JP2008239951A - Ink set, ink jet recording method and recorded matter - Google Patents

Abstract

It is possible to form a coating film having a metallic luster on a printed matter by forming an ink set including an ink composition having a high metallic specular gloss by focusing on aluminum as a relatively inexpensive metallic material. An object is to provide an ink set. Another object of the present invention is to provide an ink set having excellent storage stability by preventing gelation during storage in a two-component photocurable ink composition.
At least one selected from the group consisting of a metallic ink composition containing a metal pigment, a chromatic ink composition containing a chromatic pigment, a black ink composition containing a black pigment, and a white ink composition containing a white pigment. An ink set comprising one or more photocurable ink compositions;
In addition, a metallic ink composition containing a metal pigment, a photocurable ink composition A not containing a color material, and at least one color material selected from the group consisting of a chromatic color pigment, a black pigment, and a white pigment An ink set comprising the photocurable ink composition B contained therein.
[Selection figure] None

Description

The present invention relates to an ink set, an ink jet recording method, and a recorded matter, and more particularly, to an ink set, an ink jet recording method, and a recorded matter capable of forming a coating film having a metallic luster.

Conventionally, in order to form a coating film having a metallic luster on a printed material, gold powder made from brass, aluminum fine particles, etc., foil press printing using printing ink or metal foil using silver powder as a pigment,
A thermal transfer method using a metal foil is used.

However, a coating film made of printing ink using gold powder or silver powder has a large average particle diameter of 10 to 30 μm, and a matte metallic luster is obtained, but it is difficult to obtain a mirror gloss. there were. Also, in foil stamping or thermal transfer using metal foil, an adhesive is applied to the print medium, a smooth metal foil is pressed onto the print medium, the recording medium and the metal foil are in close contact and heated, and the metal foil and the recording medium are thermally melted. Take the method of wearing. For this reason, relatively good gloss can be obtained, but since the number of manufacturing processes increases and pressure and heat are applied during the manufacturing processes, there is a limitation that the recording medium is limited to recording media that are resistant to heat and deformation.

In recent years, many applications of inkjet in printing have been seen, and one of the applications is metallic printing. For example, Japanese Patent Laid-Open No. 2002-179960 discloses a technique in which a metal film is formed on the surface of plastic spherical particles, and an ink composition containing the pigment is subjected to a printing process by ink jet printing (Patent Document 1). ). However, in order to obtain a high metallic luster, it is necessary to deform and flatten the sphere and smooth the surface. In this technique, it is said that it is necessary to simultaneously perform the press treatment with a roller and the heat treatment. Therefore, it is inevitable that the apparatus and the manufacturing process are complicated in this respect, and the recording medium is also limited.

Japanese Patent Laid-Open No. 2003-292836 also discloses a technique using an ink composition in which a precious metal colloid such as gold or silver is dispersed (Patent Documents 2 and 3). However, when the noble metal colloid is prioritized in dispersion stability and the particle diameter is reduced to several nanometers to several tens of nanometers, color development derived from plasmon absorption appears, and a metallic luster cannot be obtained as an ink composition. In this case, a good metallic luster can be obtained by fusing the colloidal particles by drying after the coating film is heated. In addition, even if metallic gloss is obtained with these technologies, high metallic specular gloss with a specular gloss of 20 degrees, 60 degrees, and 85 degrees exceeding 200, 200, and 100 is obtained on a uniform and uniform surface. It was difficult. When the particle size is increased in favor of metallic luster, the dispersion stability is lowered, the problem of aggregation and sedimentation cannot be avoided, and the shelf life of the ink composition is remarkably reduced. Further, it is obvious that using a noble metal as a material greatly increases the cost of the ink composition, and therefore can only be used for high value-added applications, which is disadvantageous in terms of cost.
JP 2002-179960 A Japanese Patent Laid-Open No. 2003-292836 JP 2003-306625 A

The present invention focuses on aluminum as a relatively inexpensive metal material, and can form a coating film having a metallic luster on a printed matter by constructing an ink set including an ink composition having a high metallic mirror gloss. It is an object to provide a simple ink set. Furthermore, by performing printing using a photocurable ink composition, metallic printing with an arbitrary color tone is possible. Also,
An additional object of the present invention is to provide an ink set having excellent storage stability by preventing gelation during storage in a two-part photocurable ink composition.

In order to solve the above-mentioned problems, the present inventors have conducted intensive studies. As a result, due to metal pigment dispersions, ink compositions, ink jet recording methods and recorded materials using specific metal pigments, it has been impossible in the past. It was found that a printed matter having a high specular gloss was obtained. The present invention has been made on the basis of such knowledge, and provides the following inventions.

1. A metallic ink composition comprising a metal pigment;
At least one photocurable ink composition selected from the group consisting of a chromatic ink composition, a black ink composition, and a white ink composition;
Ink set with.

2. A metallic ink composition containing a metal pigment;
A photocurable ink composition A containing no coloring material;
A photocurable ink composition B containing at least one colorant selected from the group consisting of chromatic pigments, black pigments, and white pigments;
Ink set with.

3. The metal pigment is a tabular grain, the major axis on the plane of the tabular grain is X, the minor axis is Y,
When the thickness is Z, the condition that the 50% average particle diameter R50 of the equivalent circle diameter determined from the area of the XY plane of the tabular grains is 0.5 to 3 μm and R50 / Z> 5 is satisfied. 3. The ink set according to the above 1 or 2, which is a metal pigment that fills.

4). 2. The ink set according to 1, wherein the photocurable ink composition contains at least a colorant, a photopolymerization initiator, and a polymerizable compound.

5. 3. The ink set according to 2, wherein the photocurable ink composition A is non-aqueous and contains at least a photopolymerization initiator and a polymerizable compound.

6). The photocurable ink composition B is non-aqueous and contains at least a polymerizable compound,
3. The ink set according to 2 above, which does not contain a photopolymerization initiator.

7). 6. The ink set according to 4 or 5, wherein the photopolymerization initiator is at least two selected from the group consisting of bisacylphosphine oxide, monoacylphosphine oxide, α-aminoketone, and α-hydroxyketone. .

8). The polymerizable compound is an N-vinyl compound, ethylene glycol monoallyl ether,
8. The ink set according to any one of 4 to 7, which is at least one selected from the group consisting of dendritic polymers.

9. The dendritic polymer is a dendrimer and / or a hyperbranched polymer;
9. The ink set as described in 8 above.

10. A liquid container containing the ink set according to any one of 1 to 9.

11. A liquid ejecting apparatus comprising the liquid container according to 10.

12 In an inkjet recording method for performing recording by discharging droplets of an ink composition and attaching the droplets to a recording medium,
2. An ink jet recording method, wherein an image is formed using the ink set described in 1 above.

13. The metallic ink composition;
At least one selected from the group consisting of the chromatic ink composition, the black ink composition, and the white ink composition;
13. The ink jet recording method as described in 12 above, wherein an image having an arbitrary color tone is formed by simultaneously ejecting the ink.

14 After forming an image using the metallic ink composition, an image having an arbitrary color tone is formed using the chromatic color ink composition, and then the black ink composition and / or the white ink composition is ejected. 13. The inkjet recording method according to 12, wherein the formed image is subjected to a curing process simultaneously with or after ejection.

15. After the metallic ink composition was ejected to form an image, the chromatic color ink composition, the black ink composition, and the white ink composition were ejected at the same time, and formed simultaneously with or after the ejection. 13. The ink jet recording method as described in 12 above, wherein a curing process is performed on the image.

16. After forming an image using the metallic ink composition, the image is dried, and the chromatic color ink composition, the black ink composition, and the white ink composition are ejected to obtain an arbitrary color tone. 13. The ink jet recording method according to 12, wherein after the image is formed, the image is cured.

17. The inkjet recording method according to 15 or 16, wherein the curing treatment is performed by irradiating ultraviolet rays.

18. In an inkjet recording method for performing recording by discharging droplets of an ink composition and attaching the droplets to a recording medium,
3. An ink jet recording method for forming an image using the ink set described in 2 above.

19. The metallic ink composition;
The photocurable ink composition A and / or the photocurable ink composition B;
19. The ink jet recording method as described in 18 above, wherein the ink is simultaneously discharged and simultaneously or after the discharge, the formed image is subjected to a curing treatment to form an image of an arbitrary color tone.

20. After the metallic ink composition was ejected to form an image, the photocurable ink composition A and / or the photocurable ink composition B was ejected and formed simultaneously with or after the ejection. The image is subjected to a curing process to form an image of an arbitrary color tone, 18
The ink jet recording method described in 1.

21. Photocurable ink composition B containing the photocurable ink composition A and the white pigment
After the image is formed using, a curing treatment is performed by light irradiation, and then (i) the metallic ink composition, (ii) the photocurable ink composition A and / or (iii) the chromatic pigment. Alternatively, an image is formed using a photocurable ink composition B containing the black pigment,
19. The ink jet recording method as described in 18 above.

22. It was recorded by the inkjet recording method according to any one of 12 to 21 above.
Recorded matter.

According to the ink set, ink jet recording method and recorded matter of the present invention, it is possible to form an image having a high metallic gloss (so-called metallic gloss) on a recording medium by using a metallic ink composition containing a metal pigment. Furthermore, by combining the chromatic color ink composition, the black ink composition, and the white ink composition to form an ink set, an image that cannot be realized with a conventional ink set, that is, an arbitrary color tone, An image having gloss can be formed.

[Ink set of Embodiment 1]
As described above, the ink set of the present embodiment includes at least one selected from the group consisting of a metallic ink composition containing a metal pigment, a chromatic color ink composition, a black ink composition, and a white ink composition. A photocurable ink composition. This allows chromatic colors,
It is possible to form an image in which metallic metallic luster is added to black and white tones.

The metal pigment (also referred to as a metallic pigment) is a tabular grain. When the major axis on the plane of the tabular grain is X, the minor axis is Y, and the thickness is Z, the XY plane of the tabular grain is X-Y plane. The 50% average particle diameter R50 of the equivalent-circle diameter determined from the area of 0.5 to 3 μm and R50 / Z> 5
It is preferable that the metal pigment satisfy the following condition.

A “tabular grain” refers to a grain having a substantially flat surface (XY plane) and a substantially uniform thickness (Z). Since the plate-like particles are prepared by crushing a metal vapor-deposited film, metal particles having a substantially flat surface and a substantially uniform thickness can be obtained. Therefore, the major axis on the plane of the tabular grains can be defined as X, the minor axis as Y, and the thickness as Z.

“Equivalent circle diameter” is the diameter of the circle when assuming that the substantially flat surface (XY plane) of the tabular particles of the metallic pigment is a circle having the same projected area as the projected area of the particles of the metallic pigment. It is. For example, when the substantially flat surface (XY plane) of the tabular grain of the metallic pigment is a polygon, the diameter of the circle obtained by converting the projected surface of the polygon into a circle is calculated by using the diameter of the metallic pigment. It is called the equivalent-circle diameter of a tabular grain.

The 50% average particle diameter R50 of the equivalent circle diameter determined from the area of the XY plane of the tabular grains is more preferably 0.5 to 3 μm from the viewpoint of metallic luster and printing stability, and is preferably 0.75 to 0.75. 2
More preferably, it is μm.

Further, in terms of the relationship between the 50% average particle diameter R50 of the equivalent circle diameter and the thickness Z, it is preferable that R50 / Z> 5 from the viewpoint of securing a high metallic luster.

The metallic pigment is preferably aluminum or an aluminum alloy from the viewpoint of cost and ensuring a metallic luster. When an aluminum alloy is used, another metal element or non-metal element that can be added to aluminum is not particularly limited as long as it has a metallic luster, but silver, gold, platinum, nickel, chromium, tin Zinc, indium, titanium, copper and the like, and at least one of these simple substances or alloys thereof and mixtures thereof is preferably used.

The method for producing the metallic pigment includes, for example, the metal or metal compound layer and the release of the composite pigment base material having a structure in which a release resin layer and a metal or metal compound layer are sequentially laminated on the sheet-like substrate surface. The resin layer is separated from the sheet-like substrate with the interface of the resin layer as a boundary, pulverized and refined 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 metallic pigment (tabular particles) can be measured using a particle image analyzer. Examples of particle image analyzers include flow type particle image analyzers FPIA-2100, FPIA-3000, and FP manufactured by Sysmex Corporation.
IA-3000S can be used.

