JP6631159B2 - Printed matter and container using the printed matter - Google Patents

Description

  The present invention relates to a printed matter and a container using the printed matter.

  2. Description of the Related Art Conventionally, in various printed materials, it may be required to impart metallic luster in order to improve the design.

  As one means for imparting metallic luster, a film having metallic luster is used. For example, a printed matter having a metallic luster is produced by laminating a film having a metallic luster on a paper base material to prepare a substrate having a metallic luster, and further printing a pattern layer or the like on the substrate.

However, a film having a metallic luster is formed by forming a metal vapor-deposited film on the film, and thus requires a cost and is not suitable for a low-priced printed matter. Further, a substrate obtained by laminating a film having a metallic luster on a paper substrate is curled due to a difference in shrinkage between the paper and the film, and the subsequent steps (for example, a printing step on the substrate, a printed material in a container). There is a problem in that the accuracy of the processing step is reduced and the yield is reduced.
In order to solve the above problem, Patent Document 1 has been proposed.

JP-A-2003-2323

  Patent Literature 1 discloses a paper container in which a printing layer having a metallic glossy region layer including a binder resin and a metal thin film strip is formed on a paper base material.

  The paper container of Patent Document 1 has no problem in cost and curl. However, although the paper container of Patent Document 1 has a certain level of metallic luster, it does not have a high level of metallic luster.

  SUMMARY OF THE INVENTION An object of the present invention is to provide a printed material and a container having high metallic luster without using a metal vapor deposition means.

In order to solve the above problems, the present invention provides printed matter and containers according to the following [1] to [15].
[1] A hard coat layer is provided at an arbitrary position on the base material, and a gloss print layer is further provided at an arbitrary position on the hard coat layer, the gloss print layer includes metal scales, and A printed material in which the metal scale is unevenly distributed on the upper part of the glossy print layer.
[2] The printed matter according to the above [1], wherein the average length and the average thickness of the metal scale satisfy the following condition (1).
Average thickness of metal scale / average length of metal scale ≦ 0.010 (1)
[3] The printed matter according to [1] or [2], wherein the average thickness of the metal scale and the thickness of the glossy print layer satisfy the following condition (2).
10 ≦ [average length of metal scale / thickness of glossy printed layer] (2)
[4] The printed matter according to any one of [1] to [3], wherein the average length of the metal scale is 5.0 to 30.0 μm.
[5] The printed matter according to any one of [1] to [4], wherein the average thickness of the metal scale is 0.10 μm or less.

[6] The printed matter according to any one of the above [1] to [5], wherein the glossy print layer has a thickness of 0.15 to 1.50 μm.
[7] The printed matter according to any one of [1] to [6], wherein a picture is formed by the glossy print layer.
[8] The printed matter according to any one of [1] to [7], wherein the surface of the hard coat layer has a specular glossiness at 60 degrees of JIS Z8741: 1997 of 85% or more.
[9] The printed matter according to any one of [1] to [8], wherein the surface of the hard coat layer has a surface roughness PPS of less than 1 μm according to JIS P8151: 2004.
[10] The printed matter according to any one of [1] to [9], wherein the hard coat layer is a cured layer of the ionizing radiation-curable resin composition.
[11] The printed matter according to any one of [1] to [10], wherein the substrate is a paper substrate.
[12] The printed matter according to [11], wherein the base material is the paper base material, and the surface of the glossy print layer has a specular glossiness at 60 degrees in JIS Z8741: 1997 of 150% or more.
[13] Any of the above-mentioned [1] to [12], wherein a picture layer is provided at an arbitrary position on the gloss print layer and / or the hard coat layer where the gloss print layer is not formed. Printed matter described in Crab.
[14] The printed matter according to any one of [1] to [13], further including a surface protective layer on the outermost surface on the side having the glossy print layer.
[15] A container using the printed matter according to any one of [1] to [14].

  The printed matter and the container of the present invention have a high metallic luster without using a metal vapor deposition means and are extremely excellent in cost performance.

FIG. 1 is a cross-sectional view illustrating an embodiment of a printed matter of the present invention. It is sectional drawing which shows other embodiment of the printed matter of this invention.

[Print]
The printed matter of the present invention has a hard coat layer at an arbitrary place on a substrate, and further has a glossy print layer at an arbitrary place on the hard coat layer, and the glossy print layer includes metal scales. In addition, the metal scale is unevenly distributed on the glossy print layer.
Hereinafter, embodiments of the printed matter of the present invention will be described.

  1 and 2 are cross-sectional views showing one embodiment of a printed matter 10 of the present invention. 1 and 2 has a hard coat layer 2 and a gloss print layer 3 on a substrate 1 in this order. The printed matter of FIG. 2 further has a picture layer 4 and a surface protective layer 5 on the glossy printed layer 3. In addition, the glossy print layer 3 of the printed matter 10 of FIGS. 1 and 2 has an upper metal scale unevenly distributed region 31.

The material of the base material is not particularly limited as long as it is a material used for a conventional printed matter or the like. Specifically, high quality paper, medium quality paper, coated paper, synthetic paper, impregnated paper, laminated paper For example, paper such as coated paper for printing and coated paper for recording, plastic film such as polyethylene terephthalate film, polyethylene film, polypropylene film and polycarbonate film, or a composite of these is used.
In the present invention, no matter what kind of substrate is used, a high metallic luster can always be realized because a hard coat layer described later is provided on the substrate.

The thickness of the base material is not particularly limited, but is usually about 150 to 550 g / m ^{2 in} the case of a paper base, and is usually about 9 to 50 μm in the case of a plastic film base.

Hard Coat Layer In the present invention, by interposing a hard coat layer between the substrate and the glossy print layer, it is possible to sufficiently increase the metallic gloss of the glossy print layer. The reason is considered as follows.
First, the hard coat layer hardly permeates the solvent of the gloss printing layer ink. For this reason, when applying and drying the glossy printing layer ink on the hard coat layer, the solvent does not easily flow below the glossy printing layer. On the other hand, the solvent tends to flow above the glossy print layer when the solvent volatilizes during the drying process. Then, it is considered that the metal flakes float above the glossy print layer with the flow of the solvent, and the metal flakes are unevenly distributed on the upper part of the glossy print layer, so that the metal gloss of the glossy print layer can be sufficiently increased.
In addition, the surface of the above-described base material is rough, though the degree varies depending on the type. For example, paper has a rough surface due to fibers. When the glossy print layer is formed when the surface of the substrate is rough as described above, the surface of the glossy print layer is also roughened, and the metallic gloss cannot be sufficiently increased. It is considered that by alleviating the roughness of the surface, the surface of the glossy print layer is prevented from being roughened, and the metallic luster can be sufficiently increased.
In addition, when the surface of the base material is damaged, the unevenness of the scratch is reflected on the surface of the glossy print layer, so that the metallic gloss of the glossy print layer decreases. However, since the surface of the substrate composed of the base material and the hard coat layer is not easily damaged, it is considered that unevenness due to the damage is suppressed from being reflected on the surface of the glossy print layer, and the metallic gloss of the glossy print layer can be sufficiently increased. .

