 nm to 100 nm is obtained. By making it 20 nm or more, it is excellent in reflectivity and glitter, and the performance as a glitter pigment is enhanced, and by making it 100 nm or less, the increase in apparent specific gravity is suppressed and the dispersion stability of the glitter pigment is ensured. Can do.

  The content (solid content) of the glitter pigment in the ink is preferably 0.5% by mass or more and 15% by mass or less, and 0.5% by mass or more and 10% by mass or less in 100% by mass of the ink. More preferably. When the content of the glitter pigment is within the above range, the storage stability of the ink is good, and when the ink is used for ink jet recording, the discharge stability from the nozzle is good.

1.1.2. Other Components The recording ink constituting the ink media set according to the present embodiment may be water, organic solvent, humectant, resin, surfactant, preservative, pH adjustment as exemplified below, if necessary. An agent or the like may be added separately.

<Water>
Although it does not specifically limit as said water, Pure water or ultrapure water, such as ion-exchange water, ultrafiltration water, reverse osmosis water, and distilled water, is preferable. In particular, water obtained by sterilizing these waters by ultraviolet irradiation or addition of hydrogen peroxide is preferable because generation of mold and bacteria is prevented for a long period of time.

<Organic solvent>
The organic solvent is preferably a polar organic solvent such as alcohols (for example, methyl alcohol, ethyl alcohol, propyl alcohol, butyl alcohol, isopropyl alcohol, or fluorinated alcohol), ketones (for example, acetone, methyl ethyl ketone, or Cyclohexanone, etc.), carboxylic acid esters (eg, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl propionate, or ethyl propionate), or ethers (eg, diethylene glycol diethyl ether, dipropylene glycol monobutyl ether, Tetrahydrofuran or dioxane etc.) can be used.

<Humectant>
Examples of the humectant include glycerols, glycols, and saccharides. According to these humectants, nozzle clogging due to drying of the ink can be prevented, and the glitter of the glitter image can be further enhanced.

  Examples of glycerols include glycerin, diglycerin, triglycerin, trimethylolethane, trimethylolpropane, C1-10 alkyl glyceryl ether, C1-10 alkyl diglyceryl ether, C1-10 alkyl triglyceryl ether, and the like. Can be mentioned. Among these glycerols, glycerin and trimethylolpropane are preferable because they can further improve the brightness of an image.

  Examples of glycols include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, pentaethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, butylene glycol, 1,2-pentanediol, and 1,2-hexane. Examples include diol, 1,2-heptanediol, 1,2-octanediol, 1,2,6-hexanetriol, thioglycol, hexylene glycol, and polyethylene glycol. Among these glycols, 1,2-hexanediol, triethylene glycol, hexylene glycol, propylene glycol, and polyethylene glycol are preferable in that the brightness of the image can be further improved.

  Sugars include monosaccharides such as glucose, fructose and galactose; disaccharides such as maltose, sucrose, cellobiose, lactose, trehalose, ilmaltose, and gentiose; trisaccharides such as gentianose, raffinose and panose; other polysaccharides; Alcohol etc. are mentioned. As the sugar, a reduced starch saccharified product (a mixture containing a sugar alcohol) such as HS-500 (manufactured by Hayashibara Corporation) may be used.

  The humectants exemplified above may be used alone or in combination of two or more. The addition amount of the humectant is preferably 5% by mass or more and 20% by mass or less, and more preferably 8% by mass or more and 18% by mass or less with respect to the total mass of the ink.

<Resin>
Examples of the resin include acrylic resins, styrene acrylic resins, fluorene resins, urethane resins, polyolefin resins, rosin modified resins, terpene resins, polyester resins, polyamide resins, epoxy resins, vinyl chloride resins. Known resins such as resins, vinyl chloride-vinyl acetate copolymers, ethylene vinyl acetate resins, polyolefin waxes and the like can be mentioned. These resins can be used singly or in combination of two or more. These resins can improve the fixability and abrasion resistance of the glitter pigment to the recording medium, and can improve the dispersion stability of the glitter pigment in the ink. The addition amount of the resin is preferably 0.1% by mass or more and 10% by mass or less with respect to the total mass of the ink.