The metal or metal compound layer is preferably formed by vacuum deposition, ion plating or sputtering.

The metal or metal compound layer is formed with a thickness of 20 nm to 100 nm. Thereby, a pigment having an average thickness of 20 nm to 100 nm is obtained. By setting it to 20 nm or more, it is excellent in reflectivity and glitter, and the performance as a metallic pigment is enhanced. By setting it to 100 nm or less, increase in apparent specific gravity can be suppressed and dispersion stability of the metallic pigment can be secured. .

The release resin layer in the composite pigment base is an undercoat layer of the metal or metal compound layer, but is a peelable layer for improving the peelability from the sheet-like substrate surface. As the resin used for the peeling resin layer, for example, polyvinyl alcohol, polyvinyl butyral, polyethylene glycol, polyacrylic acid, polyacrylamide, cellulose derivative, polyvinyl butyral, acrylic acid polymer, or modified nylon resin is preferable.

A layer is formed by applying a solution of one or a mixture of the above to a recording medium and drying. After coating, additives such as a viscosity modifier can be contained.

The release resin layer is applied by generally used gravure coating, roll coating, blade coating, extrusion coating, dip coating, spin coating, or the like. After coating and drying, the surface is smoothed by calendaring if necessary.

Although the thickness of the resin layer for peeling is not specifically limited, 0.5-50 micrometers is preferable, More preferably, it is 1-10 micrometers. If it is less than 0.5 μm, the amount as a dispersion resin is insufficient, and 50 μm.
If it exceeds 1, it will be easily peeled off at the interface with the pigment layer.

Although it does not specifically limit as said sheet-like base material, Polyester film, such as polytetrafluoroethylene, polyethylene, a polypropylene, a polyethylene terephthalate, 6
Examples include release films such as polyamide films such as 6 nylon and 6 nylon, polycarbonate films, triacetate films, and polyimide films. A preferable sheet-like substrate is polyethylene terephthalate or a copolymer thereof.

Although the thickness of these sheet-like base materials is not specifically limited, 10-150 micrometers is preferable.
If it is 10 μm or more, there is no problem in handleability in the process or the like, and if it is 150 μm or less, it is rich in flexibility and there is no problem in roll formation, peeling and the like.

  The metal or metal compound layer may be sandwiched between protective layers. Examples of the protective layer include a silicon oxide layer and a protective resin layer.

The silicon oxide layer is not particularly limited as long as it is a layer containing silicon oxide, but is preferably formed from a silicon alkoxide such as tetraalkoxysilane or a polymer thereof by a sol-gel method.

An alcohol solution in which the silicon alkoxide or a polymer thereof is dissolved is applied and heated and fired to form a silicon oxide layer coating film.

The protective resin layer is not particularly limited as long as it is a resin that does not dissolve in the dispersion medium, and examples thereof include polyvinyl alcohol, polyethylene glycol, polyacrylic acid, polyacrylamide, and cellulose derivatives. Or it is preferable to form from a cellulose derivative.

A layer obtained by applying an aqueous solution of one or a mixture of two or more of the above resins and performing drying or the like is formed. The coating solution can contain additives such as a viscosity modifier.

The silicon oxide and the resin are applied by the same method as the application of the release resin layer.

Although the thickness of the said protective layer is not specifically limited, The range of 50-150 nm is preferable. 50
If it is less than nm, the mechanical strength is insufficient, and if it exceeds 150 nm, the strength becomes too high, so that pulverization / dispersion becomes difficult, and peeling may occur at the interface with the metal or metal compound layer.

  Further, a color material layer may be provided between the “protective layer” and the “metal or metal compound layer”.

The color material layer is introduced to obtain an arbitrary colored composite pigment, and can contain a color material capable of imparting an arbitrary color tone and hue in addition to the metallic luster and glitter of the metallic pigment used in the present invention. If it is, it will not specifically limit. Examples of the color material used for this color material layer include dyes,
Any of pigments may be used. Moreover, as a dye and a pigment, a well-known thing can be used suitably.

In this case, the “pigment” used in the color material layer is defined in the field of general pigment chemistry.
It means natural pigments, synthetic organic pigments, synthetic inorganic pigments, etc., which are different from those processed into a laminated structure such as “composite pigment” of the present invention.

A method for forming the color material layer is not particularly limited, but it is preferable to form the color material layer by coating.

Further, when the color material used in the color material layer is a pigment, it is preferable to further include a color material dispersion resin. Examples of the color material dispersion resin include a pigment, a color material dispersion resin, and other materials as necessary. It is preferable to form a resin thin film by dispersing or dissolving these additives in a solvent and forming a uniform liquid film by spin coating as a solution, followed by drying.

In the production of the composite pigment base material, it is preferable in terms of work efficiency that both the colorant layer and the protective layer are formed by coating.

As the composite pigment base material, a layer structure having a plurality of sequential laminated structures of the release resin layer and a metal or metal compound layer is also possible. At that time, the total thickness of the laminated structure composed of a plurality of metals or metal compound layers, that is, the metal or metal compound layer-exfoliation resin layer-metal or metal, excluding the sheet-like base material and the exfoliation resin layer immediately above it. The thickness of the metal compound layer or the release resin layer-metal or metal compound layer is preferably 5000 nm or less. When it is 5000 nm or less,
Even when the composite pigment raw material is rolled up, it does not easily crack or peel off and has excellent storage stability. In addition, when pigmented, it is excellent in glitter and preferable.

Moreover, although the structure where the resin layer for peeling and the metal or metal compound layer were laminated | stacked one by one on both surfaces of the sheet-like base material surface is also mentioned, it is not limited to these.

The peeling treatment method from the sheet-like substrate is not particularly limited, but is a method that is performed by immersing the composite pigment raw material in a liquid, or ultrasonic treatment is performed at the same time as the immersion in the liquid. A method of pulverizing the composite pigment separated from the treatment is preferred.

In the pigment obtained as described above, the release resin layer has a role of a protective colloid, and a stable dispersion can be obtained only by performing a dispersion treatment in a solvent. In the ink composition using the pigment, the resin derived from the release resin layer also has a function of imparting adhesiveness to a recording medium such as paper.

The metallic ink composition used for the ink set of this embodiment contains the above-described metallic pigment, an organic solvent, and a resin.

The concentration of the metallic pigment in the ink composition is preferably 0.1 to 10.0% by weight.

When the concentration of the metallic pigment in the ink composition is 0.1% by weight or more and less than 1.5% by weight, a glossy surface like a half mirror is obtained by ejecting an amount of ink that cannot sufficiently cover the printing surface, Although a feeling of gloss can be felt, it is possible to print a texture that allows the background to show through, and a high gloss metallic glossy surface can be formed by discharging a sufficient amount of ink to cover the printing surface. Therefore, for example, it is suitable for forming a half mirror image on a transparent recording medium or for expressing a highly glossy metallic glossy surface. Further, when the concentration of the metallic pigment in the ink composition is 1.5% by weight or more, the metal pigment is randomly arranged on the printed surface, so that high gloss cannot be obtained and a matte-like metallic glossy surface is formed. be able to. Therefore, for example, it is suitable for forming a shielding layer on a transparent recording medium.

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), carboxylic acid esters (eg, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl propionate, or ethyl propionate), or ethers (eg, diethyl ether, dipropyl ether, tetrahydrofuran, Alternatively, dioxane or the like can be used.

In particular, the organic solvent preferably contains one or more alkylene glycol ethers that are liquid at normal temperature and pressure.

  Alkylene glycol ethers are ethylene glycols based on methyl, n-propyl, i-propyl, n-butyl, i-butyl, hexyl and 2-ethylhexyl aliphatic, allyl with double bonds and phenyl groups. Ether and propylene glycol ether, colorless and odorless, with ether and hydroxyl groups in the molecule, so it is liquid at room temperature with both alcohol and ether properties . Moreover, there are a monoether type in which only one hydroxyl group is substituted and a diether type in which both hydroxyl groups are substituted, and these can be used in combination.

In particular, the organic solvent is preferably a mixture of alkylene glycol diether, alkylene glycol monoether, and lactone.

  As alkylene glycol monoether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol monophenyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, Diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monobutyl ether, tetraethylene glycol monomethyl ether, tetraethylene glycol Over monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether and the like.

Examples of the alkylene glycol diether include ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, triethylene glycol dibutyl ether, tetra Ethylene glycol dimethyl ether, tetraethylene glycol diethyl ether, tetraethylene glycol dibutyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, etc. It is below.

Examples of the lactone include γ-butyrolactone, δ-valerolactone, and ε-caprolactone.

By setting it as such a suitable structure, the objective of this invention can be achieved further.

Examples of the resin used in the metallic ink composition include acrylic resin, styrene-acrylic resin, rosin-modified resin, terpene resin, polyester resin, polyamide resin, epoxy resin, vinyl chloride resin, vinyl chloride-vinyl acetate copolymer. Examples include coalescence, fiber-based resin (for example, cellulose acetate butyrate, hydroxypropyl cellulose), polyvinyl butyral, polyacryl polyol, polyvinyl alcohol, polyurethane and the like.

Non-aqueous emulsion type polymer fine particles (NAD = Non Aqueous Dispersion) can also be used as the resin. This is a dispersion in which fine particles such as a polyurethane resin, an acrylic resin, and an acrylic polyol resin are stably dispersed in an organic solvent. For example,
For polyurethane resins, Sanprene IB-501, Sanprene IB- manufactured by Sanyo Chemical Industries, Ltd.
F370 and the like, and for acrylic polyol resin, N-2043- manufactured by Harima Chemicals Co., Ltd.
60MEX, N-2043-AF-1, etc. are mentioned.

The resin is preferably added in an amount of 0.1% by weight to 10% by weight in the ink composition in order to further improve the fixability of the pigment to the recording medium.

  The ink composition preferably contains at least one glycerin, polyalkylene glycol, or saccharide. The total amount of the one or more kinds of glycerin, polyalkylene glycol, or saccharide is preferably added in the ink composition in the range of 0.1 wt% to 10 wt%.

With such a preferable configuration, it is possible to stabilize ink discharge and improve the image quality of the recorded matter while suppressing drying of the ink and preventing clogging.

The polyalkylene glycol is a linear polymer compound having a repeating structure of an ether bond in the main chain, and is produced, for example, by ring-opening polymerization of a cyclic ether.

Specific examples of the polyalkylene glycol include polymers such as polyethylene glycol and polypropylene glycol, ethylene oxide-propylene oxide copolymers and derivatives thereof. As the copolymer, any copolymer such as a random copolymer, a block copolymer, a graft copolymer, and an alternating copolymer can be used.

  Preferable specific examples of the polyalkylene glycol include those represented by the following formula.

HO- (CnH2nO) m-H
(In the above formula, n represents an integer of 1 to 5, m represents an integer of 1 to 100)

In the above formula, (CnH2nO) m may be a constant or a combination of two or more numbers within the range of the integer value n. For example, when n is 3, it is (C3H6O) m,
When n is a combination of 1 and 4, it is (CH2O-C4H8O) m. The integer value m is
Within that range, it may be a constant or a combination of two or more numbers. For example,
In the above example, when m is a combination of 20 and 40, it is (CH2O) 20- (C2H4O) 40, and when m is a combination of 10 and 30, it is (CH2O) 10- (C4H8O) 30. Further, the integer values n and m may be arbitrarily combined within the above range.

Examples of the saccharide include monosaccharides such as pentose, hexose, heptose, and octose; polysaccharides such as disaccharides, trisaccharides, and tetrasaccharides; or sugar derivatives that are derivatives thereof, reduced derivatives such as deoxyacids, aldonic acid, and uronic acid. Examples include oxidized derivatives, dehydrated derivatives such as glycosene, amino acids, thiosugars, and the like. Polysaccharides refer to sugars in a broad sense and include substances that exist widely in nature, such as alginic acid, dextrin, and cellulose.

The metallic ink composition preferably contains at least one acetylene glycol surfactant and / or silicone surfactant. The surfactant is preferably added in an amount of 0.01% by weight to 10% by weight with respect to the pigment content in the ink composition.

By adopting such a suitable configuration, the wettability of the metallic ink composition to the recording medium is improved, and quick fixability can be obtained.

