JP6620518B2 - Printed matter and container using the printed matter - Google Patents

Description

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

  Conventionally, various printed materials may be required to have a metallic luster in order to improve their design properties.

  As one means for imparting metallic luster, a film having metallic luster is used. For example, a substrate having a metallic luster is produced by bonding a film having a metallic luster on a paper substrate, and a printed layer having a metallic luster is produced by printing a pattern layer or the like on the substrate.

However, a film having metallic luster is formed by forming a metal vapor-deposited film on the film, and thus requires a cost and is not suitable for an inexpensive printed matter. Furthermore, the substrate with a metallic gloss film laminated on a paper substrate is curled due to the difference in shrinkage between the paper and the film, and the subsequent process (for example, the printing process on the substrate, the printed product in the container). There is a problem that the accuracy of the processing step) is lowered and the yield is lowered.
In order to solve the above problem, Patent Document 1 is proposed.

JP 2003-2323 A

  Patent Document 1 discloses a paper container in which a printed layer having a metallic gloss region 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 with respect to cost and curl. However, the paper container of Patent Document 1 has a certain level of metallic luster, but does not have a high level of metallic luster.

  An object of this invention is to provide the printed matter and container which have high metallic luster, without using the means of metal vapor deposition.

In order to solve the above problems, the present invention provides the following printed materials and containers [1] to [18].
[1] Arithmetic average roughness of JIS B0601: 2001 when a glossy printed layer containing metal scales is present at an arbitrary position on the substrate, and the cut-off value of the surface of the glossy printed layer is 0.08 mm Ra _0.08 ) satisfies the following condition (1).
Ra _0.08 ≦ 0.100 μm (1)
[2] Ra _0.08 and the arithmetic average roughness (Ra _0.25 ) of JIS B0601: 2001 when the cut-off value of the surface of the glossy printed layer is 0.25 mm are as follows: Printed material of [1] that satisfies 2).
0.300 <Ra _0.08 / Ra _0.25 <0.500 (2)
[3] The skewness (Rsk _0.08 ) of the roughness curve of JIS B0601: 2001 when the cut-off value on the surface of the glossy print layer is 0.08 mm, and the cut-off value on the surface of the glossy print layer Printed matter according to [1] or [2], wherein the skewness (Rsk _0.25 ) of the roughness curve of JIS B0601: 2001 when the thickness is 0.25 mm satisfies the following conditions (3) and (4).
0.200 <Rsk _0.25− Rsk _0.08 <0.500 (3)
0 <Rsk _0.25 (4)
[4] The printed material according to any one of [1] to [3], wherein an average length of the metal scale and an average thickness of the glossy printed layer satisfy the following condition (5).
10 ≦ [average length of metal scale / thickness of glossy printed layer] (5)
[5] The printed matter according to any one of [1] to [4], wherein the average length of the metal scale is 5.0 to 30.0 μm.
[6] The printed material according to any one of [1] to [5], wherein the average thickness of the metal scale is 0.10 μm or less.
[7] The printed matter according to any one of [1] to [6], wherein the glossy printed layer has a thickness of 0.15 to 1.50 μm.
[8] The printed matter according to any one of [1] to [7], wherein the metal scale is unevenly distributed above the glossy printed layer.
[9] The printed material according to any one of [1] to [8], wherein a pattern is formed by the glossy printed layer.
[10] The printed matter according to any one of [1] to [9], which has a hard coat layer between the substrate and the glossy printed layer.
[11] The printed matter according to [10], wherein the surface of the hard coat layer has a specular glossiness at 60 degrees of JIS Z8741: 1997 of 85% or more.
[12] The printed material according to [10] or [11], wherein the surface roughness PPS of the surface of the hard coat layer in JIS P8151: 2004 is less than 1 μm.
[13] The printed matter according to any one of [10] to [12], wherein the hard coat layer is a cured product layer of an ionizing radiation curable resin composition.
[14] The printed material according to any one of [1] to [13], wherein the substrate is a paper substrate.
[15] The printed material according to [14], wherein the base material is the paper base material, and a mirror glossiness at 60 degrees of JIS Z8741: 1997 of the surface of the glossy printed layer is 150% or more.
[16] The printed material according to any one of [1] to [15], which has a pattern layer on the glossy printed layer.
[17] The printed matter according to any one of [1] to [16], which has a surface protective layer on the outermost surface on the side having the glossy printed layer.
[18] A container using the printed material according to any one of [1] to [17].

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

It is sectional drawing which shows one Embodiment of the printed matter of this invention. It is sectional drawing which shows other embodiment of the printed matter of this invention.

[Printed matter]
The printed matter of the present invention has a glossy printed layer containing metal scales at an arbitrary position on the substrate, and the arithmetic average roughness of JIS B0601: 2001 when the cut-off value of the surface of the glossy printed layer is 0.08 mm. (Ra _0.08 ) satisfies the following condition (1).
Ra _0.08 ≦ 0.100 μm (1)

Hereinafter, embodiments of the printed matter of the present invention will be described.
FIG.1 and FIG.2 is sectional drawing which shows one Embodiment of the printed matter 10 of this invention. The printed matter 10 in FIGS. 1 and 2 has a hard coat layer 2 and a glossy printed layer 3 in this order on a substrate 1. The printed matter in FIG. 2 further has a pattern layer 4 and a surface protective layer 5 on the glossy printed layer 3. Moreover, the glossy printed layer 3 of the printed matter 10 in FIGS. 1 and 2 has an upper metal scale unevenly distributed region 31.