  The hard coat layer is preferably formed at least in a portion corresponding to a portion where a gloss print layer described later is formed. In addition, from the viewpoint of eliminating the complexity of alignment between the hard coat layer and the glossy print layer, it is preferable that the hard coat layer be provided on the entire surface of the base material where the glossy print layer is formed. In addition, from the viewpoint of uniforming the physical properties of the substrate composed of the substrate and the hard coat layer to suppress deformation and the like of the substrate, the hard coat layer is preferably formed on the entire surface of the substrate.

  The surface of the hard coat layer (the surface of the hard coat layer on the side opposite to the substrate) is preferably smoothed. When the surface of the hard coat layer is rough, the surface area of the hard coat layer increases, and the solvent easily penetrates when forming the glossy print layer. On the other hand, when the surface of the hard coat layer is smoothed, the solvent hardly penetrates into the hard coat layer. Can be higher. Further, when the surface of the hard coat layer is rough, the unevenness of the hard coat layer is also reflected on the gloss print layer, and the surface of the gloss print layer becomes rough. On the other hand, when the surface of the hard coat layer is smoothed, the surface of the glossy print layer is also smoothed, and the metallic gloss of the glossy print layer can be sufficiently increased.

Indicators for smoothing the surface of the hard coat layer include mirror glossiness according to JIS Z8741: 1997 and arithmetic average roughness Ra according to JIS B0601: 2001.
The specular gloss at 60 degrees of JIS Z8741: 1997 on the surface of the hard coat layer is preferably 85% or more, more preferably 90% or more.

The arithmetic average roughness Ra (Ra _0.08HA ) of JIS B0601: 2001 on the surface of the hard coat layer when the cut-off value is 0.08 mm is preferably 0.080 μm or less, and 0.060 μm or less. More preferably, it is more preferably 0.040 μm or less.
Note that the cutoff value indicates the fineness of a filter that removes an undulating component (low-frequency component) from a cross-sectional curve. More specifically, the cross-sectional curve can be divided into a swell component (medium frequency component, low frequency component) and a roughness component (high frequency component), and the lower the cutoff value (the finer the filter), the lower the cutoff value. The frequency component is removed, and the ratio of the medium frequency component and the high frequency component increases. Therefore, Ra _{0.08 HA} indicates irregularities of the high frequency component of the hard coat layer, and Ra _{0.8 HA} described later indicates irregularities of the low frequency component of the hard coat layer. Then, Ra _{0.25 HA} described later indicates irregularities of the medium frequency component of the hard coat layer.
If the hard coat layer contains many irregularities of high frequency components, the surface area of the hard coat layer increases and the solvent easily penetrates, so that the metallic scales of the glossy print layer are less likely to be unevenly distributed on the upper portion, and the metallic gloss is impaired. _Therefore , it is preferable to set Ra _{0.08 HA} to the above range.

The arithmetic mean roughness Ra (Ra _0.25HA ) of JIS B0601: 2001 on the surface of the hard coat layer when the cut-off value is 0.25 mm is preferably 0.200 μm or less, and 0.175 μm or less. More preferably, it is even more preferably 0.150 μm or less.
The arithmetic average roughness Ra (Ra _0.8HA ) of JIS B0601: 2001 on the surface of the hard coat layer when the cut-off value is 0.8 mm is preferably 0.400 μm or less, and 0.370 μm or less. More preferably, it is even more preferably 0.350 μm or less.
The unevenness of the medium frequency component and the low frequency component increases the surface area, although not as large as that of the high frequency component. For this reason, it is preferable that Ra _0.25HA and Ra _0.8HA be within the above ranges. In addition, when the unevenness of the low frequency component of the hard coat layer disappears, the unevenness due to the unevenness of the low frequency component of the hard coat layer cannot be formed on the surface of the gloss print layer, and the gloss print layer is excessively smoothed. There is a tendency. In this case, the reflected light in the specular reflection direction of the glossy printing layer becomes too strong, giving a viewer uncomfortable feeling. For this reason, Ra _0.25HA is preferably 0.050 μm or more, and more preferably 0.100 μm or more. And Ra _0.8HA is preferably 0.100 μm or more, and more preferably 0.200 μm or more.

Furthermore, the JIS B0601: 2001 arithmetic mean roughness Ra (Ra _0.08BA ) of the substrate surface when the cutoff value is 0.08 mm, and the JIS of the substrate surface when the cutoff value is 0.25 mm It is preferable that the arithmetic average roughness Ra (Ra _{0.25 BA} ), Ra _{0.08 HA} and Ra _{0.8 HA of} B0601: 2001 satisfy the following condition (a ₁ ).
_{[Ra 0.25HA / Ra 0.25BA]>} [Ra 0.08HA / Ra 0.08BA] (a 1)
Furthermore, JIS B0601: 2001 arithmetic mean roughness Ra ( _Ra0.08BA ) of the substrate surface when the cutoff value is 0.08 mm, and JIS of the substrate surface when the cutoff value is 0.8 mm It is preferable that the arithmetic mean roughness Ra (Ra _0.8BA ) of B0601: 2001, the above-mentioned Ra _0.08HA and Ra _0.8HA satisfy the following condition (a ₂ ).
[Ra _0.8HA / Ra _0.8BA ]> [Ra _{0.08 HA} / Ra _{0.08 BA} ] (a ₂ )
The ratio between the Ra of the hard coat layer and the Ra of the substrate indicates the degree to which the hard coat layer reduces the irregularities of the substrate. The conditions (a ₁ ) and (a ₂ ) indicate that the degree of the hard coat layer mitigating the high-frequency component is greater than the degree of mitigating the low-frequency component of the irregularities of the substrate. I have.
As described above, increasing the surface area of the hard coat layer is largely affected by unevenness of the high frequency component. For this reason, it is preferable that the hard coat layer reduces unevenness of the high frequency component of the base material. On the other hand, if the unevenness of the low frequency component of the base material is excessively relaxed, the texture of the base material is impaired, and the reflected light in the specular reflection direction of the glossy print layer may be too strong. Therefore, satisfying the above conditions (a ₁ ) and (a ₂ ) indicating that the degree of relaxing the high frequency component is greater than the degree of relaxing the low frequency component of the unevenness of the base material is of great significance. is there.