Examples of the acetylene glycol surfactant include Surfynol 465 (trademark), Surfynol 104 (trademark) (trade name, manufactured by Air Products and Chemicals, Inc.), Olfin STG (trademark), Olfine E1010 (trademark) ( (Product name, manufactured by Nissin Chemical)
Etc. are preferable.

As the silicone surfactant, polyester-modified silicone or polyether-modified silicone is preferably used. Specific examples include BYK-347, BYK-348,
BYK-UV3500, BYK-UV3510, BYK-UV3530, BYK-UV3
570 (Bic Chemie Japan Co., Ltd.).

The metallic ink composition can be prepared by a known conventional method. For example, first, after mixing the metallic pigment, the dispersant, and the liquid medium described above, a pigment dispersion is prepared by a ball mill, a bead mill, an ultrasonic wave, a jet mill, or the like, and adjusted to have desired ink characteristics. To do. Subsequently, a binder resin, the liquid medium, and other additives (for example, a dispersion aid or a viscosity modifier) can be added with stirring to obtain a pigment ink composition.

In addition, after the composite pigment base material is subjected to ultrasonic treatment in a liquid medium to form a composite pigment dispersion,
It may be mixed with a necessary ink liquid medium, or the composite pigment raw material may be directly subjected to ultrasonic treatment in the ink liquid medium to obtain an ink composition as it is.

The physical properties of the metallic ink composition are not particularly limited. For example, the surface tension is preferably 20 to 50 mN / m. When the surface tension is less than 20 mN / m,
The ink composition may spread or ooze out on the surface of the inkjet recording printer head, making it difficult to eject ink droplets. If the surface tension exceeds 50 mN / m, the surface of the recording medium will become wet. It may not spread out and good printing may not be possible.

Next, the photocurable ink composition used for the ink set of this embodiment will be described.
The photocurable ink composition used for the ink set in the present embodiment is a chromatic ink composition,
At least one selected from the group consisting of a black ink composition and a white ink composition is provided.

The chromatic ink composition is an ink composition containing a chromatic pigment. “Chromatic colors” refers to all colors other than a series of colors (achromatic colors) ranging from white to gray to black. As a chromatic pigment,
From the viewpoint of storage stability such as light resistance, weather resistance and gas resistance, an organic pigment is preferable.

Specifically, insoluble azo pigments, condensed azo pigments, azo pigments such as azo lakes and chelate azo pigments, phthalocyanine pigments, perylene and perinone pigments, anthraquinone pigments, quinacridone pigments, dioxane pigments, thioindigo pigments, isoindolinone pigments, quinophthalone pigments, etc. Polycyclic pigments, dye chelates (eg basic dye chelates, acid dye chelates, etc.), dye rakes (basic dye rakes, acid dye rakes), nitro pigments, nitroso pigments, aniline black, daylight Examples thereof include fluorescent pigments. The above pigments can be used alone or
Two or more kinds can be used in combination.

  More specifically, for example, C.I. I. Pigment yellow 1 (fast yellow G), 2, 3, 12 (disazo yellow AAA), 13, 14, 16, 17, 24, 34, 35, 37, 42 (yellow iron oxide), 53, 55, 73, 74 75, 81, 83 (disazo yellow HR), 93, 94, 95, 97, 98, 100, 101, 104, 108, 109, 110, 117, 120, 128, 129, 138, 139, 150, 153, 154, 155, 180, 185, 213, C.I. I. Pigment Red 1, 2, 3, 5, 7, 17, 22 (Brilliant First Scarlet), 23, 31, 38, 48: 2 (Permanent Red 2B (Ba)), 48: 2 (Permanent Red 2B (Ca)) 48: 3 (Permanent Red 2B (Sr)), 48: 4 (Permanent Red 2B (Mn)), 49: 1, 52: 2, 53: 1, 57: 1 (Brilliant Carmine 6B), 60: 1, 63: 1, 63: 2, 64: 1, 81 (Rhodamine 6G rake), 83, 88, 101 (Bengara), 104, 105, 106, 112, 114, 122 (Quinacridone magenta), 123, 146, 149, 166, 168, 170, 172, 177, 178, 179, 184, 185, 190, 193, 202, 209, 219, C.I. I. Pigment violet 19, C.I. I. Pigment Blue 1, 2, 15 (phthalocyanine blue R), 15: 1, 15: 2, 15: 3 (phthalocyanine blue G), 15: 4, 15: 6 (phthalocyanine blue E), 16, 17: 1, 22 56, 60, 63, C.I. I. Pigment Green 1, 4, 7, 8, 10, 17, 18, 36, etc. can be used. Etc. can be used.

Any pigment that is not described in the color index can be used as long as it is insoluble in water.

The black ink composition is an ink composition containing a black pigment. Examples of black pigments include carbon blacks (CI pigment black 7) such as furnace black, lamp black, acetylene black, channel black, copper oxide, iron oxide (CI pigment black 11), etc. Examples thereof include organic pigments such as metals and aniline black (CI Pigment Black 1), but carbon black having a relatively low specific gravity and difficult to settle in water is preferred for inkjet use. You may use these as 1 type or a 2 types of mixture.

The white ink composition is an ink composition containing a white pigment. Examples of white pigments include Group IV element oxides such as titanium dioxide and zirconia dioxide. In addition, calcium carbonate, calcium sulfate, zinc oxide, barium sulfate, barium carbonate, silica, alumina, kaolin, clay, talc, clay, aluminum hydroxide, magnesium carbonate, white hollow resin emulsion, etc. are preferable, preferably these It is a 1 type, or 2 or more types of mixture selected from the group which consists of.

  White hollow resin emulsion refers to an oily dispersion containing hollow polymer fine particles.

  The primary particle diameter of the white pigment is preferably 1 μm or less from the viewpoint of whiteness.

Here, the “primary particle diameter” refers to the size of a particle formed by collecting single crystals or crystallites close thereto. The primary particle size of the pigment is measured by electron microscopy. This is to measure the size of pigment particles from an electron micrograph, and is more reliable by dispersing the pigment in an organic solvent, fixing it to a support film, and performing image processing and measurement from a transmission electron micrograph. The value can be determined. Specifically, the minor axis diameter and major axis diameter of each primary particle are measured, and the diameter of a circle equal to the area of the primary particle is arithmetically determined as the primary particle diameter. The pigment particles are randomly selected to obtain an average value. Other measurement methods can be used as long as the same reliability can be obtained, but when there is a substantial difference in numerical values, the value obtained by the above method is adopted.

  The chromatic color ink composition and the black ink composition may be appropriately determined, but are 0.1 to 30% by weight, preferably 0.5 to 12% by weight in the ink composition. The content of the pigment in the white ink composition is preferably 1.0% by weight or more, more preferably 5.0% by weight or more, still more preferably 10% by weight or more and 20% by weight or less from the viewpoint of whiteness. .

The pigment content of the chromatic ink composition, black ink composition and white ink composition is:
From the viewpoint of color density, it is preferably 0.1% by weight or more, more preferably 1.0% by weight or more, and further preferably 3.0% by weight or more and 10.0% by weight or less.

The photocurable ink composition used in the ink set of the present embodiment preferably uses a pigment as a coloring material and contains a dispersant for dispersing the pigment. The dispersant is
What can be used for this kind of pigment ink can be used without particular limitation, and examples thereof include a cationic dispersant, an anionic dispersant, a nonionic dispersant, and a surfactant.

Examples of anionic dispersants include polyacrylic acid, polymethacrylic acid, acrylic acid-acrylonitrile copolymer, vinyl acetate-acrylic acid ester copolymer, acrylic acid-acrylic acid alkyl ester copolymer, styrene-acrylic acid. Copolymer, styrene-methacrylic acid copolymer, styrene-acrylic acid-alkyl acrylate copolymer, styrene-methacrylic acid-alkyl acrylate copolymer, styrene-α-methylstyrene-acrylic acid copolymer Styrene-α-methylstyrene-acrylic acid-alkyl acrylate copolymer, styrene-maleic acid copolymer, vinyl naphthalene-maleic acid copolymer, vinyl acetate-ethylene copolymer, vinyl acetate-fatty acid vinyl ethylene Copolymer,
And vinyl acetate-maleic acid ester copolymer, vinyl acetate-crotonic acid copolymer, vinyl acetate-acrylic acid copolymer, and the like.

Nonionic dispersants include polyvinyl pyrrolidone, polypropylene glycol, vinyl pyrrolidone-vinyl acetate copolymer, and the like.

Surfactants as dispersants include anionic surfactants such as sodium dodecylbenzenesulfonate, sodium laurate, ammonium salt of polyoxyethylene alkyl ether sulfate, polyoxyethylene alkyl ether, polyoxyethylene alkyl ester, polyoxyethylene alkyl ester Nonionic surfactants such as oxyethylene sorbitan fatty acid ester, polyoxyethylene alkylphenyl ether, polyoxyethylene alkylamine, polyoxyethylene alkylamide, and the like. In particular, it is preferable to use a styrene- (meth) acrylic acid copolymer from the viewpoint of enhancing the dispersion stability of the pigment.

Moreover, polyoxyalkylene polyalkyleneamine or sorbitan ester can be used as another dispersing agent. Polyoxyalkylene polyalkylene polyamine (C2H4N) n- (PO) x- (EO) y-OH (wherein n, x and y each represents an integer of 1 or more, PO represents propylene oxide) , EO means ethylene oxide), for example, Discole N-503, N-506, N-509, N-512, N-515, N-518, N-520 Etc.

The photocurable ink composition used in the ink set of this embodiment preferably contains a photopolymerization initiator and a polymerizable compound in addition to the above-described color material.

The photopolymerization initiator is preferably at least one selected from the group consisting of bisacylphosphine oxide, monoacylphosphine oxide, α-aminoketone, and α-hydroxyketone.

The bisacylphosphine oxide, monoacylphosphine oxide, α-aminoketone, and α-hydroxyketone can all absorb light having a wavelength of 365 nm or more. Therefore, by selecting one or more of these compounds as a photopolymerization initiator, a highly curable ink composition suitable for ultraviolet light of 395 nm or more can be obtained. In particular, bisacylphosphine oxide and monoacylphosphine oxide have absorption in a longer wavelength range than α-aminoketone and α-hydroxyketone.

Examples of the bisacyl phosphine oxide include bis (2,4,6-trimethylbenzoyl) -phenyl phosphine oxide and the like.
819 (manufactured by Ciba Specialty Chemicals).
Examples of the monoacylphosphine oxide include 2,4,6-trimethylbenzoyl-diphenylphosphine oxide and the like, which is exemplified by Darocure TP.
It is available under the trade name of O (Ciba Specialty Chemicals).
Examples of the α-aminoketone include 2-benzyl 2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 and the like, which is Irgacure 369.
It is available under the trade name (Ciba Specialty Chemicals).
Examples of the α-hydroxyketone include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, and the like, which includes Darocur 1173, Irgacure 184, 127 (Ciba Specialty).
(Available from Chemicals).

The photocurable ink composition used in the ink set of the present embodiment can also contain at least two or more of the above-described photopolymerization initiators. As long as it contains at least 2 or more types of photopolymerization initiators as the photopolymerization initiator, other photopolymerization initiators other than the above may be used in combination.

Typical other photopolymerization initiators that can be used in combination include benzoin methyl ether, benzoin ethyl ether, isopropyl benzoin ether, isobutyl benzoin ether, 1-phenyl-1,2-propanedione-2. -(O-Ethoxycarbonyl) oxime, benzyl, diethoxyacetophenone, benzophenone, chlorothioxanthone, 2-chlorothioxanthone, isopropylthioxanthone, diethylthioxanthone, 2-methylthioxanthone, polychlorinated polyphenyl, hexachlorobenzene and the like. Preferred are isobutyl benzoin ether and 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime.

Also, Vicure 10, 30 (manufactured by Stauffer Chemical), Ir
gacure 127, 184, 500, 651, 2959, 907, 369, 379,
754, 1700, 1800, 1850, 819, 4265, OXE01, Darocu
re 1173, ITX, TPO (Ciba Specialty Chemicals), Quant
acure CTX, ITX (Aceto Chemical), Kayacure
Photopolymerization initiators available under the trade names of DETX-S (manufactured by Nippon Kayaku Co., Ltd.), ESACURE KIP150 (manufactured by Lamberti), and Lucirin TPO (manufactured by BASF) can also be used.