Surface Condition of Glossy Print Layer In the printed matter of the present invention, the surface of the glossy print layer satisfies the above condition (1). Condition (1) defines the arithmetic average roughness (Ra) of JIS B0601: 2001 when the cutoff value is 0.08 mm.
The cut-off value indicates the degree to which the swell component (medium frequency component, low frequency component) is cut from the cross-sectional curve composed of the roughness component (high frequency component) and the swell component (medium frequency component, low frequency component). This is the value shown. In other words, the cutoff value is a value indicating the fineness of the filter that cuts the swell component (medium frequency component, low frequency component). More specifically, when the cut-off value is large, the filter is coarse, so that a large swell of the swell components (medium frequency component, low frequency component) is cut, but a small swell is not cut. That is, when the cut-off value is large, the value includes a swell component (medium frequency component, low frequency component). On the other hand, if the cut-off value is small, the filter is fine, so that most of the swell component (medium frequency component, low frequency component) is cut. In other words, when the cut-off value is small, the roughness component (high frequency component) is accurately reflected with almost no swell component (medium frequency component, low frequency component).
Hereinafter, a roughness component having a cutoff value of 0.08 mm may be referred to as a high frequency component, a swell component having a cutoff value of 0.25 mm may be referred to as a medium frequency component, and a swell component having a cutoff value of 0.8 mm may be referred to as a low frequency component.

Condition (1) requires that Ra _0.08 (Ra of the high frequency component) is 0.100 μm or less. When the condition (1) is not satisfied, the ratio of the reflected light in the regular reflection direction out of the reflected light on the surface of the glossy printed layer is reduced, and the metallic gloss is lowered.
In the condition (1), the lower limit of Ra _0.08 is not particularly limited, if Ra _0.08 is a predetermined value or more, suppresses a decrease in visibility due to the regular reflection direction of the reflected light becomes too strong be able to. From such a viewpoint, the condition (1) more preferably satisfies 0.010 μm ≦ Ra _0.08 ≦ 0.070 μm, and more preferably satisfies 0.020 μm ≦ Ra _0.08 ≦ 0.050 μm.

The printed matter of the present invention has a Ra _0.08 and an arithmetic average roughness (Ra _0.25 ) of JIS B0601: 2001 when the cut-off value of the surface of the glossy printed layer is 0.25 mm. It is preferable to satisfy (2).
0.300 <Ra _0.08 / Ra _0.25 <0.500 (2)

Condition (2) defines the ratio between Ra _0.08 (Ra of the high frequency component) and Ra _0.25 (Ra of the medium frequency component). That is, the condition (2) means that not only the high frequency component Ra but also a predetermined medium frequency component Ra exists on the surface of the glossy print layer.
Satisfying the condition (2) is preferable because Ra of a low frequency component is appropriately present and the reflection intensity of the specular reflection light is suppressed from becoming too strong, and it is possible to prevent the viewer from feeling uncomfortable.
Condition (2) more preferably satisfies 0.300 <Ra _0.08 / Ra _0.25 <0.500, and satisfies 0.300 <Ra _0.08 / Ra _0.25 <0.450. Is more preferable.

The printed matter of the present invention has an Ra _0.08 and an arithmetic average roughness (Ra _0.8 ) of JIS B0601: 2001 when the cut-off value of the surface of the glossy printed layer is 0.8 mm under the following conditions: It is preferable to satisfy (2 ′).
0.050 <Ra _0.08 / Ra _0.8 <0.200 (2 ′)

The condition (2 ′) defines the ratio between Ra _0.08 (Ra of high frequency component) and Ra _0.8 (Ra of low frequency component). That is, the condition (2 ′) means that not only the high-frequency component Ra but also a predetermined low-frequency component Ra exists on the surface of the glossy printed layer.
Satisfying the condition (2 ′) is preferable because Ra of the medium frequency component is moderately present and the reflection intensity of the specularly reflected light is suppressed from becoming too strong, thereby preventing the viewer from feeling uncomfortable. .
The condition (2 ′) more preferably satisfies 0.075 <Ra _0.08 / Ra _0.8 <0.180, and satisfies 0.090 <Ra _0.08 / Ra _0.8 <0.160. More preferably.

The printed matter of the present invention has the skewness (Rsk _0.08 ) of the roughness curve of JIS B0601: 2001 and the cutoff value of the surface of the glossy printed layer when the cutoff value of the surface of the glossy printed layer is 0.08 mm. It is preferable that the skewness (Rsk _0.25 ) of the roughness curve of JIS B0601: 2001 when the thickness is 0.25 mm satisfies the following conditions (3) and (4).
0.200 <Rsk _0.25− Rsk _0.08 <0.500 (3)
0 <Rsk _0.25 (4)

The printed matter of the present invention has the skewness (Rsk _0.08 ) of the roughness curve of JIS B0601: 2001 and the cutoff value of the surface of the glossy printed layer when the cutoff value of the surface of the glossy printed layer is 0.08 mm. It is preferable that the skewness (Rsk _0.8 ) of the roughness curve of JIS B0601: 2001 when 0.8 mm satisfies the following conditions (3 ′) and (4 ′).
0.050 <Rsk _0.8 −Rsk _0.08 <0.700 (3 ′)
0 <Rsk _0.5 (4 ′)

The skewness (Rsk) of the roughness curve is an index indicating how much the height distribution of the surface composed of convex portions (crests) and concave portions (valleys) deviates from the normal distribution. For example, the value is zero, the value is negative on the surface where the concave portion is dominant, and the value is positive on the surface where the convex portion is dominant.
By satisfying the conditions (3), (4), (3 ′), and (4 ′), the high-frequency component that does not have the convex portion extremely is added to the medium-frequency component and the low-frequency component where the convex portion is moderately dominant Since it is not superposed, it has a metallic luster and a surface having appropriate diffusion with good visibility.

  In the present invention, the conditions (1) to (4), (3 ′), and (4 ′) are average values when ten measurements are performed.

The material of the base material is not particularly limited as long as it is a material conventionally used for printed matter, etc., and specifically, fine paper, medium paper, coated paper, synthetic paper, impregnated paper, laminated paper Paper such as coated paper for printing and coated paper for recording, polyethylene terephthalate film, polyethylene film, polypropylene film, plastic film such as polycarbonate film, or a composite of these.
In the present invention, even when any base material is used, a high metallic luster can always be realized by having a hard coat layer described later on the base material.