To more easily exhibit the above effect, the _{Ra 0.08HA, Ra 0.25HA, Ra 0.08BA} , and _{Ra 0.25BA} preferably satisfies the following conditions _{(b 1).}
1.5 ≦ [Ra _{0.25 HA} / Ra _{0.25 BA} ] / [Ra _{0.08 HA} / Ra _{0.08 BA} ] (b ₁ )
The condition (b ₁ ) more preferably satisfies 1.5 ≦ [Ra _{0.25 HA} / Ra _{0.25 BA} ] / [Ra _{0.08 HA} / Ra _{0.08 BA} ] ≦ 4.0, and more preferably 1.5 ≦ [ It is more preferable to satisfy Ra _{0.25 HA} / Ra _{0.25 BA} ] / [Ra _{0.08 HA} / Ra _{0.08 BA} ] ≦ 3.5.
Furthermore, in order to more easily exhibit the above effect, the _{Ra 0.08HA, Ra 0.8HA, Ra 0.08BA} , and _{Ra 0.8BA} is to satisfy the following condition _{(b 2)} preferred.
1.8 ≦ [Ra _{0.8 HA} / Ra _{0.8 BA} ] / [Ra _{0.08 HA} / Ra _{0.08 BA} ] (b ₂ )
The condition (b ₂ ) more preferably satisfies 2.2 ≦ [Ra _0.8HA / Ra _0.8BA ] / [Ra _0.08HA / Ra _0.08BA ] ≦ 4.0, and more preferably 2.5 ≦ [ It is more preferable to satisfy Ra _0.8HA / Ra _0.8BA ] / [Ra _{0.08 HA} / Ra _{0.08 BA} ] ≦ 3.5.

Specific examples of the hard coat layer include a cured product layer of the ionizing radiation-curable resin composition (hereinafter, may be referred to as a “cured product layer”), a clay coat layer, and the like. From the viewpoint of improving the permeation prevention properties, the cured product layer of the ionizing radiation-curable resin composition is preferably used.
Furthermore, when the hard coat layer is formed from the ionizing radiation curable resin composition, the hard coat layer can be instantaneously cured by irradiation with ionizing radiation. Can be suppressed from following the irregularities of the high frequency component of the base material. In other words, when the hard coat layer is formed from the ionizing radiation-curable resin composition, the hard coat layer can reduce the unevenness of the high-frequency component of the substrate. On the other hand, until the hard coat layer is cured (during the drying process), the surface shape of the hard coat layer appropriately follows the unevenness of the low frequency component of the base material. That is, when the hard coat layer is formed from the ionizing radiation-curable resin composition, the surface of the hard coat layer can be formed into a shape having moderate low frequency component irregularities while suppressing irregularities of high frequency components, The above-mentioned effects (suppression of penetration of the solvent into the hard coat layer, maintenance of the texture of the base material, etc.) can be easily exhibited.

Cured Product Layer The ionizing radiation-curable resin composition for forming the cured product layer is a composition containing a compound having an ionizing radiation-curable functional group (hereinafter, also referred to as “ionizing radiation-curable compound”). Examples of the ionizing radiation-curable functional group include an ethylenically unsaturated bond group such as a (meth) acryloyl group, a vinyl group and an allyl group, and an epoxy group and an oxetanyl group. As the ionizing radiation-curable compound (in the case of ultraviolet curing, it may be referred to as "ultraviolet-curable compound"), a compound having an ethylenically unsaturated bond group is preferable, and having two or more ethylenically unsaturated bond groups. Compounds are more preferable, and among them, polyfunctional (meth) acrylate compounds having two or more ethylenically unsaturated bonding groups are further preferable. As the polyfunctional (meth) acrylate-based compound, any of a monomer and an oligomer can be used. However, a monomer is preferable from the viewpoint of improving the anti-scratch property and the anti-penetration property due to a high crosslinking density.
Note that ionizing radiation means an electromagnetic wave or a charged particle beam having an energy quantum capable of polymerizing or cross-linking a molecule, and is usually ultraviolet (UV) or electron beam (EB). Electromagnetic waves such as X-rays and γ-rays, and charged particle beams such as α-rays and ion beams can also be used.

Among the polyfunctional (meth) acrylate monomers, examples of the bifunctional (meth) acrylate monomer include ethylene glycol di (meth) acrylate, bisphenol A tetraethoxy diacrylate, bisphenol A tetrapropoxy diacrylate, and 1,6-hexanediol. Diacrylate and the like.
Examples of the trifunctional or higher functional (meth) acrylate-based monomer include, for example, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, Examples include pentaerythritol tetra (meth) acrylate and isocyanuric acid-modified tri (meth) acrylate.
The (meth) acrylate-based monomer may have a partially modified molecular skeleton, and may be modified by ethylene oxide, propylene oxide, caprolactone, isocyanuric acid, alkyl, cyclic alkyl, aromatic, bisphenol, or the like. Can also be used.
The number of functional groups of the polyfunctional (meth) acrylate monomer is preferably from 2 to 6, and more preferably from 2 to 3.

Examples of the polyfunctional (meth) acrylate oligomer include acrylate polymers such as urethane (meth) acrylate, epoxy (meth) acrylate, polyester (meth) acrylate, and polyether (meth) acrylate.
Urethane (meth) acrylate is obtained, for example, by reacting a polyhydric alcohol and an organic diisocyanate with hydroxy (meth) acrylate.
Preferred epoxy (meth) acrylates are (meth) acrylates obtained by reacting (meth) acrylic acid with a trifunctional or higher functional aromatic epoxy resin, alicyclic epoxy resin, aliphatic epoxy resin or the like. (Meth) acrylates obtained by reacting the above aromatic epoxy resin, alicyclic epoxy resin, aliphatic epoxy resin, etc. with polybasic acid and (meth) acrylic acid, and bifunctional or more aromatic epoxy resin, (Meth) acrylate obtained by reacting an alicyclic epoxy resin, an aliphatic epoxy resin or the like with a phenol and (meth) acrylic acid.
The ionizing radiation-curable compounds may be used alone or in combination of two or more. The ionizing radiation-curable compound preferably contains a polyfunctional (meth) acrylate monomer in an amount of 50% by mass or more, more preferably 80% by mass or more.