<Surfactant>
Examples of the surfactant include acetylene glycol surfactants and polysiloxane surfactants. These surfactants can improve the penetrability by enhancing the wettability of the ink to the recording medium.

  Examples of the acetylene glycol surfactant include 2,4,7,9-tetramethyl-5-decyne-4,7-diol, 3,6-dimethyl-4-octyne-3,6-diol, 3, Examples include 5-dimethyl-1-hexyn-3-ol, 2,4-dimethyl-5-hexyn-3-ol, and the like. Moreover, a commercial item can also be utilized for acetylene glycol type-surfactant, for example, Orphine E1010, STG, Y (above, Nissin Chemical Co., Ltd. product), Surfinol 104, 82, 465, 485, TG (above , Air Products and Chemicals Inc.). Commercially available products can be used as the polysiloxane surfactant, and examples thereof include BYK-347, BYK-348, BYK-UV3500 (manufactured by Big Chemie Japan Co., Ltd.) and the like. Furthermore, other surfactants such as an anionic surfactant, a nonionic surfactant, and an amphoteric surfactant may be separately added to the recording ink.

  The addition amount of the surfactant is preferably 0.01% by mass or more and 5% by mass or less, and more preferably 0.1% by mass or more and 2% by mass or less with respect to the total mass of the ink.

<Preservative>
Examples of the preservative include sodium benzoate, sodium pentachlorophenol, sodium 2-pyridinethiol-1-oxide, sodium sorbate, sodium dehydroacetate, 1,2-dibenzthiazolin-3-one (manufactured by ICI). Proxel CRL, proxel BND, proxel GXL, proxel XL-2, proxel TN) and the like. The addition amount of the preservative is preferably 0.1% by mass or more and 2% by mass or less, and more preferably 0.2% by mass or more and 1% by mass or less with respect to the total mass of the ink.

<PH adjuster>
Examples of the pH adjuster include amines such as diethanolamine, triethanolamine, propanolamine, and morpholine, and modified products thereof; inorganic salts such as potassium hydroxide, sodium hydroxide, and lithium hydroxide; ammonium hydroxide, quaternary An ammonium hydroxide (tetramethylammonium etc.) is mentioned.

  In particular, in the case of ink containing silver particles, the pH is preferably 8 or more, and more preferably 8 or more and 10 or less. By making the pH of the silver particle-containing ink composition 8 or more basic, storage stability can be improved in terms of pH change of the ink, aggregation of silver particles, and the like.

1.1.3. Applications and physical properties of recording ink The recording ink constituting the ink media set according to the present embodiment can be suitably used in various fields, but is particularly suitable as an inkjet ink mounted on an inkjet recording apparatus. Can be used.

  The recording ink preferably has a surface tension at 20 ° C. of 20 mN / m or more and 50 mN / m, preferably 25 mN / m or more and 40 mN / m, from the viewpoint of a balance between good recording quality and reliability as an inkjet ink. The following is more preferable. The surface tension is measured by using an automatic surface tension meter CBVP-Z (manufactured by Kyowa Interface Science Co., Ltd.) by confirming the surface tension when the platinum plate is wetted with ink in an environment of 20 ° C. be able to.

  From the same viewpoint, the viscosity at 20 ° C. of the ink composition according to the present embodiment is preferably 2 mPa · s or more and 15 mPa · s or less, and more preferably 2 mPa · s or more and 10 mPa · s or less. preferable. The viscosity is measured by using a viscoelasticity tester MCR-300 (manufactured by Pysica), increasing the Shear Rate to 10 to 1000 in an environment of 20 ° C., and reading the viscosity at Shear Rate 200. Can be measured.