The thickness of the substrate is not particularly limited, but in the case of a paper substrate, the basis weight is usually about 150 to 550 g / m ² , and in the case of a plastic film substrate, it is usually about 9 to 50 μm.

Hard Coat Layer In the present invention, the metal gloss of the glossy printed layer can be made sufficiently high by interposing the hard coat layer between the substrate and the glossy printed layer. The reason is considered as follows.
First, the hard coat layer is difficult to penetrate the solvent for the ink for the glossy printing layer. For this reason, when the ink for the glossy printed layer is applied on the hard coat layer and dried, the solvent hardly flows below the glossy printed layer. On the other hand, the solvent tends to flow above the glossy printed layer when the solvent volatilizes during the drying process. Then, it is considered that the metal scales float above the glossy printed layer along with the flow of the solvent, the metal scales are unevenly distributed on the glossy printed layer, and the glossiness of the glossy printed layer can be sufficiently increased.
Moreover, although the base material mentioned above has the difference in a grade according to a kind, the surface is rough. For example, paper has a rough surface due to fibers. When the glossy printed layer is formed when the substrate surface is rough as described above, the surface of the glossy printed layer is also roughened, and the metal gloss cannot be sufficiently increased. It is considered that by reducing the roughness of the surface, it is possible to suppress the surface of the glossy printed layer from becoming rough and to sufficiently increase the metallic gloss.
Moreover, when the surface of a base material is damaged, the unevenness | corrugation of a damage | wound is reflected on the surface of a glossy printing layer, and the metallic luster of a glossy printing layer will fall. However, since the surface of the substrate composed of the base material and the hard coat layer is hard to be damaged, it is considered that unevenness due to scratches is reflected on the surface of the glossy printed layer, and the metallic gloss of the glossy printed layer can be sufficiently increased. .

  The hard coat layer is preferably formed at least at a location corresponding to a location where a glossy print layer described later is formed. In addition, from the viewpoint of eliminating the troublesome alignment between the hard coat layer and the glossy print layer, the hard coat layer is preferably provided on the entire surface of the substrate where the gloss print layer is formed. Moreover, it is preferable to form a hard-coat layer on the whole surface of a base material from a viewpoint which makes the physical property of the base | substrate which consists of a base material and a hard-coat layer uniform, and suppresses a deformation | transformation of a base | substrate.

  It is preferable that the surface of the hard coat layer (the surface opposite to the base material of the hard coat layer) is 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 does not easily penetrate into the hard coat layer, so that metal scales are easily unevenly distributed on the upper part of the glossy printed layer, and the glossy printed layer has a sufficient metallic luster. Can be high. Further, when the surface of the hard coat layer is rough, the unevenness of the hard coat layer is reflected in the glossy print layer, and the surface of the gloss print layer is also roughened. On the other hand, when the surface of the hard coat layer is smoothed, the surface of the glossy printed layer is also smoothed, and the above-described surface shape is easily obtained.

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

  In the hard coat layer, the surface roughness PPS of the hard coat layer is preferably less than 1 μm and more preferably 0.6 μm or less in the measurement based on JIS P8151: 2004. By making the surface roughness PPS of the surface less than 1 μm, the above-mentioned effects can be exhibited more remarkably.

Further, the arithmetic average roughness Ra (Ra _0.08HA ) of JIS B0601: 2001 on the hard coat layer surface 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 0.040 μm or less.
If the hard coat layer contains a lot of irregularities of high frequency components, the surface area of the hard coat layer will increase and the solvent will penetrate easily. _Therefore , it is preferable that Ra _0.08HA is within the above range.

The arithmetic average roughness Ra (Ra _0.25HA ) of JIS B0601: 2001 on the hard coat layer surface when the cut-off value is 0.25 mm is preferably 0.200 μm or less, and is 0.175 μm or less. More preferably, it is 0.150 μm or less.
Further, 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 0.350 μm or less.
The unevenness of the medium frequency component and the low frequency component is not as large as the unevenness of the high frequency component, but increases the surface area. For this reason, it is suitable to make Ra _0.25HA and Ra _0.8HA into the said range. If the irregularities of the low frequency component of the hard coat layer disappear, the irregularities due to the irregularities of the low frequency component of the hard coat layer cannot be formed on the surface of the glossy printed layer, and the glossy printed layer is excessively smoothed. There is a tendency. In this case, the reflected light in the specular reflection direction of the glossy printed layer becomes too strong, which causes discomfort to the viewer. For this reason, Ra _0.25HA is preferably 0.050 μm or more, and more preferably 0.100 μm or more. Ra _0.8HA is preferably 0.100 μm or more, and more preferably 0.200 μm or more.

Furthermore, JIS B0601: 2001 arithmetic average roughness Ra (Ra _0.08BA ) of the substrate surface when the cut-off value is 0.08 mm, and JIS of the substrate surface when the cut-off value is 0.25 mm It is preferable that the arithmetic average roughness Ra (Ra _0.25BA ) of B0601: 2001, Ra _0.08HA and Ra _0.8HA 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 average roughness Ra (Ra _0.08BA ) of the substrate surface when the cut-off value is 0.08 mm, and JIS of the substrate surface when the cut-off value is 0.8 mm It is preferable that the arithmetic average roughness Ra (Ra _0.8BA ) of B0601: 2001, Ra _0.08HA and Ra _0.8HA satisfy the following condition (a ₂ ).
[Ra _0.8HA / Ra _0.8BA ]> [Ra _0.08HA / Ra _0.08BA ] (a ₂ )
The ratio of Ra of the hard coat layer and Ra of the base material indicates the degree to which the hard coat layer relaxes the unevenness of the base material. The above conditions (a ₁ ) and (a ₂ ) indicate that the hard coat layer has a higher degree of relaxation of the high frequency component than the degree of relaxation of the low frequency component of the unevenness of the substrate. Yes.
As described above, increasing the surface area of the hard coat layer is greatly affected by the unevenness of the high-frequency component. For this reason, it is preferable that a hard-coat layer eases the unevenness | corrugation of the high frequency component of a 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 regular reflection direction of the glossy printed layer may become too strong. Therefore, satisfying the above conditions (a ₁ ) and (a ₂ ) indicating that the degree of relaxation of the high-frequency component is larger than the degree of relaxation of the low-frequency component of the unevenness of the substrate has a great significance. is there.