When the ionizing radiation curable compound is an ultraviolet curable compound, the ionizing radiation curable composition (ultraviolet curable resin composition) preferably contains additives such as a photopolymerization initiator and a photopolymerization accelerator. .
Examples of the photopolymerization initiator include one or more selected from acetophenone, benzophenone, α-hydroxyalkylphenone, Michler's ketone, benzoin, benzylmethyl ketal, benzoylbenzoate, α-acyl oxime ester, thioxanthone, and the like.
Further, the photopolymerization accelerator can reduce the polymerization inhibition due to air during curing and can increase the curing speed. For example, p-dimethylaminobenzoic acid isoamyl ester, p-dimethylaminobenzoic acid ethyl ester, etc. One or more selected ones are mentioned.
The ionizing radiation-curable resin composition may contain additives such as a light stabilizer, an antioxidant, and a leveling agent.
The ionizing radiation-curable resin composition may contain a resin component (thermoplastic resin or thermosetting resin) other than the ionizing radiation-curable compound. However, in order to easily achieve the above-described effects, the proportion of the ionizing radiation-curable compound in all the resin components of the ionizing radiation-curable resin composition is preferably 90% by mass or more, and more preferably 95% by mass or more. It is more preferable that the content be 100% by mass.

  The cured material layer preferably has a thickness of 2 μm or more from the viewpoint of smoothing the substrate and preventing damage. In addition, when the cured product layer is too thick, the workability is reduced, so the thickness of the cured product layer is more preferably 3 to 20 μm, further preferably 4 to 10 μm, and more preferably 5 to 7 μm. Is even more preferred.

    The cured product layer can be formed by applying an ink for a cured product layer containing the ionizing radiation-curable resin composition and, if necessary, a solvent, onto a substrate, drying, and irradiating with ionizing radiation. When no solvent is contained in the cured product layer ink, drying is unnecessary.

Clay coat layer The clay layer contains clay and a binder resin.
Any clay can be used without particular limitation as long as it is generally called clay or clay.Furthermore, kaolin, talc, bentonite, smectite, vermiculite, mica, chlorite, Kibushi clay, gairome clay can be used. , Halloysite, etc. can be used.

  The clay coat layer preferably contains pigments such as calcium carbonate, titanium dioxide, amorphous silica, expandable barium sulfate, and satin white, in addition to clay. By using calcium carbonate or titanium dioxide as the pigment, the smoothness of the surface of the clay coat layer can be easily improved. Furthermore, calcium carbonate is preferably used because it is inexpensive.

  Examples of the binder resin include latex-based binder resins (eg, styrene-butadiene latex, acrylic latex-vinyl acetate-based latex), and water-soluble binder resins (eg, starch (modified starch, oxidized starch, hydroxyethyl etherified starch, phosphoric acid) Esterified starch), polyvinyl alcohol, casein, etc.).

The mass ratio of clay: pigment: binder resin in the clay coat layer is preferably 1 to 20:50 to 90:10 to 30.
The clay coat layer may contain additives such as a pigment dispersant, an antifoaming agent, an antifoaming agent, a viscosity modifier, a lubricant, a water-proofing agent, a water retention agent, a coloring material, and a printability improving agent. Good.

  The thickness of the clay coat layer is preferably from 5 to 40 μm, more preferably from 10 to 30 μm, and even more preferably from 15 to 25 μm, from the viewpoint of smoothness of the substrate, prevention of scratches and balance of workability. More preferred.

  The clay coat layer can be formed by applying an ink for a clay coat layer obtained by diluting a material constituting the clay coat layer with a solvent onto a substrate and drying the ink.

Glossy printing layer The glossy printing layer is a layer located on the hard coat layer, and is formed by printing the glossy printing layer ink. By forming the layer imparting metallic luster by printing instead of vapor deposition, the cost can be reduced and curling can be suppressed.
The glossy print layer is preferably formed in contact with the hard coat layer. Also, as shown in FIG. 1, the glossy print layer is formed in a desired pattern on a part of the area on the hard coat layer so that characters, numerals, figures, symbols, landscapes, people, animals, characters, etc. It may be formed, or may be formed in all regions on the hard coat layer as shown in FIG.

  In the present invention, it is necessary that the glossy print layer contains metal flakes and that the metal flakes are unevenly distributed above the glossy print layer (the side opposite to the hard coat layer of the glossy print layer). By unevenly distributing the metal flakes on the upper portion of the glossy print layer, it is possible to increase the metallic luster and improve the adhesion between the glossy print layer and the hard coat layer.

  The metal flakes can be unevenly distributed on the upper portion of the glossy printing layer in the process of forming the glossy printing layer. More specifically, the solvent flows upward when the solvent of the ink for the glossy printing layer is volatilized during the heating and drying process of the glossy printing layer. Then, it is considered that the metal flakes emerge with the flow of the solvent, and the metal flakes are unevenly distributed above the glossy print layer. In particular, in the present invention, since the hard coat layer where the solvent hardly penetrates is located below the glossy print layer, the solvent can be suppressed from flowing downward, and the solvent almost flows upward, so that the upper part of the glossy print layer It is considered that metal scales are easily distributed unevenly. In particular, when the hard coat layer is a cured product layer of the ionizing radiation-curable resin composition, it is considered that uneven distribution of metal scales can be made more remarkable.

The degree of uneven distribution of the metal scales can be confirmed by imaging the cross section of the printed matter with an electron microscope and determining the density difference in the glossy printed layer of the photographed image. More specifically, the unevenly distributed portion of the metal scale is observed as white because of the remarkable electron reflection, and the portion substantially not containing the metal scale is observed as gray.
The ratio of the thickness of the uneven distribution region of the metal flakes in the glossy print layer [(the thickness of the uneven distribution region of the metal flakes / the total thickness of the glossy print layer)] is 10 to 60% from the viewpoint of the balance between the metallic gloss and the adhesion. Preferably, it is 20 to 50%, more preferably 25 to 45%.