1.1.4. Method for Preparing Recording Ink The recording ink can be produced by dispersing and mixing the above components by an appropriate method. After sufficiently stirring each of the components described above, the target recording ink can be obtained by performing filtration in order to remove coarse particles and foreign matters that cause clogging.

1.2. Recording Medium An example of a recording medium constituting the ink media set according to the present embodiment will be described with reference to the drawings. FIG. 1 is a cross-sectional view schematically showing an example of a recording medium constituting the ink media set according to the present embodiment.

  As shown in FIG. 1, in the recording medium 100, a receiving layer 12 for increasing ink absorbency is formed above a substrate 10, and an inorganic particle-containing layer 14 is further formed above the receiving layer 12. Has been.

  The substrate 10 is preferably formed of a synthetic resin having heat resistance, dimensional stability, rigidity, transparency, and the like. For example, polyester (polyethylene terephthalate, etc.), cellulose triacetate, polycarbonate, polyolefin (low density polyethylene, Examples include olefin homopolymers such as high-density polyethylene, polypropylene, polybutene, and polypentene or copolymers such as ethylene-propylene copolymer), sheets (including films) formed from polyvinyl chloride, polyimide, and the like. The average thickness of the substrate is usually about 20 to 250 μm. In addition, a sheet material other than a synthetic resin sheet such as synthetic paper or coated paper can be used as the substrate 10 depending on the application.

  From the viewpoint of improving the adhesiveness, the substrate 10 may be provided with a primer layer as necessary, or after receiving a corona discharge treatment, the receiving layer 12 may be formed thereon.

  An undercoat layer may be provided between the substrate 10 and the receiving layer 12 so as to be preferably in contact with the receiving layer 12. By forming the undercoat layer, ink absorbability is further improved. This undercoat layer is formed by applying and drying above the base material 10 in advance before the receiving layer 12 is formed, and mainly contains a water-soluble polymer or polymer latex that can form a film. . The material for the undercoat layer is preferably a water-soluble polymer such as gelatin, polyvinyl alcohol, polyvinyl pyrrolidone, or water-soluble cellulose, and more preferably gelatin. Furthermore, the undercoat layer preferably contains a surfactant or a hardener.

  For the receiving layer 12, a receiving layer solution (coating solution) is prepared, and the coating solution is applied above the substrate 10 using a roll coater, an air knife coater, a bar coater, a rod coater, a bread coater, a comma coater, or the like. It can be formed by drying with hot air. The average thickness of the receiving layer 12 is preferably 3 μm or more and 50 μm or less, more preferably 15 μm or more and 45 μm or less. If the thickness of the receiving layer 12 is too thin, the ink absorption capacity becomes insufficient, and the surface drying property of the ink may be lowered. If the thickness of the receiving layer 12 is too thick, there is a risk of film cracking, leading to an increase in cost, which is not preferable.

  The receiving layer 12 is usually formed on one side of the substrate 10, but may be formed on both sides. When the receiving layers 12 are provided on both surfaces of the base material 10, an anti-curl effect can be obtained. Further, when the receiving layer 12 is formed on one side of the substrate 10, a back coat layer mainly composed of a polyurethane resin may be formed on the opposite surface of the substrate 10. Here, “mainly comprising a polyurethane resin” means that the polyurethane resin is contained in an amount of 50% by mass or more, preferably 70% by mass or more, more preferably 80% by mass or more based on the total solid content of the backcoat layer. Say. By providing the back coat layer mainly composed of polyurethane resin, the conveyance accuracy in the printer is improved.

  As a coating liquid for producing the receiving layer 12, a coating liquid mainly composed of a binder resin can be used, and other additives can be further contained.

  The binder resin preferably contains a hydrophilic binder from the viewpoint of high transparency and high ink permeability. Examples of such hydrophilic binders include cationic urethane resins, completely or partially saponified polyvinyl alcohol, and cation-modified polyvinyl alcohol. Among these, a cationic urethane resin is particularly preferable.