The polymerizable compound is preferably at least one selected from the group consisting of an N-vinyl compound, ethylene glycol monoallyl ether, and a dendritic polymer (dendritic polymer) from the viewpoint of storage stability.

The ink composition A and the ink composition B are allyl compounds as polymerizable compounds,
More preferred are allyl ether compounds, ethylene glycol monoallyl ether, trimellilol propane diallyl ether, trimethylol propane monoallyl ether, glycerin monoallyl ether, allyl glycidyl ether, and pentaerythritol triallyl ether, particularly preferably ethylene glycol monoallyl. It preferably contains allyl ether, trimellilol propane diallyl ether and / or N-vinyl compound.
Ethylene glycol monoallyl ether and / or N-vinyl compounds are monofunctional radically polymerizable monomers, and are less prone to unwanted polymerization due to dark reactions during storage, and are suitable for use. In particular, allyl ether compounds such as ethylene glycol monoallyl ether and trimelliol propane diallyl ether have the property that they do not polymerize alone even when carbon radicals generated by the decomposition of the photoradical polymerization initiator are present.
The N-vinyl compound is preferably N-vinylformamide from the viewpoint of curability.
The added amount of the N-vinyl compound and ethylene glycol monoallyl ether is 50-9.
It is preferably 5% by weight.

The dendritic polymer (dendritic polymer) is preferably a hyperbranched polymer and / or a dendrimer from the viewpoint of ink viscosity reduction.

Here, the “hyperbranched polymer” is a tree-like multibranched polymer composed of a large number of branches, and the molecular structure is not necessarily regular. The hyperbranched polymer is preferably a hyperbranched polymer having a functional group branched with dipentaerythritol as a core. Hyperbranched polymer is manufactured by Osaka Organic Chemical Industry Co., Ltd.
AR-501, 502, etc. are available.
In the present invention, “Biscoat” manufactured by Osaka Organic Chemical Industry is used as the hyperbranched polymer.
# 1000 "and" STAR-501 "were used. This "Biscoat # 1000", "S
“TAR-501” is a hyperbranched polymer having dipentaerythritol as a core and functional groups branched, and “Biscoat # 1000” contains ethylene glycol diacrylate as a dilution monomer, and has a viscosity of 273 mPa · s. It has a base number of 14 (acrylic group), and “STAR-501” contains dipentaerythritol hexaacrylate as a dilution monomer and has a viscosity of 210 Pa · s and a functional group number of 20 to 99 (acrylic group). Both have an acryloyl group on the outermost side, and can be suitably used.
In addition, dendrimers have high stereoregularity, which increases the number of production steps and costs. However, hyperbranched polymers are not so high in stereoregularity and can be synthesized relatively easily, which is advantageous in terms of cost.

“Dendrimer” is a dendritic multi-branched polymer consisting of a large number of branches, a compound having a regular molecular structure and having no defects, and is a commonly used linear polymer. In comparison, reactive functional groups can be densely and concentratedly arranged on the outermost surface.

The addition amount of the dendritic polymer is preferably 1.0 to 30.0% by weight.

Moreover, other polymeric compounds other than the polymeric compound mentioned above may be included. The other polymerizable compound is not particularly limited as long as it is polymerized by radicals or ions generated from a photopolymerization initiator. Such a polymerizable compound refers to a molecule that can be a structural unit of a basic structure of a polymer. Such a polymerizable compound is also called a photopolymerizable monomer, and includes a monofunctional monomer, a bifunctional monomer, and a polyfunctional monomer.

As typical examples of such polymerizable compounds, monofunctional monomers include (2-methyl-2-ethyl-1,3-dioxolan-4-yl) methyl acrylate, (2-methyl-2-isobutyl- 1,3-dioxolan-4-yl) methyl acrylate, phenoxyethyl acrylate, isobornyl acrylate, methoxydiethylene glycol monoacrylate, acroylmorpholine, lauryl methacrylate, allyl glycol, 2-hydroxyethyl methacrylate, cyclohexyl methacrylate, oxetane A methacrylate etc. can be mentioned.

Bifunctional monomers include ethylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, tripropylene glycol diacrylate, 1,9-nonanediol diacrylate, polyethylene glycol #
400 diacrylate, tetraethylene glycol dimethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, 2-hydroxy-
Examples thereof include 1,3-dimethacryloxypropane and hydroxypioperic acid ester neopentine glycol diacrylate.

As the polyfunctional monomer, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, trimethylolpropane EO adduct triacrylate,
Trimethylolpropane PO adduct triacrylate, glycerin EO adduct triacrylate, glycerin EO modified triacrylate, glycerin PO adduct triacrylate, pentaerythritol triacrylate, dipentaerythritol hexaacrylate, hydrogen phthalate- (2,2 , 2-triacroyloxymethyl) ethyl, dipentaerystol polyacrylate, trimethylolpropane diallyl ether, pentaerythritol triallyl ether, glycerin monoallyl ether, and the like.

The photocurable ink composition may contain a polymerization accelerator, and the polymerization accelerator may contain fine particles having a polymerizable functional group.
Although it does not specifically limit as a polymerization accelerator, It is preferable to contain any one or more of an amine compound, a thioxanthone, and polymeric fine particles, for example, Darocur EHA and EDB which are aminobenzoates (made by Ciba Specialty Chemicals) ), Thioxanthone, isopropylthioxanthone, dimethylthioxanthone, diethylthioxanthone, polymerizable fine particles having a polymerizable functional group introduced on the surface thereof, and the like.

The mechanism for promoting the polymerization of fine particles introduced with a polymerizable functional group is not necessarily clear, but radicals generated by photopolymerization initiators that absorb ultraviolet rays and are cleaved are trapped and stabilized on the surface of the fine particles and introduced into the surface of the fine particles. It is presumed that the polymerization reaction is facilitated by easily starting the polymerization reaction with the polymerizable functional group and the polymerizable compound adsorbed on the surface.

The fine particles having a polymerizable functional group are not particularly limited, but are generally called extender pigments, and examples thereof include inorganic compounds such as silica, alumina, titania, calcium oxide, and particularly, silica, alumina, and the like. Transparent materials can also be suitably used, and silica is particularly preferable among them.

The polymerizable functional group possessed by the fine particles is not particularly limited, and examples thereof include an acryloyl group and a methacryloyl group, and can also be a polymerizable functional group having one or more double bonds. .

The size of the fine particles is not particularly limited, but those having a particle size of 10 to 200 nm are preferable.

The method for preparing the fine particles having a polymerizable functional group is not particularly limited, but silica fine particles having a large number of hydroxyl groups are produced by a sol-gel reaction of a silane compound such as tetraethoxysilane, and the polymerizable functional group is imparted to the hydroxyl groups. The method of making it react with such a compound (silane coupling agent) is mentioned.

  The content of the fine particles having a polymerizable functional group is not particularly limited and should be appropriately selected according to the use form, conditions, the relationship between the viscosity of the ink composition and the polymerizable property, and the like. It is preferable that it is 10 mass% or less with respect to the whole thing.

  The addition amount of the polymerization accelerator is preferably 0.01 to 5.0% by weight.

The ink composition A and / or the ink composition B may contain at least one type of HALS-based thermal radical polymerization inhibitor in order to improve the storage stability of the ink composition.
The HALS thermal radical polymerization inhibitor is preferably a hindered phenol compound or a HALS compound, and the hindered phenol compound is Irgasta.
b Examples of UV-22 and HALS compounds include Irgastab UV-10 (manufactured by Ciba Specialty Chemicals).
Either one of the ink compositions A and B or both the ink compositions A and B may contain a sensitivity improver.
The ink composition A and / or the ink composition B may contain a coumarin compound or a thioxanthone compound as a sensitivity improver.
The sensitivity improver is a compound that absorbs light of the wavelength irradiated to the ink composition A and / or B for the purpose of photocuring and is excited to generate radicals by extracting hydrogen, and generates radicals by energy transfer. It is a compound that performs radical generation by electron transfer.
When coumarin compounds absorb ultraviolet light and enter an excited state, they not only have a sensitizing effect by causing energy transfer with other molecules, but also emit fluorescence when falling to the ground state. It is considered that the sensitivity is improved by the absorption of the fluorescence generated by light irradiation by the polymerization initiator. The two-part photocurable ink set of the present invention is particularly effective for printed matter having a film thickness. In the case of thick printed matter, the irradiation light is difficult to reach the inside, but the coumarin compound acts as described above and emits fluorescence from the inside of the ink, so the sensitivity is improved and the internal curability is also excellent. A printed matter can be obtained.
Preferred examples of the coumarin compound include Coumarin, 4-methylcoumarin, 7-hydroxycoumarin, 7-amino-4-methylcoumarin, 7-hydroxy-4-
Trifluoromethylcoumarin, 3- (2-benzothiazoyl) -7- (diethylamino)
Coumarin, 7-acetoxy-3- (2-benzoxazoyl) coumarin, 6,7-diethoxy-4- (trifluoromethyl) coumarin, 2,3,6,7-tetrahydro-9-methyl-1H, 5H- A quinolizino (9,1-gh) coumarin etc. are mentioned.
Preferable examples of the thioxanthone compound include thioxanthone, isopropylthioxanthone, 2,4-diethylthioxanthone, chlorothioxanthone and the like.
The concentration of the sensitivity improver is 0.00 in the ink composition A and / or the ink composition B.
The content is preferably from 01% by weight to 1.0% by weight.

The above-mentioned photocurable ink composition can be prepared by a known conventional method. For example, a desired photocurable ink composition can be obtained by mixing the pigment dispersion and the ink solvent and then filtering.

[Liquid container and liquid ejecting apparatus]
According to this embodiment, it is possible to provide a liquid container that contains the ink set described above. Moreover, according to this embodiment, a liquid ejecting apparatus provided with the said liquid container can be provided.

[Inkjet recording method]
The ink jet recording method of this embodiment is an ink jet recording method in which an ink jet head is driven to eject ink composition droplets, and the ink droplets are attached to a recording medium to perform recording. An image is formed.

When the metallic ink composition containing the metal pigment described above is used alone, it is JIS Z8.
The measured values of 20 °, 60 °, and 85 ° specular gloss specified in 741 are 20 at the same time.
An image having a metallic luster showing a numerical value of 0, 200, 100 or more can be formed. By using this metallic ink composition, an image having a desired metallic luster can be formed from a matte image to a glossy image.

Specifically, when images having 20, 60, and 85 degree specular gloss values of 200 to less than 400, 200 to less than 400, and 100 or more as defined in JIS Z8741 are formed at the same time. An image having a matte tone (matte tone) metallic luster can be obtained.

In addition, images with measured values of 20 °, 60 °, and 85 ° specular gloss specified by JIS Z8741 that are simultaneously 400 or more and less than 600, 400 or more and less than 600, and 100 or more are reflected in the formed image. It is possible to obtain a glossy metallic luster so that the indented object can be slightly discriminated.

Furthermore, images having a metallic luster in which the measured values of 20 °, 60 °, and 85 ° specular gloss specified in JIS Z8741 are simultaneously 600 or more, 600 or more, and 100 or more have sharpness. , Gloss enough to clearly distinguish the object reflected in the formed image,
A metallic luster having a so-called “mirror gloss” can be obtained.

The metallic ink composition containing a metal pigment and at least one photocurable ink composition selected from the chromatic ink composition, the black ink composition, and the white ink composition are simultaneously ejected. To form an image. As a result, a metallic color tone can be imparted to the color tone of the chromatic pigment, black pigment, and white pigment.

When the metallic ink composition containing the metal pigment and the photocurable ink composition such as the chromatic color ink composition, the black ink composition, and the white ink composition are separately ejected, for example, the metal It is preferable to form an image using the chromatic ink composition after forming an image having metallic luster using a metallic ink composition containing a pigment.

The metallic pigment hardly penetrates into the ink receiving layer regardless of whether or not the recording medium has the ink receiving layer, and is attached to the recording medium. On the other hand, when the pigment contained in the chromatic ink composition is ejected onto a recording medium having an ink receiving layer, it easily penetrates into the ink receiving layer. For this reason, first, a metallic ink composition containing a metallic pigment is ejected to form a metallic pigment adhesion layer on a recording medium, and a chromatic ink pigment is adhered on the metallic pigment composition. It becomes possible to develop colors more vividly.