The metal scale preferably satisfies the following condition (1).
Average thickness of metal scale / average length of metal scale ≦ 0.010 (1)
By setting the [average thickness of the metallic scale / average length of the metallic scale] to 0.010 or less, the horizontal direction of the glossy print layer (perpendicular to the thickness direction of the glossy print layer) at the time of applying the glossy print layer ink. Direction), the metal scales are less likely to tilt. For this reason, when the solvent flows over the glossy printing layer in the process of drying glossy printing, the metal flakes are easily subjected to the force of the solvent flow, and the metal flakes tend to be unevenly distributed on the upper part of the glossy printing layer, Since the scales are easily arranged in parallel, the metallic luster can be easily increased. In addition, the adverse effects of tilting the metal flakes increase with an increase in the content of the metal flakes. However, when the above condition (1) is satisfied, the content of the metal flakes is increased because the metal flakes are difficult to tilt. And the metal luster can be increased.
If the average thickness of the metal flakes is too small with respect to the average length of the metal flakes, there is a possibility that the handleability becomes difficult or sufficient metallic luster cannot be exhibited.
Therefore, the condition (1) preferably satisfies 0.001 ≦ average thickness of metal scale / average length of metal scale ≦ 0.010, and 0.002 ≦ average thickness of metal scale / average length of metal scale. It is more preferable that the thickness satisfies the condition of ≦ 0.008, more preferably 0.002 ≦ the average thickness of the metal scale / the average length of the metal scale ≦ 0.005.

In addition, at the time of applying the glossy printing layer ink, from the viewpoint of further suppressing the inclination of the metal scale with respect to the horizontal direction of the glossy printing layer, and from suppressing the metal scales protruding from the surface of the glossy printing layer. It is preferable that the average length of the metal scale and the thickness of the glossy print layer satisfy the following condition (2).
10 ≦ average length of metal scale / thickness of glossy printed layer (2)
If the [average length of metal flakes / thickness of glossy print layer] is too large, metal flakes may protrude from the surface of the glossy print layer. Therefore, condition (2) is 15 ≦ average of metal flakes. It is more preferable that the length / thickness of the glossy printing layer ≦ 60, and it is even more preferable that 25 ≦ the average length of the metal scale / thickness of the glossy printing layer ≦ 50.

Examples of the material of the metal scale include metals and alloys such as aluminum, gold, silver, brass, titanium, chromium, nickel, nickel chrome, and stainless steel.
The metal scale can be obtained, for example, by peeling a metal thin film obtained by vacuum-depositing the metal or alloy on a plastic film from the plastic film, and pulverizing and stirring the peeled metal thin film.

The average length of the metal scale is preferably from 5.0 to 30.0 μm, and more preferably from 8.0 to 20.0 μm, from the viewpoints of dispersion suitability, uneven distribution and arrangement of the metal scale.
In addition, the average thickness of the metal scales is preferably 0.10 μm or less, more preferably 0.08 μm or less, and still more preferably 0.06 μm or less, from the viewpoint of uneven distribution and arrangement of the metal scales. . In addition, the average thickness of the metal scale is preferably 0.01 μm or more, and more preferably 0.02 μm or more, from the viewpoint of handleability and high metallic luster.

The average length and average thickness of the metal scales are the average values of 100 metal scales. The length and thickness of each metal scale can be measured by using a laser interference type three-dimensional shape analyzer in a state where the metal scale is spread on a smooth base material. The length of each metal scale means the maximum diameter when observing the individual metal scale from a plane in an arbitrary direction, and the thickness of each metal scale is obtained when the individual metal scale is observed from the cross-sectional direction. Means the maximum thickness. In addition, the maximum diameter when observing the individual metal flakes from a plane in an arbitrary direction is intended to unify the directions in which the maximum diameters of the individual metal flakes are measured. For example, when the X-axis direction on the screen on which the measurement result of the three-dimensional shape analyzer is image-processed is set to an arbitrary direction (measurement direction), the maximum diameter is measured in a direction parallel to the X-axis. Even if the maximum diameter exists in a direction that is not parallel to the X axis, it is not considered as the maximum diameter.
As the laser interference type three-dimensional shape analyzer, for example, a product name “Shape Analysis Laser Microscope VK-X Series” manufactured by Keyence Corporation may be mentioned.

It is preferable that the glossy print layer further contains a binder resin.
Examples of the binder resin include a thermoplastic resin such as a polyester resin, a urethane resin, an epoxy resin, a melamine resin, an alkyd resin, a phenol resin, an acrylic resin, and a cellulose resin, and a thermosetting resin. Further, as the binder resin, a cured product of the above-described ultraviolet curable resin composition may be used.

  The compounding ratio of the binder resin to the metal flakes is preferably 55:45 to 30:70, more preferably 50:50 to 35:65 in terms of the solid content mass ratio. By setting the metal scale to 45 or more with respect to the binder resin 55, it becomes easy to obtain sufficient metallic luster, and by setting the metal scale to 70 or less with respect to the binder resin 30, the printability of the glossy print layer and the print quality of the printed matter are improved. Workability can be easily improved. In the present invention, since the hard coat layer is provided below the glossy print layer, even if a large amount of metal scales is used as described above, the metal scales can be unevenly distributed above the glossy print layer.

The thickness of the glossy print layer is preferably from 0.15 to 1.50 μm, more preferably from 0.20 to 1.00 μm, from the viewpoint of uneven distribution and arrangement of metal scales, and from the viewpoint of concealment. , 0.25 to 0.75 μm.
The thickness of the glossy print layer is determined by measuring the thickness at 20 locations from an image of a cross section taken using, for example, a scanning electron microscope (SEM), a transmission electron microscope (TEM), or a scanning transmission electron microscope (STEM). Then, it can be calculated from the average value of the 20 values. When the film thickness to be measured is on the order of μm, it is preferable to use SEM, and when it is on the order of nm, it is preferable to use TEM or STEM. In the case of SEM, the acceleration voltage is preferably 1 kV to 10 kV and the magnification is preferably 1000 to 7000 times. In the case of TEM or STEM, the acceleration voltage is preferably 10 kv to 30 kV and the magnification is preferably 50,000 to 300,000.
The thickness of the layers other than the glossy print layer can be measured in the same manner as described above.

  The glossy printing layer may contain a coloring agent such as titanium oxide, zinc white, carbon black, iron oxide, iron yellow, ultramarine, metallic pigment, pearl pigment, etc. in order to make the glossy printing layer a desired color. .