  The binder resin may contain an emulsion resin in addition to the hydrophilic binder. Examples of such emulsion resins include conjugated diene polymer latexes such as maleic anhydride resins, styrene-butadiene copolymers, and methyl (meth) acrylate-butadiene copolymers; acrylic polymer latexes; ethylene vinyl acetate copolymers. Vinyl polymer latex such as polymers; or functional group-modified polymer latex with functional group-containing monomers such as carboxyl groups of these various polymers; aqueous adhesion of thermosetting synthetic resins such as melamine resins and urea resins Agents: Synthetic resin adhesives such as polymethyl methacrylate, polyurethane resin, unsaturated polyester resin, vinyl chloride-vinyl acetate copolymer, polyvinyl butyral, alkyd resin and the like.

  Furthermore, in the coating liquid, as other additives, inorganic particles, dispersants, thickeners, fluidity improvers, antifoaming agents, foam suppressors, mold release agents, foaming agents, penetrating agents, coloring dyes, Color pigments, fluorescent brighteners, antioxidants, ultraviolet absorbers, preservatives, water resistance agents, hardeners, and the like can be appropriately blended as necessary.

  The inorganic particle-containing layer 14 is formed above the receiving layer 12 and may be a single layer or a stack of two or more layers. Here, an inorganic particle content layer means the layer which contains 70 mass% or more of inorganic particles with respect to the total solid of this layer, Preferably it is 80 mass% or more, More preferably, it is 90 mass% or more.

  The inorganic particle-containing layer 14 becomes the outermost surface of the recording medium 100, that is, the recording surface. Since the recording medium 100 has the inorganic particle-containing layer 14 on the recording surface, it is possible to easily arrange the glitter pigment, so that a glitter image with reduced unevenness can be formed. Thereby, an image excellent in glitter can be recorded on the recording medium 100.

  The average thickness of the inorganic particle-containing layer 14 is preferably 0.1 μm or more and 3 μm or less, more preferably 0.5 μm or more and 2 μm or less. If the inorganic particle-containing layer 14 is too thin, it is difficult to arrange the glitter pigment, so that the glitter of the recorded image may be lowered. If the thickness of the inorganic particle-containing layer 14 is too thick, the transparency may decrease, leading to an increase in cost, which is not preferable.

  The average thickness of the inorganic particle-containing layer 14 with respect to the average thickness of the receiving layer 12 is preferably 0.01 times or more and 0.1 times or less, more preferably 0.02 times or more and 0.05 times or less. When the ratio of the average thickness is within the above range, the recording medium is excellent in transparency, and the recording medium is excellent in balance between glitter and ink absorbability.

  The inorganic particles contained in the inorganic particle-containing layer 14 include light calcium carbonate, heavy calcium carbonate, kaolin, talc, calcium sulfate, barium sulfate, titanium dioxide, zinc oxide, zinc sulfide, zinc carbonate, satin white, aluminum silicate. Diatomaceous earth, calcium silicate, magnesium silicate, synthetic amorphous silica, colloidal silica, pseudoboehmite, aluminum hydroxide, alumina, lithopone, zeolite, hydrohalosite, magnesium carbonate, magnesium hydroxide and the like. Among these, alumina, synthetic amorphous silica or colloidal silica is preferable, and alumina is more preferable from the viewpoint of improving the glitter of recorded images. The particle diameter of the inorganic particles is preferably 5 to 500 nm, more preferably 10 to 100 nm, and particularly preferably 10 to 50 nm from the viewpoint of facilitating arranging the glitter pigment.

  The inorganic particle-containing layer 14 can contain a hydrophilic binder, a surfactant, a pH adjuster and the like in addition to the inorganic particles. The inorganic particle-containing layer 14 is prepared by coating or drying a coating liquid in which the above materials are dispersed or dissolved in an appropriate solvent such as water or an organic solvent. Can be formed.

  The recording medium constituting the ink media set according to the present embodiment is preferably substantially transparent. Here, the term “substantially transparent” is not limited to a material that completely transmits light, but includes a material that is referred to as a transparent material, that is, translucent and slightly colored. As a specific example, when measured according to JIS K7136, JIS K7361, and ASTM D1003, the parallel transmittance is 84% or more and the haze is 5% or less.