In order to make the above effect easier to _exhibit , it is preferable that the Ra _0.08HA , Ra _0.25HA , Ra _0.08BA , and Ra _0.25BA satisfy the following condition (b ₁ ).
1.5 ≦ [Ra _0.25HA / Ra _0.25BA ] / [Ra _0.08HA / Ra _0.08BA ] (b ₁ )
More preferably, the condition (b ₁ ) _satisfies 1.5 ≦ [Ra _0.25HA / Ra _0.25BA ] / [Ra _0.08HA / Ra _0.08BA ] ≦ 4.0, and 1.5 ≦ [ More preferably, Ra _0.25HA / Ra _0.25BA ] / [Ra _0.08HA / Ra _0.08BA ] ≦ 3.5 is satisfied.
Furthermore, in order to make the above effects easier to _exhibit , it is preferable that the Ra _0.08HA , Ra _0.8HA , Ra _0.08BA , and Ra _0.8BA satisfy the following condition (b ₂ ).
1.8 ≦ [Ra _0.8HA / Ra _0.8BA ] / [Ra _0.08HA / Ra _0.08BA ] (b ₂ )
The condition (b ₂ ) preferably satisfies 2.2 ≦ [Ra _0.8HA / Ra _0.8BA ] / [Ra _0.08HA / Ra _0.08BA ] ≦ 4.0, and 2.5 ≦ [ More preferably, Ra _0.8HA / Ra _0.8BA ] / [Ra _0.08HA / Ra _0.08BA ] ≦ 3.5 is satisfied.

Specific examples of the hard coat layer include a cured product layer of an ionizing radiation curable resin composition (hereinafter sometimes referred to as “cured product layer”), a clay coat layer, and the like. From the viewpoint of making the penetration preventing property better, it is preferably a cured product layer of an ionizing radiation curable resin composition.
Furthermore, when the hard coat layer is formed from an ionizing radiation curable resin composition, the hard coat layer can be instantaneously cured by irradiation with ionizing radiation. Can be prevented from following the unevenness of the high-frequency component of the substrate. In other words, when the hard coat layer is formed from the ionizing radiation curable resin composition, the unevenness of the high-frequency component of the substrate can be alleviated by the hard coat layer. 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 irregularities of the low frequency component of the substrate. That is, when the hard coat layer is formed from an ionizing radiation curable resin composition, the surface of the hard coat layer can be shaped to have moderate low frequency component irregularities while suppressing irregularities of high frequency components, The effects described above (suppression of solvent penetration into the hard coat layer, maintenance of the texture of the base material, etc.) can be easily exhibited.

The ionizing radiation curable resin composition for forming the cured product layer cured product layer contains a compound having an ionizing radiation curable functional group (hereinafter sometimes referred to as “ionizing radiation curable compound”). It is. 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, an epoxy group, and an oxetanyl group. As the ionizing radiation curable compound, a compound having an ethylenically unsaturated bond group is preferable, a compound having two or more ethylenic unsaturated bond groups is more preferable, and among them, having two or more ethylenically unsaturated bond groups, Polyfunctional (meth) acrylate compounds are more preferred. 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 scratch resistance and penetration resistance due to high crosslinking density.
The ionizing radiation means an electromagnetic wave or a charged particle beam having an energy quantum capable of polymerizing or cross-linking molecules, and usually ultraviolet (UV) or electron beam (EB) is used. 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 polyfunctional (meth) acrylate monomers, bifunctional (meth) acrylate monomers include ethylene glycol di (meth) acrylate, bisphenol A tetraethoxydiacrylate, bisphenol A tetrapropoxydiacrylate, and 1,6-hexanediol. Examples include diacrylate.
Examples of the tri- or higher functional (meth) acrylate monomer include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, di Examples include pentaerythritol tetra (meth) acrylate and isocyanuric acid-modified tri (meth) acrylate.
The (meth) acrylate-based monomer may be modified by partially modifying the molecular skeleton, and is modified with ethylene oxide, propylene oxide, caprolactone, isocyanuric acid, alkyl, cyclic alkyl, aromatic, bisphenol, or the like. Can also be used.
2-6 are preferable and, as for the number of functional groups of a polyfunctional (meth) acrylate monomer, 2-3 are more preferable.

Moreover, 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 by reaction of polyhydric alcohol and organic diisocyanate with hydroxy (meth) acrylate, for example.
A preferable epoxy (meth) acrylate is a (meth) acrylate obtained by reacting (meth) acrylic acid with a tri- or higher functional aromatic epoxy resin, alicyclic epoxy resin, aliphatic epoxy resin or the like. (Meth) acrylates obtained by reacting the above aromatic epoxy resins, alicyclic epoxy resins, aliphatic epoxy resins and the like with polybasic acids and (meth) acrylic acid, and bifunctional or higher functional aromatic epoxy resins, It is a (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 can be used alone or in combination of two or more. The ionizing radiation curable compound preferably contains 50% by mass or more, more preferably 80% by mass or more of a polyfunctional (meth) acrylate monomer.

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-acyloxime ester, thioxanthones, and the like.
The photopolymerization accelerator can reduce polymerization inhibition by air during curing and increase the curing speed. For example, p-dimethylaminobenzoic acid isoamyl ester, p-dimethylaminobenzoic acid ethyl ester, etc. One or more selected may be 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 effect described above, the proportion of the ionizing radiation curable compound in the total resin components of the ionizing radiation curable resin composition is preferably 90% by mass or more, and 95% by mass or more. It is more preferable that the content is 100% by mass.