In addition, after forming an image having a metallic luster using the metallic ink composition containing the metal pigment, an image having an arbitrary color metallic luster is formed using the chromatic color ink composition, and then the black ink An image can also be formed using the composition and / or a white ink pigment.

  Examples of the method for discharging the ink composition include the methods described below.

As a first method, there is an electrostatic suction method, in which a strong electric field is applied between the nozzle and the acceleration electrode placed in front of the nozzle, and ink is continuously ejected from the nozzle in the form of droplets. This is a method in which a print information signal is applied to the deflection electrode while the ink droplet is flying between the deflection electrodes and recorded, or a method in which the ink droplet is ejected in response to the print information signal without being deflected.

The second method is a method in which ink droplets are forcibly ejected by applying pressure to the ink liquid with a small pump and mechanically vibrating the nozzle with a crystal resonator or the like. The ejected ink droplet is charged simultaneously with the ejection, and a printing information signal is given to the deflection electrode and recorded while the ink droplet flies between the deflection electrodes.

The third method is a method using a piezoelectric element (piezo element), in which pressure and a print information signal are simultaneously applied to an ink liquid by a piezoelectric element to eject and record ink droplets.

The fourth method is a method in which the volume of ink is rapidly expanded by the action of thermal energy.
In this method, ink liquid is heated and bubbled by a microelectrode in accordance with a print information signal, and ink droplets are ejected and recorded.

Any of the above methods can be used for the ink jet recording method of this embodiment, and the ink jet cartridges of the respective methods can be filled.

After the droplets of the photocurable ink composition are discharged, a treatment for curing and / or drying the droplets attached to the recording medium is performed according to a conventional method.

As an example of the curing treatment, for example, after the metallic ink composition is ejected to form an image, the chromatic ink composition is ejected, and simultaneously with or after the ejection, the image formed There is a method of performing a curing process. Further, after forming the image by discharging the metallic ink composition, the chromatic color ink composition, the black ink composition, and the white ink composition are discharged at the same time, and at the same time as or after the discharge. There is also a method of performing a curing process on the processed image. Furthermore, after forming an image using the metallic ink composition, an image having an arbitrary color tone is formed using the chromatic color ink composition, and then the black ink composition and / or the white ink composition is discharged. There is also a method of performing a curing process on the formed image simultaneously with or after the ejection.

  Thereby, a full-color image having metallic gloss can be formed.

Further, as an example of combining the drying process and the curing process, for example, after forming an image using the metallic ink composition, the image is dried and the chromatic ink composition and the black ink composition are combined. After the product and the white ink composition are discharged to form an image having an arbitrary color tone, the image is cured.

  Thereby, a full-color image having metallic gloss can be formed.

The curing treatment is preferably performed by irradiating with ultraviolet rays. UV irradiation
It is preferable to select preferable conditions as appropriate depending on the amount and thickness of the ink composition deposited on the substrate or the recording medium. Therefore, although it cannot specify exactly | strictly, it is preferable that the wavelength of the light radiated | emitted from a light irradiation apparatus is the range of 350-450 nm, for example.

  The irradiation amount of ultraviolet rays is 10 mJ / cm 2 or more and 10,000 mJ / cm 2 or less, and preferably 50 mJ / cm 2 or more and 6,000 mJ / cm 2 or less. If it is the amount of ultraviolet irradiation within such a range, the curing reaction of the photocurable ink composition can be sufficiently performed.

Examples of the ultraviolet irradiation include lamps such as metal halide lamps, xenon lamps, carbon arc lamps, chemical lamps, low pressure mercury lamps, and high pressure mercury lamps. For example, Fusion
A commercially available product such as an H lamp, D lamp, or V lamp manufactured by System can be used.

From the viewpoint of reducing energy consumption, it is particularly preferable to irradiate ultraviolet rays with an ultraviolet light emitting semiconductor element such as an ultraviolet light emitting diode (ultraviolet LED) or an ultraviolet light emitting semiconductor laser.

The recording medium is not particularly limited, and various recording media such as plain paper, inkjet dedicated paper (matte paper, glossy paper), glass, plastic, film, metal, and printed wiring board can be used.

When the recording medium has an ink receiving layer, it is preferable to print the recording medium without heating from the viewpoint of not causing thermal damage.

On the other hand, when the recording medium does not have an ink receiving layer, it is preferable to print by heating the recording medium from the viewpoint of increasing the drying speed and obtaining high gloss.

Heating is a method of heating by bringing a heat source into contact with the recording medium, infrared or microwave (2,
A method of heating without contacting the recording medium, such as irradiating an electromagnetic wave having a maximum wavelength of about 450 MHz) or blowing hot air.

The heating is preferably performed before printing and / or simultaneously with printing and / or after printing. In other words, the recording medium may be heated before printing, simultaneously, or after printing, and may be heated throughout printing. The heating temperature depends on the type of the recording medium, but is preferably 30 to 80 ° C, more preferably 40 to 60 ° C.

[Recordings]
The recorded matter of this embodiment is recorded by the above-described ink jet recording method using the ink set described above. Since this recorded matter was obtained by the above-described ink jet recording method using the above-described ink set, a recorded matter having a metallic tone image having an arbitrary color tone can be obtained.

[Ink set of Embodiment 2]
As described above, the ink set of the present embodiment is a group consisting of a metallic ink composition containing a metal pigment, a photocurable ink composition A containing no color material, a chromatic pigment, a black pigment, and a white pigment. Photocurable ink composition B containing at least one colorant selected from
And. As a result, it is possible to form an image in which metallic metallic luster is added to chromatic, black, and white tones.

In the second embodiment, instead of at least one photocurable ink composition selected from the group consisting of the chromatic ink composition, black ink composition, and white ink composition used in the first embodiment described above. In addition, a photocurable ink composition A containing no coloring material, a chromatic pigment,
Embodiment 1 is the same as Embodiment 1 except that the photocurable ink composition B contains at least one colorant selected from the group consisting of a black pigment and a white pigment. Therefore, the matters described in the first embodiment are similarly applied to the second embodiment as to the matters regarding the metallic ink composition containing the metal pigment.

  Next, the photocurable ink composition used for the ink set of this embodiment will be described. The photocurable ink compositions A and B used for the ink set in this embodiment were selected from the group consisting of a photocurable ink composition A that does not contain a coloring material, a chromatic pigment, a black pigment, and a white pigment. A two-component photocurable ink composition comprising a photocurable ink composition B containing at least one colorant.

The photocurable ink composition A is non-aqueous and preferably contains at least a photopolymerization initiator and a polymerizable compound.

The photopolymerization initiator used in the photocurable ink composition A is the same as the photopolymerization initiator preferably used in Embodiment 1 described above, and the above-mentioned matters are similarly applied.

The photocurable ink composition A can also contain at least two or more of the photopolymerization initiators described above. As long as it contains at least 2 or more types of photopolymerization initiators as the photopolymerization initiator, other photopolymerization initiators other than the above may be used in combination.

Other photopolymerization initiators that can be used in combination are the same as the other photopolymerization initiators exemplified in Embodiment 1 described above, and the above-mentioned matters are similarly applied.

  The addition amount of the photopolymerization initiator is preferably 0.1 to 15% by weight.

On the other hand, the photocurable ink composition B is preferably non-aqueous, contains at least a polymerizable compound, and does not contain the above-described photopolymerization initiator.

From the viewpoint of storage stability, the polymerizable compound used in the photopolymerizable ink compositions A and B is selected from the group consisting of an N-vinyl compound, ethylene glycol monoallyl ether, and a dendritic polymer (dendritic polymer). It is preferable that it is at least one selected.

N-vinylformamide and ethylene glycol monoallyl ether are monofunctional radically polymerizable monomers and have a low tendency to cause unwanted polymerization due to a dark reaction during storage.
Suitable for use.

If the amount of N-vinylformamide and / or ethylene glycol monoallyl ether added is less than 20% by weight, problems such as viscosity, dispersion stability and storage stability of the ink composition occur.
If it exceeds 0% by weight, the curability and film strength of the two-component photocurable ink composition may be insufficient. More preferably, it is in the range of about 20% by weight to 70% by weight.

The dendritic polymer (dendritic polymer) is the same as that exemplified in the first embodiment, and the above-mentioned matters are similarly applied.

  The dendritic polymer (dendritic polymer) used in the present embodiment is solid at room temperature, and preferably has a number average molecular weight in the range of 1000 to 100,000, particularly preferably in the range of 2000 to 50000. used. When the molecular weight is lower than the above range, the fixed image becomes fragile, and when the molecular weight is higher than the above range, the viscosity of the ink becomes too high even if the addition amount is lowered, which is practical in terms of ejection characteristics. Is not.

Moreover, other polymeric compounds other than the polymeric compound mentioned above may be included. The other polymerizable compounds are the same as those exemplified in the above-described embodiment 1,
The same applies as well.

  The polymerization accelerator and the addition amount thereof are the same as those in the first embodiment.

For the photocurable ink composition A and / or the photocurable ink composition B, a surfactant can be used. For example, polyester-modified silicone or polyether-modified silicone is used as a silicone-based surfactant. It is particularly preferable to use polyether-modified polydimethylsiloxane or polyester-modified polydimethylsiloxane. Specific examples include BYK-347, BYK-348, BYK-UV3500, 3510, 3530, and 3570 (manufactured by Big Chemie Japan Co., Ltd.).

The photocurable ink composition A or the photocurable ink composition B may contain a polymerization accelerator. Although it does not specifically limit as a polymerization accelerator, It is preferable to contain any one or more of an amine compound, a thioxanthone, and polymeric fine particles, for example, Darocur EHA and EDB which are aminobenzoates (made by Ciba Specialty Chemicals) ), Thioxanthone, isopropylthioxanthone, dimethylthioxanthone, diethylthioxanthone, polymerizable fine particles having a polymerizable functional group introduced on the surface thereof, and the like.

Further, the ink composition A or the ink composition B preferably contains a thermal radical polymerization inhibitor. Thereby, the storage stability of the ink composition is improved. As thermal radical polymerization inhibitors, those blended in general polymerizable compositions can be used, such as phenolic antioxidants, hindered amine light stabilizers, phosphorus antioxidants, and broad (meta) In addition to hydroquinone monomethyl ether used for acrylic monomers, hydroquinone, t-
Examples thereof include butylcatechol and pyrogallol, but HALS compounds are preferable, and Irgastab UV-10 (manufactured by Ciba Specialty Chemicals) is exemplified.

Moreover, the ink set of this embodiment contains a color material only in the photocurable ink composition B.
The coloring material used in this case is preferably a pigment from the viewpoint of durability of the printed matter. The pigment contained in the photocurable ink composition B is at least one selected from the group consisting of chromatic color pigments, black pigments, and white pigments.

The pigment used in the photocurable ink composition B is an inorganic pigment without any particular limitation.
Organic pigments can be used.

As the chromatic color pigment, black pigment, and white pigment, the chromatic color pigment, black pigment, and white color contained in each of the chromatic color ink composition, the black ink composition, and the white ink composition used in Embodiment 1 described above. The same applies to pigments and the above applies.

The content of the chromatic pigment and the black pigment is preferably 0.1% by weight or more, more preferably 1.0% by weight or more, and still more preferably 3.0% from the viewpoint of the gloss of the printed matter and the bronzing phenomenon suppressing effect. % By weight to 10.0% by weight. The content of the white pigment is preferably 1.0% by weight or more, more preferably 5.0% by weight or more, still more preferably 10% by weight or more and 20% by weight or less from the viewpoint of whiteness.

The photocurable ink composition B preferably uses a pigment as a colorant and contains a dispersant for dispersing the pigment. As the dispersant, those that can be used for this kind of pigment ink can be used without particular limitation, and examples thereof include a cationic dispersant, an anionic dispersant, a nonionic dispersant, and a surfactant.

Examples of the anionic dispersant, the nonionic dispersant, the surfactant as the dispersant, and other dispersants are the same as those used in the photocurable ink composition used in Embodiment 1 described above. .