2. Recording Method The recording method according to the present embodiment is characterized in that recording is performed on the recording surface of the recording medium described above using the recording ink described above. Since the recording medium described above has an inorganic particle-containing layer serving as a recording surface above the receiving layer, the glossy pigment is easily arranged on the recording surface and the glossiness is increased. Moreover, since it has a receiving layer, it is excellent in the surface drying property of the ink.

  The recording method according to the present embodiment may use the above-described recording medium and the above-described recording ink, and can be suitably used in various fields. Can be used particularly preferably. As an ink jet recording apparatus, for example, a method of converting characters into a mechanical signal using an electrostrictive element and intermittently ejecting ink stored in an ink jet head to record characters and symbols on the surface of the recording medium (piezo method) ); A method of recording characters and symbols on the surface of a recording medium by rapidly heating the ink stored in the ink jet head at a location very close to the discharge portion to generate bubbles, and discharging intermittently by volume expansion due to the bubbles ( And the like using a recording method. The recording ink is particularly suitable for an ink jet recording apparatus using a piezo method as a recording means.

3. EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited to these examples.

3.1. Preparation of recording ink 3.1.1. Preparation of ink containing silver particles 1000 g of polyvinylpyrrolidone (weight average molecular weight 10,000) was dissolved in 500 g of propylene glycol to obtain a first solution. Next, 128 g of silver nitrate as a silver precursor was dissolved in 500 ml of propylene glycol to obtain a second solution. Next, the first solution and the second solution were mixed at 120 ° C. for 90 minutes to reduce the silver precursor, and polyvinyl pyrrolidone was adsorbed on the surface of the generated silver particles. Then, the formed silver particles (silver colloid particles) were separated by centrifugation, and the separated silver particles were dispersed in water so that the solid content concentration was 20% by mass. The average particle diameter of the obtained silver particles was 35 nm. The average particle size of the silver particles was measured using “Microtrac UPA” (manufactured by Nikkiso Co., Ltd.). The measurement conditions were a refractive index of 0.2-3.9i, a solvent (water) refractive index of 1.333, and a measured particle shape of spherical.

  Subsequently, 6 parts by mass of the silver particles (concentration in terms of solid content) obtained above, 5 parts by mass of glycerin, 5 parts by mass of 1,2-hexanediol, acetylene glycol surfactant (manufactured by Air Products and Chemicals Inc., product) Name “Surfinol 465”) 1 part by mass and 0.3 part by mass of triethanolamine were added, and ion exchange water was added thereto to make a total of 100 parts by mass, and these were sufficiently mixed and stirred. Then, it filtered with the metal filter with a hole diameter of 5 micrometers, and deaerated using the vacuum pump. Thus, the silver ink (ink containing silver particles) shown in Table 1 was obtained.

3.1.2. Preparation of ink containing aluminum particles On a PET film having a film thickness of 100 μm, cellulose acetate butyrate (butylation rate: 35 to 39%, manufactured by Kanto Chemical Co., Ltd.) 3.0% by mass and diethylene glycol diethyl ether (Nippon Emulsifier Co., Ltd.) (Manufactured) A resin layer coating solution consisting of 97% by mass was uniformly applied by a bar coating method and dried at 60 ° C. for 10 minutes to form a resin layer thin film on the PET film.

  Subsequently, the aluminum vapor deposition layer with an average film thickness of 20 nm was formed on said resin layer using the vacuum vapor deposition apparatus (The vacuum device make, VE-1010 type vacuum vapor deposition apparatus).

  Next, the laminate formed by the above method is simultaneously peeled, refined, and dispersed in diethylene glycol diethyl ether using a VS-150 ultrasonic disperser (manufactured by ASONE), and integrated ultrasonic dispersion treatment time. An aluminum pigment dispersion having a duration of 12 hours was prepared.