  The cured product layer preferably has a thickness of 2 μm or more from the viewpoint of smoothing the base material and preventing scratches. In addition, when the cured product layer is too thick, workability deteriorates, and thus 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. It is even more preferable.

  A hardened | cured material layer can be formed by apply | coating an ink for cured | curing material layers containing the ionizing radiation curable resin composition and the dilution solvent added as needed on a base material, drying, and ionizing radiation irradiation. In addition, drying is unnecessary when the solvent is not contained in the ink for cured | curing material layers.

Clay coat layer The clay coat 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, gyrome clay , Halloysite and the like 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 binder resins (eg, styrene butadiene latex, acrylic latex vinyl acetate latex), water-soluble binder resins (eg, starch (modified starch, oxidized starch, hydroxyethyl etherified starch, phosphoric acid). Esterified starch), polyvinyl alcohol, casein and the like.

The mass ratio of clay: pigment: binder resin in the clay coat layer is preferably 1-20: 50-90: 10-30.
The clay coat layer may contain additives such as pigment dispersants, antifoaming agents, antifoaming agents, viscosity modifiers, lubricants, water resistance agents, water retention agents, colorants, and printability improvers. Good.

  The thickness of the clay coat layer is preferably 5 to 40 μm, more preferably 10 to 30 μm, and more preferably 15 to 25 μm, from the viewpoint of smoothing the base material, preventing scratches and workability. Further preferred.

  The clay coat layer can be formed by applying and drying a clay coat layer ink obtained by diluting a material constituting the clay coat layer in a solvent on a substrate.

Glossy Print Layer The glossy print layer is a layer located on the hard coat layer, and is formed by printing a glossy print layer ink. Thus, by forming the layer which gives metallic luster not by vapor deposition but by printing, the cost can be reduced and the occurrence of curling can be suppressed.
The glossy printed layer is preferably formed in contact with the hard coat layer. In addition, as shown in FIG. 1, the gloss printed layer is formed in a desired pattern in a partial area on the hard coat layer, and a pattern such as letters, numbers, figures, symbols, landscapes, persons, animals, characters, etc. It may be formed or may be formed in the entire region on the hard coat layer as shown in FIG.

  Moreover, in this invention, it is required to include a metal scale in a glossy printed layer. It is preferable that the metal scale is unevenly distributed on the upper part of the glossy printed layer (the side opposite to the hard coat layer of the glossy printed layer). When the metal scales are unevenly distributed on the glossy printed layer, the metallic gloss can be increased, and the adhesion between the glossy printed layer and the hard coat layer can be improved.

  The metal scale can be unevenly distributed on the upper part of the glossy printed layer in the process of forming the glossy printed layer. More specifically, when the solvent for the glossy printing layer ink volatilizes during the heat drying process of the glossy printing layer, the solvent flows upward. And it is thought that a metal scale floats with the flow of a solvent, and a metal scale is unevenly distributed in the upper part of a glossy printed layer. In particular, in the present invention, since the hard coat layer in which the solvent does not easily penetrate is located in the lower layer of the glossy printing layer, the flow of the solvent can be suppressed downward, and the solvent flows almost upward. It is thought that metal scales are likely to be unevenly distributed. In particular, when the hard coat layer is a cured product layer of the ionizing radiation curable resin composition, it is considered that the uneven distribution of the 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 checking the density difference in the glossy printed layer of the photographed image. More specifically, the unevenly-distributed portion of the metal scale is observed white because the reflection of electrons is remarkable, and the portion substantially not containing the metal scale is observed in gray.
The ratio of the thickness of the unevenly distributed area of the metal scale in the glossy printed layer [(the thickness of the unevenly distributed area of the metal scale / total thickness of the glossy printed layer)] is 10 to 60% from the viewpoint of the balance between the metallic gloss and the adhesiveness. It is preferably 20 to 50%, more preferably 25 to 45%.

It is preferable that the metal scale satisfies the following condition (5).
Average thickness of metal scale / average length of metal scale ≦ 0.010 (5)
By setting [the average thickness of the metal scale / the average length of the metal scale] to 0.010 or less, when the ink for the glossy printing layer is applied, the glossy printing layer in the horizontal direction (perpendicular to the thickness direction of the glossy printing layer) The metal scales are less likely to tilt with respect to the direction of For this reason, when the solvent flows above the glossy printed layer during the gloss printing drying process, the metal scales are easily subjected to the force of the solvent flow, and the metal scales are likely to be unevenly distributed above the glossy printed layer. Since the scales are easily arranged in parallel, the metallic luster can be easily improved. In addition, the adverse effects caused by the inclination of the metal scale increase with the increase in the content of the metal scale, but when the above condition (5) is satisfied, the metal scale is difficult to tilt, so that the content of the metal scale is increased. It is easy to improve the metallic luster.
In addition, when the average thickness of a metal scale becomes thin too much with respect to the average length of a metal scale, a handleability may become difficult or sufficient metal luster may not be expressed.
Therefore, the condition (5) preferably satisfies 0.001 ≦ average thickness of metal scale / average length of metal scale ≦ 0.01, and 0.002 ≦ average thickness of metal scale / average length of metal scale. It is more preferable to satisfy | fill thickness <= 0.008, and it is still more preferable to satisfy | fill 0.002 <= average thickness of a metal scale / average length of a metal scale <= 0.005.

In addition, at the time of applying the ink for the glossy printed layer, from the viewpoint of suppressing the metal scale from tilting with respect to the horizontal direction of the glossy printed layer, and suppressing the metal scale from protruding from the surface of the glossy printed layer. The average length of the metal scale and the thickness of the glossy printed layer preferably satisfy the following condition (6).
10 ≦ average length of metal scale / thickness of glossy printed layer (6)
In addition, when [average length of metal scale / thickness of glossy printed layer] is too large, metal scale may protrude from the surface of the glossy printed layer. Therefore, condition (6) is: 12 ≦ average of metal scale It is more preferable to satisfy the length / thickness of the glossy printed layer ≦ 60, and it is further preferable to satisfy 25 ≦ average length of the metal scale / thickness of the glossy printed layer ≦ 50.