  From the viewpoint of metallic luster, the specular gloss at 60 degrees in JIS Z8741: 1997 on the surface of the glossy print layer (the surface opposite to the hard coat layer side of the glossy print layer) is preferably 150% or more, It is more preferably at least 200%, further preferably at least 250%. The upper limit of the specular gloss of the surface of the glossy print layer is about 500%.

Further, the arithmetic average roughness Ra (Ra _0.08GL ) of JIS B0601: 2001 on the surface of the glossy print layer when the cutoff value is set to 0.08 mm may be 0.100 μm or less from the viewpoint of metallic luster. preferable. Note that Ra _0.08GL is preferably not too small from the viewpoint of suppressing the reflection in the regular reflection direction and improving the visibility. _{Therefore, Ra 0.08GL} is more preferably 0.010μm ≦ _{Ra 0.08GL} ≦ 0.070μm, more preferably from 0.020μm ≦ _{Ra 0.08GL} ≦ 0.050μm.

The arithmetic average roughness Ra (Ra _0.25GL ) of JIS B0601: 2001 on the surface of the glossy print layer when the cutoff value is 0.25 mm is 0.250 μm or less from the viewpoint of metallic luster. Preferably, it is 0.200 μm or less, more preferably 0.150 μm or less. Note that Ra _0.25GL is preferably 0.125 μm or more from the viewpoint of suppressing reflection in the regular reflection direction and improving visibility.

The arithmetic mean roughness Ra (Ra _0.8GL ) of JIS B0601: 2001 on the surface of the glossy print layer when the cutoff value is 0.8 mm may be 0.500 μm or less from the viewpoint of metallic luster. Preferably, it is 0.450 μm or less, more preferably 0.400 μm or less. From the viewpoint of suppressing reflection in the specular reflection direction and improving visibility, Ra _0.8GL is preferably 0.250 μm or more.

The glossy printing layer can be formed by applying a glossy printing layer ink obtained by diluting a component for forming the glossy printing layer with a solvent on the hard coat layer, drying the coating, and irradiating ultraviolet rays as needed.
The gloss printing layer ink preferably contains a solvent in an amount of 600 to 1100 parts by mass with respect to 100 parts by mass of the total solid content, from the viewpoint of balancing uneven distribution of metal scale and drying efficiency.
Since the permeability of the solvent varies depending on the resin composition of the hard coat layer, the type of a suitable solvent cannot be unconditionally determined. For example, ethyl acetate, isopropyl alcohol (IPA), ethanol, normal propyl acetate (NPAC), and A mixture or the like can be used.

Picture layer The picture layer is formed on any part of the gloss print layer and / or the hard coat layer where the gloss print layer is not formed, for the purpose of enhancing the design of the printed matter.
The picture layer is formed by printing or the like. The picture layer can be formed by multicolor printing using normal yellow, red, blue, and black process colors, or by multicolor printing using a special color prepared by preparing a plate of each color constituting the picture. . The design of the design layer can be used without particular limitation as long as the design is used in normal printing (for example, characters, numbers, figures, symbols, landscapes, people, animals, characters, etc.).

As the ink used for forming the picture layer, an ink obtained by appropriately mixing a coloring agent such as a pigment and a dye, an extender pigment, a solvent, a stabilizer, a plasticizer, a catalyst, a curing agent and the like in a binder resin is used.
There is no particular limitation on the binder resin, for example, acrylic resin, styrene resin, polyester resin, urethane resin, chlorinated polyolefin resin, vinyl chloride-vinyl acetate copolymer resin, polyvinyl butyral resin, alkyd resin And petroleum resins, ketone resins, epoxy resins, melamine resins, fluorine resins, silicone resins, cellulose derivatives, rubber resins, and the like. These resins can be used alone or in combination of two or more.

  The thickness of the picture layer can be appropriately adjusted in the range of about 0.1 to 20 μm in consideration of the form of the picture layer and the intended design. The picture layer may contain additives such as an antioxidant and an ultraviolet absorber as long as the effects of the present invention are not impaired.

Surface protective layer The printed matter of the present invention preferably has a surface protective layer on the outermost surface on the side having the glossy print layer. By forming the surface protective layer, the scratch resistance and weather resistance of the printed matter can be improved. For this effect, the surface protective layer is preferably formed so as to cover the entire area of the glossy print layer and the picture layer provided as necessary, and more preferably to be formed so as to cover the entire area of the hard coat layer. preferable.

The surface protective layer is preferably formed from a curable resin. From this viewpoint, the surface protective layer is preferably a cured layer of the thermosetting resin composition, but is more preferably a cured layer of the ultraviolet curable resin composition.
When the surface protective layer is formed from an ultraviolet-curable resin composition, the surface protective layer can be instantaneously cured by irradiation with ultraviolet light. It is possible to suppress the following of the irregularities of the high frequency component of the picture layer, etc., and to increase the metallic luster on the surface of the surface protective layer. On the other hand, before the ultraviolet curable resin composition is irradiated with ultraviolet rays (until the curing of the ultraviolet curable resin composition starts), the surface shape of the surface protective layer is a lower layer (for example, a gloss print layer or the like). Appropriately follows irregularities of low frequency components. For this reason, the surface protection layer will maintain the irregularities of the low-frequency component in a small amount, and the surface of the surface protection layer is excessively smoothed, so that the reflected light in the regular reflection direction becomes too high, It is possible to prevent the viewer from feeling uncomfortable. In order to make it easier to achieve the above-mentioned effects, it is preferable that the ultraviolet curable resin composition does not contain a solvent.

As the UV-curable resin composition for forming the surface protective layer, the same UV-curable resin composition as exemplified for the glossy print layer can be used.
The surface protective layer preferably contains an ultraviolet absorber and / or a light stabilizer in order to improve weather resistance.
The UV-curable resin composition may contain a resin component (thermoplastic resin or thermosetting resin) other than the UV-curable compound. However, in order to easily achieve the above-described effects, the proportion of the ultraviolet curable compound in all the resin components of the ultraviolet curable resin composition is preferably 90% by mass or more, and more preferably 95% by mass or more. More preferably, it is even more preferably 100% by mass.

  The surface protective layer can be formed by applying an ink for a surface protective layer containing a UV-curable resin composition and a solvent to be added as necessary onto a substrate, drying the composition, and irradiating with ionizing radiation. When no solvent is contained in the ink for the surface protective layer, drying is unnecessary.