According to a preferred embodiment of the present invention, these pigments can be used as a photopolymerizable ink composition B as a pigment dispersion obtained by dispersing in a water-based medium with a dispersant or a surfactant.
As a preferable dispersant, a dispersant conventionally used for preparing a pigment dispersion, for example, a polymer dispersant can be used.

In addition, the ink set of the present embodiment, when the ink composition contains a color material, yellow,
In addition to the basic four colors magenta, cyan, and black, the same series of dark and light colors may be used for each color. For example, in addition to magenta, light light magenta, dark red, and cyan, in addition to light light cyan, dark blue, and violet. Or, neutral colors such as green and orange are also included. In addition to achromatic black, its light gray, light black, dark matte black, and also achromatic white, cream, ivory, plus metallic, silver, gold , Copper, chrome silver and the like.

If necessary, leveling additives, matting agents, polyester resins for adjusting film properties, polyurethane resins, vinyl resins, acrylic resins, rubber resins, polyacryl polyol resins, polyoxyalkylene polymers Alkylene amine resins and waxes can be added. In addition, the ink composition A or the ink composition B of the present invention includes, as other publicly known other components that can be used in a two-part photocurable ink, a wetting agent, a penetrating solvent, pH
A conditioner, preservative, fungicide, etc. may be added.

The ink set of the present embodiment includes a photocurable ink composition A and a photocurable ink composition B.
After mixing, the curing reaction is performed by light irradiation. As long as mixing is performed before the curing reaction, it may be performed before printing or after printing. That is, the mixing and printing may be in a form in which the ink composition A and the ink composition B are attached to the same position on the recording medium, or the ink composition A and the ink composition B are mixed to form a recording medium. It may be in the form of being attached to.

[Liquid container and liquid ejecting apparatus]
According to this embodiment, it is possible to provide a liquid container that contains the ink set described above. Moreover, according to this embodiment, a liquid ejecting apparatus provided with the said liquid container can be provided.

[Inkjet recording method]
The ink jet recording method of this embodiment is an ink jet recording method in which an ink jet head is driven to eject ink composition droplets, and the ink droplets are attached to a recording medium to perform recording. An image is formed.

When the metallic ink composition containing the metal pigment described above is used alone, as in the first embodiment, it is 20 degrees, 60 degrees, 85 defined in JIS Z8741.
It is possible to form an image having a metallic luster in which the measured values of the specular gloss are respectively 200, 200, and 100 or more at the same time. By using this metallic ink composition,
From a matte image to a glossy image, an image having a desired metallic luster can be formed. A specific example of the metallic gloss image to be formed is the same as in the first embodiment.

The metallic ink composition and the photocurable ink composition A and / or the photocurable ink composition B can be simultaneously ejected to form an image. As a result, a metallic color tone can be imparted to the color tone of the chromatic pigment, black pigment, and white pigment.

When discharging the metallic ink composition containing the metal pigment and the photocurable ink composition such as the chromatic ink composition, the black ink composition, the white ink composition separately, for example, the metallic It is preferable that after the ink composition is ejected to form an image, the photocurable ink composition A and / or the photocurable ink composition B is ejected to form an image having an arbitrary color tone.

The metallic pigment hardly penetrates into the ink receiving layer regardless of whether or not the recording medium has the ink receiving layer, and is attached to the recording medium. On the other hand, when the pigment contained in the chromatic ink composition is ejected onto a recording medium having an ink receiving layer, it easily penetrates into the ink receiving layer. For this reason, first, a metallic ink composition containing a metal pigment is ejected to form an adhesion layer of the metallic pigment on the recording medium, and the pigment contained in the photocurable ink composition B is adhered thereon, and then the photocuring is performed. The color of the pigment of the type ink composition B can be more vividly developed.

Examples of the method for discharging the ink composition include the first to fourth methods described in the first embodiment.

Any of the above methods can be used for the ink jet recording method of this embodiment, and the ink jet cartridges of the respective methods can be filled. However, from the viewpoint of not causing thermal damage to the ink composition, it is an inkjet head non-heating method.
It is preferable to select the first, second and third methods.

After the droplets of the photocurable ink composition are discharged, a treatment for curing and / or drying the droplets attached to the recording medium is performed according to a conventional method.

As an example of the curing treatment, for example, after forming an image using the photocurable ink composition A and the photocurable ink composition B containing the white pigment, the curing treatment is performed by light irradiation, (I) the metallic ink composition; and (ii) the photocurable ink composition A.
And / or (iii) a photocurable ink composition B containing the chromatic pigment or the black pigment.
There is a method of forming an image using
Thereby, a full-color image having metallic gloss can be formed.

As another example, after the metallic ink composition is ejected to form an image, the photocurable ink composition A and / or the photocurable ink composition B are simultaneously ejected to form an image, There is a method of performing a curing process on the formed image simultaneously with or after the ejection.
Thereby, a full-color image having metallic gloss can be formed.

Further, as an example of combining the drying treatment and the curing treatment, for example, after the metallic ink composition is discharged to form an image, the image is dried, and the photocurable ink composition A and / or Alternatively, there is a method in which the photocurable ink composition B is discharged at the same time to form an image, and the formed image is cured at the same time or after the discharge.
Thereby, a full-color image having metallic gloss can be formed.

It is preferable to perform the said hardening process by irradiating an ultraviolet-ray similarly to Embodiment 1 mentioned above, The said matter applies similarly for the detail.

[Recordings]
The recorded matter of this embodiment is recorded by the above-described ink jet recording method using the ink set described above. Since this recorded matter was obtained by the above-described ink jet recording method using the above-described ink set, a recorded matter having a metallic tone image having an arbitrary color tone can be obtained.

1. Metallic ink composition (1) Preparation of metallic pigment dispersion On a PET film having a film thickness of 100 μm, 3.0% by weight of cellulose acetate butyrate (butylation rate: 35 to 39%, manufactured by Kanto Chemical Co., Inc.) and diethylene glycol diethyl ether ( A resin layer coating solution consisting of 97% by weight (manufactured by Nippon Emulsifier Co., Ltd.) was uniformly applied by the bar coating method and dried at 60 ° C. for 10 minutes to form a resin layer thin film on the PET film.

Next, 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 (VE-1010 type vacuum vapor deposition apparatus by a vacuum device company).

Next, the laminate formed by the above method was added in diethylene glycol diethyl ether with V
Using a S-150 ultrasonic disperser (manufactured by ASONE), peeling, miniaturization, and dispersion treatment were simultaneously performed to prepare a metallic pigment dispersion having an integrated ultrasonic dispersion treatment time of 12 hours.

The obtained metallic pigment dispersion was filtered with 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. Thereby, the metallic pigment dispersion was concentrated, and then the concentration of the metallic pigment dispersion was adjusted to obtain a metallic pigment dispersion 1 having a concentration of 5% by weight.

Moreover, the metallic pigment dispersion liquid 2 which has a metallic pigment which changed vapor deposition conditions and / or ultrasonic dispersion time was obtained.

Then, using a particle diameter / particle size distribution measuring apparatus (FPIA-3000S manufactured by Sysmex Corporation), 50% average particle diameter R50 of the equivalent diameter of the major axis (X direction) -minor axis (Y direction) plane of each metallic pigment, The average film thickness Z was measured, and based on the measured values of R50 and Z obtained, R5
0 / Z was calculated. The results are shown in Table 1.

(2) Preparation of metallic ink composition A metallic pigment ink composition having the composition shown in Table 2 was prepared using the metallic pigment dispersion prepared by the above method. After mixing and dissolving the solvent and additives to make an ink solvent,
The metallic pigment dispersion is added to the ink solvent, and further mixed and stirred with a magnetic stirrer at room temperature and normal pressure for 30 minutes to obtain a metallic pigment ink composition (S1, S2, S
3).

In Table 2, diethylene glycol diethyl ether (DEGdEE), dipropylene glycol monobutyl ether (DPGmBE) and tetraethylene glycol dimethyl ether (TEGdME) manufactured by Nippon Emulsifier Co., Ltd. were used. Further, γ-butyrolactone was manufactured by Kanto Chemical. N-2043-AF-1 and N-2043-60M
EX (polyacryl polyol resin emulsion) manufactured by Harima Kasei Co., Ltd.
K-3500 (surfactant) manufactured by Big Chemie Japan was used. The unit is% by weight.

2. Color ink composition (1) Preparation of polymerizable fine particles and dispersion thereof Silica sol IPA-ST (manufactured by Nippon Chemical Industry Co., Ltd., isopropyl alcohol (hereinafter referred to as “IPA”) dispersion having a silica concentration of 30 wt%) 88.1 parts by weight Was added to a 200 ml Erlenmeyer flask, and 7.9 parts by weight of a silane coupling agent Silaace S710 (3-methacryloxy Spropyltrimethoxysilane, manufactured by Chisso Corporation) was added. While stirring with a magnetic stirrer, 4 parts by weight of 0.05 mol / L hydrochloric acid was added, and the reaction was carried out with stirring at room temperature for 24 hours. As a result, IPA dispersion A containing polymerizable fine particles (MPS) having a methacryl group was obtained.

  To a 300 ml round bottom flask, 70 parts by weight of N-vinylformamide (hereinafter also referred to as “NVF”, beam set 770, manufactured by Arakawa Chemical Industries) and 100 parts by weight of the above dispersion A are added, and IPA is added using a rotary evaporator. Was distilled off to obtain a dispersion B containing 30 wt% of polymerizable fine particles.

(2) Preparation of pigment dispersion (2-1) (Yellow) Pigment dispersion C
As a pigment which is a coloring material, C.I. I. Pigment Yellow (PY) 74, polyurethane resin (average molecular weight of about 20,000) (hereinafter also referred to as “dispersant”), and NVF are mixed in a ratio of pigment: dispersant: NVF = 15: 5: 80. Then, it was dispersed in a sand mill (manufactured by Yaskawa Seisakusho) with glass beads (diameter 1.7 mm, 1.5 times the weight of the mixture) for 2 hours. Thereafter, the glass beads were separated to obtain a pigment dispersion C (pigment concentration 15 wt%).

(2-2) (Magenta) Pigment dispersion D
The pigment is C.I. I. A pigment dispersion D (pigment concentration: 15 wt%) was prepared in the same manner as the pigment dispersion C except that the pigment red (PR) 122 was used.

(2-3) (Cyan) Pigment dispersion E
The pigment is C.I. I. Pigment dispersion E (pigment concentration: 15 wt%) was prepared in the same manner as Pigment dispersion C, except that Pigment Blue (P.B.) 15: 3 was used.

(2-4) (Black) Pigment dispersion liquid F
The pigment is C.I. I. A pigment dispersion F (pigment concentration: 15 wt%) was prepared in the same manner as the pigment dispersion C except that the pigment black (P.Bk.) 7 was used.

(2-5) (White) Pigment dispersion G
The titanium-containing ore was dissolved with sulfuric acid to obtain a titanium sulfate solution. The hydrous titanium oxide obtained by hydrolyzing this titanium sulfate solution was 0.50 part by weight of ammonium phosphate, 0.30 part by weight of potassium sulfate, and 0.000 part of aluminum sulfate with respect to 100 parts by weight in terms of TiO2. 30 parts by weight were added and the hydrous titanium oxide was heated in a laboratory rotary muffle furnace until the product temperature reached 1,020 ° C. When the produced titanium dioxide fine particles were cooled to room temperature and observed with a transmission electron micrograph, it was found to be anatase type having an average primary particle diameter of 0.13 μm.

15 parts by weight of titanium dioxide fine particles as a surface-treated white pigment, polyoxyalkylene-added polyalkyleneamine as a dispersant
N-518) 5 parts by weight and 80 parts by weight of ethylene glycol monoallyl ether (hereinafter referred to as “AG”) were mixed and zirconium beads (1.0
(mm diameter) was filled with 1.5 times the amount of the slurry and dispersed for 2 hours, and then the beads were removed to obtain 60 wt% pigment dispersion G of titanium dioxide fine particles.