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

The average length of the metal scale is preferably 5.0 to 30.0 μm, more preferably 8.0 to 20.0 μm, from the viewpoints of dispersion suitability, uneven distribution, and arrangement of the metal scale.
Further, the average thickness of the metal scale is preferably 0.10 μm or less, more preferably 0.08 μm or less, and further 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 viewpoints of handleability and high metallic luster.

Let the average length and average thickness of a metal scale be an average value of 100 metal scales. In addition, the length and thickness of each metal scale can be measured by using a laser interference type three-dimensional shape analysis apparatus in a state where the metal scale is dispersed on a smooth substrate. The length of the individual metal scale means the maximum diameter when the individual metal scale is observed from a plane in an arbitrary direction, and the thickness of the individual metal scale is the thickness when the individual metal scale is observed from the cross-sectional direction. It means the maximum thickness. In addition, the maximum diameter when each metal scale is observed from a plane in an arbitrary direction is intended to unify the direction in which the maximum diameter of each metal scale is measured. For example, when the X-axis direction on the screen obtained by image processing of the measurement result of the three-dimensional shape analyzer is an arbitrary direction (measurement direction), the maximum diameter is measured in a direction parallel to the X-axis. Even if there is a maximum diameter in a direction that is not parallel to the X axis, it is not regarded as the maximum diameter.
Examples of the laser interference type three-dimensional shape analysis apparatus include a trade name “Shape Analysis Laser Microscope VK-X Series” manufactured by Keyence Corporation.

The glossy printed layer preferably further contains a binder resin.
Examples of the binder resin include polyester resins, urethane resins, epoxy resins, melamine resins, alkyd resins, thermoplastic resins such as phenol resins, acrylic resins, and cellulose resins, and thermosetting resins. Moreover, you may use the hardened | cured material of the ultraviolet curable resin composition mentioned above as binder resin.

  The blending ratio of the binder resin and the metal scale is preferably 55:45 to 30:70, more preferably 50:50 to 35:65 in terms of solid content. By setting the metal scale to 45 or more with respect to the binder resin 55, it becomes easy to obtain a 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 printed layer, the printed matter Workability can be improved easily. In addition, in this invention, since it has a hard-coat layer under a glossy printing layer, even if it uses a lot of metal scales as mentioned above, a metal scale can be unevenly distributed on the upper part of a glossy print layer.

The thickness of the glossy printed layer is preferably 0.15 to 1.50 μm, more preferably 0.20 to 1.00 μm from the viewpoint of uneven distribution and arrangement of the metal scales and the concealability. 0.25 to 0.75 μm is more preferable.
In addition, the thickness of the glossy printed layer is measured at, for example, 20 thicknesses from a cross-sectional image taken using a scanning electron microscope (SEM), a transmission electron microscope (TEM), or a scanning transmission electron microscope (STEM). And it can calculate from the average value of the value of 20 places. 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 times.
The thickness of layers other than the glossy printed layer can also be measured by the same method as above.

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

  The specular glossiness at 60 degrees of JIS Z8741: 1997 on the surface of the glossy printed layer (surface opposite to the hard coat layer side of the glossy printed layer) is preferably 150% or more, and 200% or more. Is more preferable, and more preferably 250% or more. The upper limit of the specular gloss on the surface of the glossy printed layer is about 500%.

In addition, the arithmetic average roughness Ra (Ra _0.08GL ) of JIS B0601: 2001 on the surface of the glossy printed layer when the cut-off value is 0.08 mm is 0.100 μm or less from the viewpoint of metallic gloss. preferable. Note that Ra _0.08GL is preferably not too small from the viewpoint of improving visibility by suppressing reflection in the regular reflection direction. _{Therefore, Ra 0.08GL} is more preferably 0.010μm ≦ _{Ra 0.08GL} ≦ 0.070μm, more preferably from 0.020μm ≦ _{Ra 0.08GL} ≦ 0.050μm.

Further, the arithmetic average roughness Ra (Ra _0.25GL ) of JIS B0601: 2001 on the surface of the glossy printed layer when the cut-off value is 0.25 mm is 0.250 μm or less from the viewpoint of metallic gloss. Preferably, it is 0.200 μm or less, more preferably 0.150 μm or less. From the viewpoint of improving the visibility by suppressing reflection in the regular reflection direction, Ra _0.25GL is preferably 0.125 μm or more.

Further, the arithmetic average roughness Ra (Ra _0.8GL ) of JIS B0601: 2001 on the surface of the glossy printed layer when the cutoff value is 0.8 mm is 0.500 μm or less from the viewpoint of metallic gloss. Preferably, it is 0.450 μm or less, more preferably 0.400 μm or less. From the viewpoint of improving visibility by suppressing reflection in the regular reflection direction, Ra _0.8GL is preferably 0.250 μm or more.

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

Pattern Layer The printed material of the present invention preferably has a pattern layer at any location between the substrate and the surface protective layer for the purpose of enhancing the design of the printed material. For example, the pattern layer can be formed at any location on the glossy printed layer and / or on the substrate where the glossy printed layer is not formed.
The pattern layer is formed by printing or the like. The pattern layer can be formed by multicolor printing with normal yellow, red, blue, and black process colors, or can be formed by multicolor printing with special colors prepared by preparing individual color plates constituting the pattern. . The pattern of the pattern layer can be used without any particular limitation as long as it is a pattern used in normal printing (for example, letters, numbers, figures, symbols, landscapes, people, animals, characters, etc.).