  The thickness of the surface protective layer is preferably from 0.5 to 5.0 μm, and more preferably from 0.8 to 1.5 μm.

[container]
The container of the present invention uses the above-described printed matter of the present invention.
The container is not particularly limited, and includes a beverage container, a food container, and the like. The container of the present invention has excellent glossiness and excellent design. In addition, since curling of the printed matter is suppressed, it is possible to prevent occurrence of troubles due to curling in the manufacturing process of the container.

  Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

1. Measurement and Evaluation The printed matter produced in the examples and comparative examples was measured and evaluated as follows. The results are shown in Table 1 or Table 2.

1-1. Specular glossiness For the printed materials of Examples 1 to 6 and Comparative Examples 1 to 4 and the intermediates of the printed materials, using a micro-TRI-gloss of BYK Gardner as a measuring device, a mirror surface at 60 degrees of JIS Z8741: 1997. The gloss was measured.

1-2. Surface roughness PPS
For the printed matter of Examples 1 to 6 and the intermediate of the printed matter, the surface roughness of the surface of the hard coat layer was measured using a Parker Print-Surf model Ver. 58-06-00 manufactured by TESTING MACHINES INC. As a measuring instrument. The PPS was measured according to JIS P8151: 2004.

1-3. Curl For the printed materials of Examples 1 to 6 and Comparative Examples 1 to 3, JAPAN TAPPI No. The curl depth was measured under the conditions of a temperature of 25 ° C. and a humidity of 75% RH based on the “curl depth measuring method” of 15-1.

1-4. Surface roughness measurement (cutoff value 0.08mm, 0.25mm, 0.8mm)
Surfaces based on JIS B0601: 2001 when the cutoff values are 0.08 mm, 0.25 mm, and 0.8 mm for the surfaces of the glossy printed layers or vapor-deposited films of the printed materials of Examples 1 to 4 and Comparative Examples 1 to 3. The roughness was measured using a surface roughness measuring device (model number: SE2555N / manufactured by Kosaka Laboratory Co., Ltd.) under the following measurement conditions. The measurement of Ra was performed under the following measurement conditions using a trade name SE-340 manufactured by Kosaka Laboratory Co., Ltd.
[Stylus of surface roughness detector]
SE2555N (trade name: 2 μm, apex angle: 90 degrees, material: diamond) manufactured by Kosaka Laboratory Co., Ltd.
[Measurement conditions of surface roughness measuring instrument]
・ Evaluation length (reference length): 5 times the cutoff value λc ・ Feeding speed of the stylus: 0.5 mm / s
・ Spare length: (cut-off value λc) × 2
-Vertical magnification: 2000 times-Horizontal magnification: 10 times

2. Production of printed matter [Example 1]
The ink 1 for a hard coat layer having the following formulation was applied to the entire coated surface side of the substrate (single-sided ivory paper having a basis weight of 235 g / m ² ) so that the thickness after drying was 6 μm, dried, and irradiated with ultraviolet rays. Then, a hard coat layer (a cured product layer of the ionizing radiation-curable resin composition) was formed.
Next, the gloss printing layer ink 2 having the following formulation was applied to the entire surface of the hard coat layer so that the thickness after drying was 0.30 μm, and dried to form a gloss printing layer. Obtained. In addition, the thickness of the region of the glossy printed layer of Example 1 where metal flakes were not substantially present was 0.20 μm, and the thickness of the metal flake unevenly distributed region was 0.10 μm.

<Ink for hard coat layer 1>
-70 parts of ionizing radiation-curable compound (BASF Japan, trade name: Lumogen OVD Primer301)
(Mixture of bifunctional acrylate monomer and trifunctional acrylate monomer)
・ Solvent (ethyl acetate) 30 parts

<Ink 2 for glossy print layer>
4.8 parts of binder resin (nitrified cotton) (manufactured by DIC Graphics)
(Product name: XS-763 Medium NT-No. 1)
・ 7.2 parts of aluminum scale (average length 14 μm, average thickness 0.04 μm)
・ Solvent (ethyl acetate, IPA, ethanol, NPAC) 88 parts

[Example 2]
A printed material of Example 2 was obtained in the same manner as in Example 1 except that the thickness of the glossy print layer was changed to 0.50 μm. The thickness of the gloss-printed layer of Example 2 where the metal scale was substantially absent was 0.30 μm, and the thickness of the metal scale uneven distribution area was 0.20 μm.

[Example 3]
A printed material of Example 3 was obtained in the same manner as in Example 1 except that the thickness of the glossy print layer was changed to 0.70 μm. The thickness of the glossy print layer of Example 3 in the region where metal flakes were not substantially present was 0.42 μm, and the thickness of the metal flake unevenly distributed region was 0.28 μm.

[Example 4]
A printed material of Example 4 was obtained in the same manner as in Example 1 except that the thickness of the glossy print layer was changed to 1.00 μm. In addition, the thickness of the region of the glossy print layer of Example 3 where metal flakes were not substantially present was 0.60 μm, and the thickness of the metal flake unevenly distributed region was 0.40 μm.

[Example 5]
A printed matter of Example 5 was obtained in the same manner as in Example 1 except that the thickness of the hard coat layer was changed to 5 μm and the thickness of the glossy print layer was changed to 1.0 μm. The thickness of the region of the glossy print layer of Example 5 where metal flakes were not substantially present was 0.60 μm, and the thickness of the metal flake unevenly distributed region was 0.40 μm.

[Example 6]
A printed material of Example 6 was obtained in the same manner as in Example 5, except that the substrate was coated cardboard (basis weight: 350 g / m ² ).

[Comparative Example 1]
The ink 2 for the glossy printing layer of Example 1 was changed to the ink 3 for the glossy printing layer having the following formulation, and was applied so that the thickness after drying was 1.5 μm, and the ink 1 for the hard coat layer was applied to the substrate. A printed material of Comparative Example 1 was obtained in the same manner as in Example 1 except that the printing was not performed.
<Ink 3 for glossy print layer>
・ 6 parts of binder resin (nitrified cotton) (manufactured by DIC Graphics)
(Product name: XS-763 Medium NT-No. 1)
-6 pieces of aluminum pieces (Toyo Aluminum Co., Ltd., trade name: TD-180T)
(Average length 15 μm, average thickness more than 0.2 μm)
・ Solvent (ethyl acetate, IPA, ethanol, NPAC) 88 parts

[Comparative Example 2]
A vapor deposition film having a 50 nm-thick aluminum vapor-deposited film was prepared on a 12 μm-thick biaxially stretched PET film. The surface on the coated side of the base material (single-sided ivory paper having a basis weight of 235 g / m ² ) and the surface on the PET film side of the vapor-deposited film were formed by sand lamination to form a low-density polyethylene (LDPE) having a thickness of 15 μm. The printed material of Comparative Example 2 was obtained while being extruded so as to obtain a printed material (not a printed material, but referred to as a printed material for convenience).