  The obtained aluminum pigment dispersion was filtered through a SUS mesh filter having an opening of 5 μm to remove coarse particles. Subsequently, the filtrate was put into a round bottom flask, and diethylene glycol diethyl ether was distilled off using a rotary evaporator. Thus, the aluminum pigment dispersion was concentrated, and then the concentration of the aluminum pigment dispersion was adjusted to obtain an aluminum pigment dispersion having a concentration of 5% by mass.

  Then, using a particle size distribution analyzer (manufactured by Sysmex Corporation, FPIA-3000S), the obtained aluminum pigment has a 50% average particle diameter R50 of the equivalent circle diameter of the major axis (X direction) -minor axis (Y direction) plane and When the average film thickness Z was measured, R50 was 1.03 μm and Z was 0.02 μm. Furthermore, based on the measured values of R50 and Z obtained, R50 / Z was calculated to be 51.5.

  47.8 parts by mass of diethylene glycol diethyl ether, 45 parts by mass of dipropylene glycol monobutyl ether, 6 parts by mass of N-2043-60MEX (manufactured by Harima Chemicals Co., Ltd., resin emulsion), polysiloxane surfactant (manufactured by Big Chemie Japan Co., Ltd.) , Trade name “BYK-3500”) 0.2 parts by mass was mixed and dissolved to form an ink solvent, and then 1 part by mass of the aluminum pigment (solid content equivalent concentration) prepared above was added to the ink solvent. Further, the mixture was stirred and mixed with a magnetic stirrer at room temperature and normal pressure for 30 minutes to obtain aluminum inks (inks containing aluminum particles) shown in Table 2.

3.2. Production of recording media A polypropylene sheet was prepared as a substrate. A cationic urethane resin (manufactured by DIC Corporation, trade name “Hydrain CP-7020”) was applied to one side of the base material using a bar coater so that the basis weight was 100 g / m ^2, and a drying furnace at 80 ° C. And dried for 2 minutes to prepare a receiving layer.

  Next, 2.5 g of alumina sol (average particle size: 100 to 500 nm) is mixed with 100 parts by mass of a cationic urethane resin (manufactured by DIC Corporation, trade name “Hydrain CP-7020”), and further 5 times with water. A coating solution was prepared by dilution.

On the receptor layer prepared above, the coating solution obtained above is applied so that the basis weight is 2.5 g / m ^2, and is dried in a drying furnace at 80 ° C. for 5 minutes to contain an inorganic particle-containing layer. Was made. In this way, recording media 1 shown in Tables 1 and 2 were produced.

  Recording media 2 to 4 shown in Tables 1 and 2 were produced in the same manner as the recording medium 1 except that the coating liquid was prepared using the inorganic particles shown in Tables 1 and 2. Further, the recording medium 5 shown in Tables 1 and 2 is the same as the recording medium 1 described above, and only the receiving layer is formed on the substrate.

The inorganic particles shown in Table 1 and Table 2 are as follows.
Alumina sol 100 (manufactured by Nissan Chemical Industries, Ltd., amorphous feather-like particles having an average length of about 100 nm and an average width of about 10 nm)
・ Alumina sol 520 (Nissan Chemical Industries, Ltd., plate-like particles having an average particle size of 10 to 20 nm)
・ Colloidal silica (manufactured by Nissan Chemical Industries, Ltd., trade name “Snowtex AK”, average particle size 76 nm)

3.3. Evaluation test 3.3.1. Transparency evaluation of recording media Using a haze meter (manufactured by Nippon Denshoku Industries Co., Ltd., model “NDH 5000”), the parallel transmittance (%) and haze (%) of each recording medium prepared above were determined. , And measured according to ASTM D1003 and JIS K7136, respectively. The results are also shown in Table 1 and Table 2. When the parallel transmittance is 84% or more and the haze is 5% or less, it can be evaluated that the recording medium is substantially transparent.