(3) Preparation of ink composition (3-1) Yellow pigment ink composition (Y1)
To a light-shielding container, 20 parts by weight of pigment dispersion B and 10 parts by weight of pigment dispersion C are added, 29 parts by weight of NVF, tripropylene glycol diacrylate (hereinafter also referred to as “TPGDA”, Aronix M-220, Toa Gosei) 25 parts by weight, glycerin EO-modified triacrylate (hereinafter also referred to as “AGE3”, HK ester A-Gly-3E, Shin-Nakamura Chemical Co., Ltd.) 10 parts by weight, Irgacure 819 (bis (2,4,6-trimethyl) Benzoyl) -phenylphosphine oxide, manufactured by Ciba Specialty Chemicals) 4.0 parts by weight, Irgacure 369 (2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, Ciba Specialty Chemicals) 1.0 parts by weight, Darocur EHA (2) 1 part by weight of ethylhexyl-4-dimethoxyaminobenzoate (manufactured by Ciba Specialty Chemicals Co., Ltd.), stirred and mixed with a magnetic stirrer for 1 hour, and filtered using a 5 μm membrane filter in an environment shielded from ultraviolet rays. A yellow ink composition having the composition shown in Table 3 was prepared.

(3-2) Magenta, Cyan, and Black Pigment Ink Compositions Similarly, each ink composition having the composition shown in Table 3 using pigment dispersions D, E, and F instead of pigment dispersion C: Magenta Ink composition (M1), cyan ink composition (C1),
A black ink composition (Bk1) was prepared.

(3-3) White ink composition (W)
A solvent other than AG, a pigment and a dispersant in the formulation components shown below and various additives are mixed and completely dissolved to prepare an ink solvent, and then the pigment dispersion G is gradually added to the ink solvent while stirring. After completion of the dropwise addition, the mixture was mixed and stirred at room temperature for 30 minutes. Then, it filtered with a 5-micrometer membrane filter and prepared the white ink composition shown in Table 4. In the following composition, “AG” means ethylene glycol monoallyl ether manufactured by Nippon Emulsifier Co., Ltd.
“Irgacure 127” means a polymerization initiator manufactured by Ciba Specialty Chemicals, and “Darocur EDB” means a polymerization accelerator of the company, “BYK-UV357”.
“0” means a silicone-based surfactant manufactured by Big Chemie Japan, and “Irgast”
“ab UV10” means a polymerization inhibitor manufactured by Ciba Specialty Chemicals.

(3-4) Yellow, Magenta, Cyan, Black, White Pigment Ink Composition In the same manner as above, each ink composition having the composition shown in Table 5: yellow ink composition (Y2), magenta ink composition ( M2), a cyan ink composition (C2), a black ink composition (Bk2), and a white ink composition (W2) were prepared.

3. Ink set Using each ink composition obtained in 1 and 2 above, an ink set was composed of combinations shown in Table 6.

4). Printing evaluation test (1) Printing evaluation test 1
Using the ink set shown in 3 above, Roland D.C. G. An ink jet printer SJ-540 manufactured by Co., Ltd. is used, and an ink composition corresponding to each corresponding color row, that is, a black ink composition, a yellow ink composition, a magenta ink composition, and a cyan ink composition are respectively black rows. The yellow, magenta, and cyan columns were filled, the metallic ink composition was filled in the light cyan column, and the white ink composition was filled in the light magenta column. Printing was performed according to the following printing pattern. For recording media, vinyl chloride sheet cut into A4 size (Viewcal 2000 (white): manufactured by Sakurai Co., Ltd.), PET film (PG-50L: manufactured by Lamy Corporation), polycarbonate film (Iupilon FE-2000: Mitsubishi Engineering Plastics) Used). And sensory evaluation of the printed matter was performed based on the following evaluation criteria. The results are shown in Table 7.
AA: A metallic gloss sufficient to clearly distinguish the reflected object was obtained.
A: A metallic gloss that can slightly distinguish an object reflected in an image was obtained.
B: A metallic gloss with a matte tone (matte tone) was obtained.
C: A metallic gloss was not obtained.

The printing pattern using the ink set is as follows.
a. Print pattern 1
After forming an image using a metallic ink composition at a heating temperature of 50 ° C., an image is formed on the metallic image using chromatic color ink, and a peak is applied to the image as an ultraviolet irradiation device. Ultraviolet light emitting diode NICHIAi-LED with wavelength of 365nm
“NCCU033” and ultraviolet light emitting diode NICHIA “N” with a peak wavelength of 380 nm
CCU001 "(both manufactured by Nichia Corporation), light emitting diode E1 having a peak wavelength of 395 nm
What was produced using S40-0P0C6-01 (made by Toyoda Gosei) was used. The irradiation conditions of the ultraviolet irradiation apparatus were such that the irradiation intensity at wavelengths of 365 nm, 380 nm, and 395 nm was 20 mW / cm 2 on the irradiation surface, that is, 60 mW / cm 2 in total. Then, the sample is irradiated with ultraviolet rays for 5 seconds, and the integrated light quantity per one ultraviolet irradiation treatment is 300 m.
Curing treatment was performed by irradiating ultraviolet rays under conditions of J / cm 2.

b. Print pattern 2
An image was formed by discharging the metallic ink composition at a heating temperature of 50 ° C., and then an image was further formed using the chromatic color ink composition. An ultraviolet light emitting diode NICHIAi-LED having a peak wavelength of 365 nm is used as an ultraviolet irradiation device for the formed image.
“NCCU033” and ultraviolet light emitting diode NICHIA “N” with a peak wavelength of 380 nm
CCU001 "(both manufactured by Nichia Corporation), light emitting diode E1 having a peak wavelength of 395 nm
What was produced using S40-0P0C6-01 (made by Toyoda Gosei) was used. The irradiation conditions of the ultraviolet irradiation apparatus were such that the irradiation intensity at wavelengths of 365 nm, 380 nm, and 395 nm was 20 mW / cm 2 on the irradiation surface, that is, 60 mW / cm 2 in total. Then, the sample is irradiated with ultraviolet rays for 5 seconds, and the integrated light quantity per one ultraviolet irradiation treatment is 300 m.
Curing treatment was performed by irradiating ultraviolet rays under conditions of J / cm 2. Subsequently, the black ink composition and the white ink composition were simultaneously ejected, and simultaneously with or after the ejection, the formed image was irradiated with ultraviolet rays under the same conditions as described above, and was subjected to a curing treatment. .

c. Print pattern 3
After forming an image using a metallic ink composition at a heating temperature of 50 ° C., and subsequently forming an image by ejecting the chromatic ink composition, the black ink composition, and the white ink composition, For this image, ultraviolet light emitting diodes NICHIAi-LED “NCCU033” having a peak wavelength of 365 nm and ultraviolet light emitting diodes NICHIA “NCCU001” (both manufactured by Nichia Corporation) having a peak wavelength of 395 nm are emitted as ultraviolet irradiation devices. What was produced using diode E1S40-0P0C6-01 (made by Toyoda Gosei) was used. The irradiation conditions of the ultraviolet irradiation apparatus were such that the irradiation intensity at the wavelengths of 365 nm, 380 nm, and 395 nm was 20 mW / cm 2 on the irradiation surface, that is, 60 mW / cm 2 in total. Then, the sample was irradiated with ultraviolet rays for 5 seconds, and the ultraviolet ray was irradiated under the condition that the integrated light quantity per one ultraviolet irradiation treatment was 300 mJ / cm 2, and the curing treatment was performed.

d. Print pattern 4
After forming an image using the metallic ink composition at a heating temperature of 50 ° C., the image was subjected to a drying treatment at 60 ° C. for 15 minutes, followed by a chromatic ink composition, the black ink composition, After the white ink composition is ejected to form an image, an ultraviolet light emitting diode NICHIAi-LED having a peak wavelength of 365 nm is applied to the image as an ultraviolet irradiation device.
“NCCU033” and ultraviolet light emitting diode NICHIA “N” with a peak wavelength of 380 nm
CCU001 "(both manufactured by Nichia Corporation), light emitting diode E1 having a peak wavelength of 395 nm
What was produced using S40-0P0C6-01 (made by Toyoda Gosei) was used. The irradiation conditions of the ultraviolet irradiation apparatus were such that the irradiation intensity at wavelengths of 365 nm, 380 nm, and 395 nm was 20 mW / cm 2 on the irradiation surface, that is, 60 mW / cm 2 in total. Then, the sample is irradiated with ultraviolet rays for 5 seconds, and the integrated light quantity per one ultraviolet irradiation treatment is 300 m.
Curing treatment was performed by irradiating ultraviolet rays under conditions of J / cm 2.

As shown in Table 7, by the inkjet recording method using the ink set,
It was possible to obtain a recorded matter having a metallic image with an arbitrary color tone.

1. Metallic ink composition The metallic pigment ink composition prepared in the same manner as in Example 1 (S1, S2, S3)
Was used.

2. Color Ink Composition (1) Preparation of Dendritic Polymer In the present invention, a hyperbranched polymer or a dendrimer was used as the dendritic polymer.
As the hyperbranched polymer, “STAR-501” manufactured by Osaka Organic Chemical Industry was used. This “STAR-501” is a hyperbranched polymer in which a functional group is branched with dipentaerythritol as a core, and dipentaerythritol hexaacrylate is contained as a dilution monomer, viscosity: 210 Pa · s, number of functional groups: 20 ~ 99 (acrylic group).

Dendrimers 7 and 9 were synthesized as follows.
A reaction vessel having a capacity of 1 L was charged with 31 g of ethylenediamine, 256 g of dimethyl acrylate, and 300 g of methanol, and reacted for 6 hours while stirring at 40 ° C. in a nitrogen stream.
After completion of the reaction, the resulting mixture was distilled off methanol using a rotary evaporator, added to a large excess of diethyl ether and purified by reprecipitation. 500 g of methanol was added to the obtained reaction product 1 and dissolved, and the following reaction was performed.

A methanol solution containing the reaction product 1 was placed in a reaction vessel with a capacity of 2 L, 240 g of ethylenediamine was added, and the reaction was performed for 6 hours while stirring at 27 ° C. under a nitrogen stream. After the reaction
Similarly, after purification by methanol distillation and reprecipitation operation, 1000 g of methanol was added to the obtained reaction product 2 and dissolved, and the following reaction was performed.

A methanol solution containing the reaction product 2 was placed in a reaction vessel having a capacity of 5 L, 667 g of dimethyl acrylate was added, and the reaction was performed for 6 hours while stirring at 40 ° C. under a nitrogen stream. After the reaction, methanol was distilled off in the same manner, and after purification by reprecipitation operation, 2000 g of methanol was added to the obtained reaction product 3 to dissolve it, and the next reaction was performed.

A methanol solution containing the reaction product 3 was placed in a reaction vessel, 361 g of ethylenediamine was added, and the reaction was carried out for 6 hours while stirring at 27 ° C. in a nitrogen stream. After the reaction, methanol was distilled off in the same manner, and after purification by reprecipitation operation, acetone obtained by dehydration treatment using 2000 g of molecular sieve was added to the obtained reaction product 4 and dissolved to carry out the next reaction.

1,000 g of an acetone solution containing the reaction product 4 in a reaction vessel was collected, and Karenz BEI
(1,1-Bis (acryloyloxymethyl) ethyl isocyan
(ate, Showa Denko Co., Ltd.) 2153 g was added, stirred and mixed under a nitrogen stream, then DABC
1 g of O (1,4-Diazabicyclo [2,2,2] octane, manufactured by Tokyo Chemical Industry Co., Ltd.) was further added, mixed with stirring, and the reaction temperature was raised to 50 ° C., followed by reaction for 6 hours.

After completion of the reaction, acetone was distilled off using a rotary evaporator, and then 6838 g of ethylene glycol monoallyl ether was added to prepare an ethylene glycol monoallyl ether solution 8 of 30% by weight concentration of dendrimer 7.
In this case, the number of acryloyl groups arranged on the outermost surface per molecule of dendrimer 7 is 72.

Moreover, after distilling acetone from the acetone solution containing the reactive organism 4 using a rotary evaporator, 6838 g of ethylene glycol monoallyl ether is added to prepare an ethylene glycol allyl ether solution 10 of dendrimer 9 having a concentration of 30% by weight. did. This dendrimer 9 does not have a radical polymerizable reactive group on the outermost surface.