As the ink used for forming the pattern layer, an ink obtained by appropriately mixing a binder resin with a colorant such as a pigment or dye, an extender pigment, a solvent, a stabilizer, a plasticizer, a catalyst, or a curing agent is used.
The binder resin is not particularly limited. For example, acrylic resin, styrene resin, polyester resin, urethane resin, chlorinated polyolefin resin, vinyl chloride-vinyl acetate copolymer resin, polyvinyl butyral resin, alkyd resin. , Petroleum resins, ketone resins, epoxy resins, melamine resins, fluorine resins, silicone resins, fiber derivatives, rubber resins, and the like. These resins can be used alone or in admixture of two or more.

  The thickness of the pattern layer can be appropriately adjusted in the range of about 0.1 to 20 μm in consideration of the form of the pattern layer and the target design property. The pattern 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 material of the present invention preferably has a surface protective layer on the outermost surface on the side having the glossy printed 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 printed layer and the picture layer provided as necessary, and more preferably 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. The surface protective layer is preferably a cured layer of a thermosetting resin composition, but more preferably a cured layer of an ultraviolet curable resin composition.
When the surface protective layer is formed of an ultraviolet curable resin composition, the surface protective layer can be instantaneously cured by irradiation with ultraviolet rays. Therefore, in the process of forming the surface protective layer, the surface shape of the surface protective layer is the lower layer (for example, It is possible to suppress following the unevenness of the high-frequency component of the pattern layer and the like, and to increase the metallic luster of the surface of the surface protective layer. On the other hand, until 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 the lower layer (for example, glossy printing layer). Appropriately follows the irregularities of the low-frequency component. For this reason, the surface protective layer will retain irregularities of low frequency components in a small amount, and the surface of the surface protective layer is excessively smoothed, so that the reflected light in the regular reflection direction becomes too high, It can suppress giving a viewer a discomfort. In addition, in order to make the said effect easier to achieve, it is preferable that an ultraviolet curable resin composition does not contain a solvent.

As the ultraviolet curable resin composition for forming the surface protective layer, the same ultraviolet curable resin composition as exemplified for the glossy printing layer can be used.
The surface protective layer preferably contains an ultraviolet absorber and / or a light stabilizer in order to improve the weather resistance.

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

[container]
The container of the present invention is formed using the above-described printed material of the present invention.
Examples of the container include, but are not limited to, a beverage container and a food container. The container of the present invention has an excellent gloss and is excellent in design. In addition, since curling of the printed matter is suppressed, it is possible to prevent a trouble caused by curling from occurring during the manufacturing process of the container.

  EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by this example.

1. Measurement and Evaluation The following measurements and evaluations were performed on the printed materials prepared in Examples and Comparative Examples and the printed materials of Reference Examples. The results are shown in Table 1.

1-1. Specular Gloss The mirror surface at 60 degrees of JIS Z8741: 1997 was used for the printed materials of Examples 1 to 4 and Comparative Examples 1 to 3 and the intermediates of the printed materials using a BYK Gardner micro-TRI-gloss as a measuring device. Gloss was measured.

1-2. Surface roughness PPS
The surface roughness of the surface of the hard coat layer was measured using the Parker Print-Surf model Ver. 58-0600 of TESTING MACHINES INC. As a measuring instrument for the printed materials of Examples 1 to 4 and the intermediates of the printed materials. PPS was measured according to JIS P8151: 2004.

1-3. Curl About the printed matter of Examples 1-4 and Comparative Examples 1-3, 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 “Curl depth measurement method” of 15-1.

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

2. Production of printed matter [Example 1]
On the entire coated surface side of the base material (single-sided ivory paper having a basis weight of 235 g / m ² ), the hard coat layer ink 1 having the following formulation was applied, dried, and irradiated with ultraviolet rays so that the thickness after drying was 6 μm. A hard coat layer (cured product layer of ionizing radiation curable resin composition) was formed.
Next, on the entire surface of the hard coat layer, the glossy printing layer ink 1 having the following formulation was applied and dried so that the thickness after drying was 0.30 μm to form a glossy printing layer, and the printed matter of Example 1 was obtained. Obtained. In addition, the thickness of the area | region where the metal scale of the glossy printing layer of Example 1 substantially does not exist was 0.20 micrometer, and the thickness of the metal scale uneven distribution area was 0.10 micrometer.

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

<Glossy printing layer ink 1>
・ Binder resin (nitrified cotton) 4.8 parts (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 matter of Example 2 was obtained in the same manner as in Example 1 except that the thickness of the glossy printed layer was changed to 0.50 μm. In addition, the thickness of the area | region where the metal scale of the glossy printing layer of Example 2 does not substantially exist was 0.30 micrometer, and the thickness of the metal scale uneven distribution area was 0.20 micrometer.

[Example 3]
A printed matter of Example 3 was obtained in the same manner as Example 1 except that the thickness of the glossy printed layer was changed to 0.70 μm. In addition, the thickness of the area | region where the metal scale of the glossy printed layer of Example 3 does not substantially exist was 0.42 μm, and the thickness of the metal scale unevenly distributed area was 0.28 μm.

[Example 4]
A printed matter of Example 4 was obtained in the same manner as in Example 1 except that the thickness of the glossy printed layer was changed to 1.00 μm. In addition, the thickness of the area | region where the metal scale of the glossy printed layer of Example 4 does not substantially exist was 0.60 μm, and the thickness of the metal scale unevenly distributed area was 0.40 μm.