[Comparative Example 3]
The ink 1 for the hard coat layer of Example 1 was changed to a thermoplastic resin 1 having the following formulation, and extruded using an extrusion coating method to a thickness of 15 μm, and the ink 1 for the hard coat layer was not applied to the substrate. A printed matter of Comparative Example 3 was obtained in the same manner as in Example 1 except for the above.
<Thermoplastic resin 1>
-Low density polyethylene resin (density: 0.923 g / cm ³ , melt index (MI): 3.8, melting point 109 ° C)

[Comparative Example 4]
On the coated side of the substrate (single-sided ivory paper having a basis weight of 235 g / m ^2), coated with a gloss print layer ink 2 at a coverage of 1 g / m ^2, and dried, to form a gloss print layer, Comparative Example 4 was obtained. In the printed matter of Comparative Example 3, the ink soaked into the base material, and it was difficult to determine the thickness after drying.

From the results shown in Table 1, it can be seen that the printed materials of Examples 1 to 6 have excellent metallic luster of 150% or more in specular gloss without using a metal vapor deposition means.
On the other hand, the printed matter of Comparative Example 1 was inferior in specular gloss (metallic gloss) because no metallic scale was used. The printed matter of Comparative Example 2 had excellent specular gloss (metallic luster) because of the use of vapor-deposited PET, but was curled. Further, the printed matter of Comparative Example 2 had an excessively high specular gloss (metallic gloss), which caused discomfort to the viewer. The printed matter of Comparative Example 3 had a glossy print layer containing metal flakes, but the thermoplastic resin layer disposed below the glossy print layer did not exhibit the effect of the hard coat layer, so that the mirror glossiness was low. (Metallic luster) could not be increased. The printed matter of Comparative Example 4 had a glossy print layer containing metal scales, but did not have a hard coat layer below the glossy print layer, so that the solvent and the resin were applied to the substrate when the glossy print layer was formed. It was soaked that the specular gloss (metallic luster) could not be increased.

  In addition, from the results in Table 2, it can be confirmed that Ra is equal to the glossy printed layer of the printed matter of Examples 1 to 4 and the vapor deposition film of the printed matter of Comparative Example 2. This indicates that the glossy printed layers of Examples 1 to 4 have the same smoothness as the metal deposited film.

[Example 7]
A picture layer was formed by gravure printing at an arbitrary position on the glossy printed layer of the printed matter obtained in Example 2. Next, the surface protective layer ink 4 having the following formulation is applied to the entire surface of the outermost surface of the printed matter so as to have a thickness of 1.0 μm after drying, and irradiated with ultraviolet rays to form a surface protective layer (solvent-free ultraviolet curable type). A cured product layer of a resin composition) was formed to obtain a printed material of Example 7.
<Surface protective layer ink 4 (solvent-free type)>
・ 100 parts of UV curable compound (manufactured by DIC Graphics, trade name: UV clear low odor coat varnish S)
・ Solvent 0 parts

  The printed matter of Example 7 was able to further improve the design property while maintaining the metallic luster of the glossy print layer.

  INDUSTRIAL APPLICABILITY The printed matter and the container of the present invention are useful in that high metallic luster can be imparted without using metal deposition means.

1: base material 2: hard coat layer 3: gloss print layer 31: metal scale uneven distribution area 4: picture layer 5: surface protective layer 10: printed matter

Claims (15)

A hard coat layer at an arbitrary position on the substrate, further comprising a gloss print layer at an arbitrary position on the hard coat layer, wherein the gloss print layer contains metal flakes, and the gloss print layer Printed matter, wherein the metal scales are unevenly distributed on the upper part of the sheet, and the hard coat layer is a cured layer of the ionizing radiation-curable resin composition containing no pigment . The printed matter according to claim 1, wherein the average length and the average thickness of the metal scale satisfy the following condition (1).
Average thickness of metal scale / average length of metal scale ≦ 0.010 (1) The printed matter according to claim 1 or 2, wherein the average length of the metal scale and the thickness of the glossy print layer satisfy the following condition (2).
10 ≦ [average length of metal scale / thickness of glossy printed layer] (2) The printed matter according to any one of claims 1 to 3, wherein the average length of the metal scale is 5.0 to 30.0 µm. The printed matter according to any one of claims 1 to 4, wherein an average thickness of the metal scale is 0.10 µm or less. The printed matter according to any one of claims 1 to 5, wherein the glossy print layer has a thickness of 0.15 to 1.50 µm. The printed matter according to any one of claims 1 to 6, wherein a picture is formed by the glossy print layer. The printed matter according to any one of claims 1 to 7, wherein the surface of the hard coat layer has a specular glossiness at 60 degrees of JIS Z8741: 1997 of 85% or more. The printed matter according to any one of claims 1 to 8, wherein the surface of the hard coat layer has a surface roughness PPS according to JIS P8151: 2004 of less than 1 µm.   The printed matter according to any one of claims 1 to 9, wherein the base material is a paper base material. The substrate is the paper substrate, and the surface of the glossy print layer is JIS Z8741: 1997.
The printed matter according to claim 10, wherein the specular gloss at 60 degrees is 150% or more. The pattern layer according to any one of claims 1 to 11, wherein a picture layer is provided at an arbitrary position on the gloss print layer and / or the hard coat layer where the gloss print layer is not formed. Printed matter. The surface protective layer is provided on the outermost surface on the side having the glossy print layer.
Printed matter described in item. The printed matter according to any one of claims 1 to 13, wherein a value of the following formula (3) indicating a thickness ratio of the uneven distribution region of the metal scale in the glossy print layer is 10 to 60%.
[Thickness of uneven distribution region of metal scale / thickness of glossy print layer] × 100 (3) A container using the printed matter according to any one of claims 1 to 14 .