(2) Preparation of pigment dispersion The pigment dispersion was prepared by the method shown below. As a coloring agent, C.I. I. Pigment black 7 (carbon black) 15 parts, Discol N-509 (manufactured by Dainichi Seika Kogyo Co., Ltd.) 3.5 parts as a dispersant, ethylene glycol monoallyl ether (manufactured by Nippon Emulsifier Co., Ltd.) as a monomer. In addition, the whole was made 100 parts and mixed and stirred to obtain a mixture. This mixture was subjected to a dispersion treatment for 6 hours together with zirconia beads (diameter 1.5 mm) using a sand mill (manufactured by Yaskawa Seisakusho). Thereafter, zirconia beads were separated by a separator to obtain a black pigment dispersion.

In the same manner, a pigment dispersion corresponding to each color, that is, a cyan pigment dispersion (C.I.
Pigment Blue 15: 3), magenta pigment dispersion (CI Pigment Violet-19), yellow pigment dispersion (CI Pigment Yellow 155) and white pigment dispersion (titanium dioxide fine particles).

(3) Preparation of Ink Composition A1 and Ink Compositions B1-5 Ink Composition A1 and Ink Compositions B1-5 were prepared with the compositions shown in Table 8 below. That is, the monomers, photoradical polymerization initiator, polymerization accelerator, surfactant, and thermal radical polymerization inhibitor shown in Table 8 were mixed and completely dissolved. Next, when the pigment dispersion was contained, the pigment dispersion was gradually dropped into the solvent while stirring, and after completion of the dropping, the mixture was stirred at room temperature for 1 hour. Then, each ink composition A1 and ink composition B1-5 are filtered with a 5 μm membrane filter, and a transparent ink composition (ink composition A1), a black ink composition (ink composition B1), and a yellow ink composition are filtered. (Ink composition B2), magenta ink composition (ink composition B3), cyan ink composition (ink composition B4), and white ink composition (ink composition B5). The numerical values in the table indicate “% by weight”.

In the table, “NVF” means N-vinylformamide manufactured by Arakawa Chemical Industries, Ltd.
“AG” means ethylene glycol monoallyl ether manufactured by Nippon Emulsifier Co., Ltd.
“R-501” means a hyperbranched polymer manufactured by Osaka Organic Chemical Industry Co., Ltd.
"Cure 819" and "Irgacure 127" mean a photo radical polymerization initiator manufactured by Ciba Specialty Chemicals, "Darocur EHA" means a polymerization accelerator manufactured by Ciba Specialty Chemicals, and "BYK-UV3570" means Big Chemie. “Irgastab UV-10” means a thermal radical polymerization inhibitor manufactured by Ciba Specialty Chemicals.

（４）インク組成物Ａ２、インク組成物Ｂ６〜１０の調製
前記（３）と同様にして、下記の表９に示す組成のインク組成物Ａ２、インク組成物Ｂ
６〜１０を調製し、透明インク組成物（インク組成物Ａ２）、ブラックインク組成物（イ
ンク組成物Ｂ１６）、イエローインク組成物（インク組成物Ｂ７）、マゼンタインク組成
物（インク組成物Ｂ８）、シアンインク組成物（インク組成物Ｂ９）及びホワイトインク
組成物（インク組成物Ｂ１０）とした。表中の数値は「重量％」を示す。

(4) Preparation of Ink Composition A2 and Ink Composition B6-10 Ink Composition A2 and Ink Composition B having the compositions shown in Table 9 below in the same manner as (3) above.
6 to 10 were prepared, and a transparent ink composition (ink composition A2), a black ink composition (ink composition B16), a yellow ink composition (ink composition B7), and a magenta ink composition (ink composition B8). Cyan ink composition (ink composition B9) and white ink composition (ink composition B10). The numerical values in the table indicate “% by weight”.

In the table, “Biscoat # 1000” means a hyperbranched polymer manufactured by Osaka Organic Chemical Industry.

3. Ink set Using each of the ink compositions obtained in 1 and 2 above, an ink set was composed of the combinations shown in Table 10.

4). Evaluation Test (1) Printing Evaluation Test Using the ink set shown in 3 above, Roland D.C. G. Using two SJ-540 inkjet printers, one inkjet printer (IJP)
-1) black ink in metallic ink composition (S1, S2 or S3), ink composition A
1, A2 (transparent ink composition) was filled in a light cyan row, and ink compositions B5 and B10 (white ink composition) were filled in a light magenta row.

Another ink jet printer (IJP-2) has ink compositions corresponding to the corresponding color arrays, that is, ink compositions B1 and B6 (black ink composition), ink compositions B2 and B7 (yellow ink composition). Product), ink compositions B3, B8 (magenta ink composition), ink compositions B4, B9 (cyan ink composition) are filled in the black column, yellow column, magenta column, cyan column, respectively, and ink composition A1, A2 (transparent ink composition) was filled in the light cyan row, and ink compositions B5 and B10 (white ink composition) were filled in the light magenta row. Printing was performed according to the following printing pattern.

The recording medium is a vinyl chloride sheet (Viewcal 2000) cut to A4 size.
(White): Sakurai Co., Ltd.), PET film (PG-50L: Lamy Corporation Co., Ltd.), polycarbonate film (Iupilon FE-2000: Mitsubishi Engineering Plastics Co., Ltd.) were used. And sensory evaluation of the printed matter was performed based on the following evaluation criteria. The results are shown in Table 5.
AA: A metallic gloss sufficient to clearly distinguish the reflected object was obtained.
A: A metallic gloss that can slightly distinguish an object reflected in an image was obtained.
B: A metallic gloss with a matte tone (matte tone) was obtained.
C: A metallic gloss was not obtained.

The printing pattern using the ink set is as follows.
a. Print pattern 1
Using IJP-1, the metallic ink composition S1, the ink compositions A1 and A2 (transparent ink composition), and the ink composition B under heating conditions where the surface temperature of the recording medium is 50 ° C.
5, B6 to B10 (white ink composition) were simultaneously ejected to form an image. afterwards,
The image was irradiated with ultraviolet rays using an ultraviolet irradiation device to perform a curing process.

As an ultraviolet irradiation device, an ultraviolet light emitting diode NICHIA having a peak wavelength of 365 nm is used.
i-LED “NCCU033” and UV light emitting diode NI having a peak wavelength of 380 nm
What was produced using CHIA “NCCU001” (both manufactured by Nichia Corporation) and light emitting diode E1S40-0P0C6-01 (manufactured by Toyoda Gosei) having a peak wavelength of 395 nm was used.

Irradiation conditions of the ultraviolet irradiation apparatus are 365 nm, 380 nm, and 395 nm on the irradiation surface.
The irradiation intensity of each wavelength was set to 20 mW / cm 2, that is, 60 mW / cm 2 in total. Then, the sample was irradiated with ultraviolet rays for 5 seconds under the condition that the integrated light quantity per one ultraviolet irradiation treatment was 300 mJ / cm2.

b. Print pattern 2
Using IJP-1, an image was formed using the metallic ink composition S1 under heating conditions where the surface temperature of the recording medium was 50 ° C. Thereafter, using the IJP-2, ink compositions A1, A2 (transparent ink compositions) and B1-B5, B6-B10 are formed on the image.
(Black, yellow, magenta, cyan, and white color ink compositions) were simultaneously ejected to form an image. And the ultraviolet-ray was irradiated with respect to the image on the conditions similar to the said printing pattern 1, and the hardening process was performed.

c. Print pattern 3
Using the IJP-1, ink compositions A1 and A2 (transparent ink composition) and B5 and B10 (white ink composition) were simultaneously ejected onto a recording medium to form a white image. Thereafter, the image was irradiated with ultraviolet rays under the same conditions as in the print pattern 1 to perform a curing process.

Subsequently, an image was formed using the metallic ink composition S1 using the IJP-1 under heating conditions where the surface temperature was 50 ° C. Thereafter, further using the IJP-2, the ink compositions A1, A2 (transparent ink composition) and B1-B5, B6-B1 are formed on the metallic image.
0 (black, yellow, magenta, cyan, and white color ink compositions) was simultaneously ejected to form an image. And the ultraviolet-ray was irradiated with respect to the image on the irradiation conditions similar to the above, and the hardening process was performed.

In addition, printing evaluation of the printing patterns 1-3 was implemented similarly to the above using S2 and S3 instead of the metallic ink composition S1.

  As shown in Table 11, a recorded matter having a metallic tone image having an arbitrary color tone could be obtained by the inkjet recording method using the ink set.

Claims (22)

A metallic ink composition comprising a metal pigment;
At least one photocurable ink composition selected from the group consisting of a chromatic ink composition, a black ink composition, and a white ink composition;
Ink set with. A metallic ink composition containing a metal pigment;
A photocurable ink composition A containing no coloring material;
A photocurable ink composition B containing at least one colorant selected from the group consisting of chromatic pigments, black pigments, and white pigments;
Ink set with. The metal pigment is a tabular grain, and when the major axis on the plane of the tabular grain is X, the minor axis is Y, and the thickness is Z, a circle obtained from the area of the XY plane of the tabular grain 3. The ink set according to claim 1, wherein the ink set is a metal pigment having a 50% average particle diameter R50 of an equivalent diameter of 0.5 to 3 μm and satisfying a condition of R50 / Z> 5. The ink set according to claim 1, wherein the photocurable ink composition contains at least a colorant, a photopolymerization initiator, and a polymerizable compound. The ink set according to claim 2, wherein the photocurable ink composition A is non-aqueous and contains at least a photopolymerization initiator and a polymerizable compound. The photocurable ink composition B is non-aqueous and contains at least a polymerizable compound,
The ink set according to claim 2, which does not contain a photopolymerization initiator. The ink according to claim 4 or 5, wherein the photopolymerization initiator is at least two selected from the group consisting of bisacylphosphine oxide, monoacylphosphine oxide, α-aminoketone, and α-hydroxyketone. set. The ink set according to any one of claims 4 to 7, wherein the polymerizable compound is at least one selected from the group consisting of an N-vinyl compound, ethylene glycol monoallyl ether, and a dendritic polymer. The ink set according to claim 8, wherein the dendritic polymer is a dendrimer and / or a hyperbranched polymer.   The liquid container which accommodated the ink set of any one of Claims 1-9.   A liquid ejecting apparatus comprising the liquid container according to claim 10. In an inkjet recording method for performing recording by discharging droplets of an ink composition and attaching the droplets to a recording medium,
An ink jet recording method for forming an image using the ink set according to claim 1. The metallic ink composition;
At least one selected from the group consisting of the chromatic ink composition, the black ink composition, and the white ink composition;
The inkjet recording method according to claim 12, wherein an image having an arbitrary color tone is formed by simultaneously discharging the inks. After forming an image using the metallic ink composition, an image having an arbitrary color tone is formed using the chromatic color ink composition, and then the black ink composition and / or the white ink composition is ejected. The inkjet recording method according to claim 12, wherein a curing process is performed on the formed image simultaneously with or after ejection. After discharging the metallic ink composition to form an image, the chromatic ink composition,
The inkjet recording method according to claim 12, wherein the black ink composition and the white ink composition are ejected simultaneously, and the formed image is subjected to a curing process simultaneously with or after the ejection. After forming an image using the metallic ink composition, the image is dried, and the chromatic color ink composition, the black ink composition, and the white ink composition are ejected to obtain an arbitrary color tone. The inkjet recording method according to claim 12, wherein after the image is formed, a curing process is performed on the image. The inkjet recording method according to claim 15 or 16, wherein the curing treatment is performed by irradiating ultraviolet rays. In an inkjet recording method for performing recording by discharging droplets of an ink composition and attaching the droplets to a recording medium,
An ink jet recording method for forming an image using the ink set according to claim 2. The metallic ink composition;
The photocurable ink composition A and / or the photocurable ink composition B;
The inkjet recording method according to claim 18, wherein an image having an arbitrary color tone is formed by performing a curing process on the formed image simultaneously with or after the ejection. After the metallic ink composition was ejected to form an image, the photocurable ink composition A and / or the photocurable ink composition B was ejected and formed simultaneously with or after the ejection. The inkjet recording method according to claim 18, wherein the image is cured to form an image having an arbitrary color tone. After forming an image using the photocurable ink composition A and the photocurable ink composition B containing the white pigment, a curing treatment is performed by light irradiation, and (i) the metallic ink composition and An image is formed using (ii) the photocurable ink composition A and / or (iii) the photocurable ink composition B containing the chromatic pigment or the black pigment. The inkjet recording method as described. It was recorded by the inkjet recording method according to any one of claims 12 to 21.
Recorded matter.