[Comparative Example 1]
The glossy printing layer ink 1 of Example 1 was changed to the glossy printing layer ink 2 of the following formulation, applied so that the thickness after drying was 1.5 μm, and the hardcoat layer ink 1 was applied to the substrate A printed matter of Comparative Example 1 was obtained in the same manner as in Example 1 except that this was not done.
<Glossy printing layer ink 2>
・ Binder resin (nitrified cotton) 6 parts (manufactured by DIC Graphics)
(Product name: XS-763 Medium NT-No. 1)
・ 6 pieces of aluminum pieces (product name: TD-180T, manufactured by Toyo Aluminum Co., Ltd.)
(Average length 15μm, average thickness over 0.2μm)
・ Solvent (ethyl acetate, IPA, ethanol, NPAC) 88 parts

[Comparative Example 2]
A vapor deposition film having an aluminum vapor deposition film having a thickness of 50 nm was prepared on a biaxially stretched PET film having a thickness of 12 μm. The surface on the coated surface side of the base material (single-sided ivory paper with a basis weight of 235 g / m ² ) and the surface on the PET film side of the deposited film are made of low-density polyethylene (LDPE) with a thickness of 15 μm using a sand laminating method. As a result, the printed matter of Comparative Example 2 was obtained (exactly not a printed matter, but referred to as a printed matter for convenience).

[Comparative Example 3]
The hard coat layer ink 1 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 hard coat layer ink 1 was not applied to the substrate. A printed matter of Comparative Example 3 was obtained in the same manner as Example 1 except that.
<Thermoplastic resin 1>
Low density polyethylene resin (density: 0.923 g / cm ³ , melt index (MI): 3.8, melting point 109 ° C.)

From the results of Table 1, it can be confirmed that the gloss printed layers of the printed materials of Examples 1 to 4 and the vapor deposited film of the printed material of Comparative Example 2 have the same Ra.
Furthermore, it can be seen from the results in Table 1 that the printed materials of Examples 1 to 4 have an excellent metallic luster with a specular gloss of 150% or more without using metal vapor deposition means.
On the other hand, the printed materials of Comparative Examples 1 and 3 were inferior in specular gloss (metal gloss) because they did not use metal scales. Since the printed matter of Comparative Example 2 uses vapor-deposited PET, the specular glossiness (metallic gloss) is excellent, but curls are generated. In addition, the printed matter of Comparative Example 2 had an excessive specular gloss (metallic luster) and was uncomfortable for the viewer. The printed matter of Comparative Example 3 has a glossy printed layer containing metal scales, but the thermoplastic resin layer disposed under the glossy printed layer did not exhibit the effect of the hard coat layer, resulting in a specular glossiness. (Metallic luster) could not be increased.

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

1: Base material 2: Hard coat layer 3: Glossy print layer 31: Metal scale unevenly distributed region 4: Picture layer 5: Surface protective layer 10: Printed matter

Claims (18)

Arithmetic average roughness (Ra ₀ .0) according to JIS B0601: 2001, having a glossy printed layer containing metal scales at an arbitrary location on the substrate, and having a cut-off value of 0.08 mm on the surface of the glossy printed layer _{. 08} ) and the arithmetic mean roughness (Ra _0.25 ) of JIS B0601: 2001 when the cut-off value of the surface of the glossy printed layer is 0.25 mm , the following conditions (1) and (2) Printed material that satisfies.
Ra _0.08 ≦ 0.100 μm (1)
0.300 <Ra _0.08 / Ra _0.25 <0.500 (2) The skewness (Rsk _0.08 ) of the roughness curve of JIS B0601: 2001 when the cut-off value on the surface of the glossy print layer is 0.08 mm, and the cut-off value on the surface of the glossy print layer is 0.25 mm The printed matter according to claim 1, wherein the skewness (Rsk _0.25 ) of the roughness curve of JIS B0601: 2001 satisfies the following conditions (3) and (4).
0.200 <Rsk _0.25− Rsk _0.08 <0.500 (3)
0 <Rsk _0.25 (4) Arithmetic average roughness (Ra ₀ .0) according to JIS B0601: 2001, having a glossy printed layer containing metal scales at an arbitrary location on the substrate, and having a cut-off value of 0.08 mm on the surface of the glossy printed layer _{. 08)} is, to meet the following conditions (1),
The skewness (Rsk _0.08 ) of the roughness curve of JIS B0601: 2001 when the cut-off value on the surface of the glossy print layer is 0.08 mm, and the cut-off value on the surface of the glossy print layer is 0.25 mm A printed matter satisfying the following conditions (3) and (4) with the skewness (Rsk _0.25 ) of the roughness curve of JIS B0601: 2001 .
Ra _0.08 ≦ 0.100 μm (1)
_{0.200 <Rsk 0.25 -Rsk 0.08 <0.500} (3)
0 <Rsk _0.25 (4) The printed matter according to any one of claims 1 to 3, wherein an average length of the metal scale and an average thickness of the glossy printed layer satisfy the following condition (6).
10 ≦ [average length of metal scale / thickness of glossy printed layer] (6)   The printed matter according to any one of claims 1 to 4, wherein an average length of the metal scale is 5.0 to 30.0 µm.   The printed matter according to claim 1, 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 6, wherein the glossy printed layer has a thickness of 0.15 to 1.50 µm.   The printed matter according to any one of claims 1 to 7, wherein the metal scale is unevenly distributed above the glossy printed layer.   The printed matter according to any one of claims 1 to 8, wherein a pattern is formed by the glossy printed layer.   The printed matter according to any one of claims 1 to 9, further comprising a hard coat layer between the substrate and the glossy printed layer.   The printed matter according to claim 10, wherein the surface of the hard coat layer has a specular glossiness of 60% or more according to JIS Z8741: 1997 of 85% or more.   The printed matter according to claim 10 or 11, wherein the surface roughness PPS of the surface of the hard coat layer in JIS P8151: 2004 is less than 1 µm.   The printed matter according to any one of claims 10 to 12, wherein the hard coat layer is a cured product layer of an ionizing radiation curable resin composition.   The printed matter according to claim 1, wherein the substrate is a paper substrate.   The printed matter according to claim 14, wherein the base material is the paper base material, and the specular glossiness at 60 degrees of JIS Z8741: 1997 of the surface of the glossy printed layer is 150% or more.   The printed matter according to claim 1, further comprising a pattern layer on the glossy printed layer.   The printed matter according to any one of claims 1 to 16, further comprising a surface protective layer on the outermost surface having the glossy printed layer.   A container formed using the printed matter according to claim 1.