3.3.2. Glossiness Evaluation A glossiness evaluation sample was prepared using an inkjet printer PX-G930 (trade name, manufactured by Seiko Epson Corporation) equipped with a cartridge filled with the recording ink (silver ink or aluminum ink) prepared above. I went.

  Printing ink droplets were ejected from the nozzles of the printer, and printing was performed on each recording medium shown in Tables 1 and 2 at a resolution of 1440 × 1440 dpi. The printing pattern was a 40% duty pattern for each ink. These were used as samples for evaluating glossiness.

In this specification, the “Duty value” is a value calculated by the following equation.
Duty (%) = (number of actual ejection dots / (vertical resolution × horizontal resolution)) × 100
(In the formula, “number of actual ejection dots” is the number of actual ejection dots per unit area, and “vertical resolution” and “horizontal resolution” are resolutions per unit area.)

  About each obtained glossiness evaluation sample, using a gloss meter (made by Nippon Denshoku Industries Co., Ltd., trade name “GlossMeter model number VGP5000”), “60 ° regular reflection gloss” according to JIS Z8741: 1997. It was measured. The “60 ° specular glossiness” was measured three times for each gloss evaluation sample, and the average value of the measured values was obtained. The average values obtained are listed in Tables 1 and 2.

3.4. Evaluation results Table 1 shows the evaluation results when silver ink was used, and Table 2 shows the evaluation results when aluminum ink was used.

  According to the results in Tables 1 and 2, the glitter images (Examples 1 to 8) recorded on the recording media 1 to 4 having the inorganic particle-containing layer on the recording surface have the inorganic particle-containing layer. It was found that the glossiness was clearly improved as compared with the glittering images (Comparative Examples 1 and 2) recorded on the recording medium 5 having no recording.

  It was also found that when the inorganic particles contained in the inorganic particle-containing layer are alumina particles, the glossiness of the recorded image is particularly improved.

  From the above examples and comparative examples, it can be said that the advantageous effects of the ink media set according to the present invention have been demonstrated.

  The present invention is not limited to the embodiments described above, and various modifications are possible. For example, the present invention includes substantially the same configuration (for example, a configuration having the same function, method, and result, or a configuration having the same purpose and effect) as the configuration described in the embodiment. In addition, the invention includes a configuration in which a non-essential part of the configuration described in the embodiment is replaced. In addition, the present invention includes a configuration that achieves the same effect as the configuration described in the embodiment or a configuration that can achieve the same object. In addition, the invention includes a configuration in which a known technique is added to the configuration described in the embodiment.

DESCRIPTION OF SYMBOLS 10 ... Board | substrate, 12 ... Receiving layer, 14 ... Inorganic particle content layer, 100 ... Recording medium

Claims (8)

A set of recording ink and recording media,
The recording ink contains a glitter pigment,
The recording medium has a receiving layer on at least one surface of a substrate, further has at least one inorganic particle-containing layer above the receiving layer, and has the inorganic particle-containing layer on the recording surface. Ink media set.   The ink media set according to claim 1, wherein an average thickness of the inorganic particle-containing layer is 0.1 μm or more and 3 μm or less.   The ink media set according to claim 1 or 2, wherein an average thickness of the receiving layer is 3 µm or more and 50 µm or less.   The ink media set according to any one of claims 1 to 3, wherein an average thickness of the inorganic particle-containing layer is 0.01 times or more and 0.1 times or less with respect to an average thickness of the receiving layer.   The ink media set according to any one of claims 1 to 4, wherein the inorganic particles contained in the inorganic particle-containing layer are alumina particles.   The ink media set according to any one of claims 1 to 5, wherein the parallel transmittance of the recording medium is 84% or more and haze is 5% or less.   The ink media set according to any one of claims 1 to 6, wherein the glitter pigment is a particle containing silver or aluminum.   A recording medium having a receiving layer on at least one surface of the base material, further having at least one inorganic particle-containing layer above the receiving layer, and having the inorganic particle-containing layer on the recording surface. A recording method for recording using a recording ink containing a pigment.

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