JP2016088095A - Printed matter, container using the printed matter, manufacturing method of printed matter and selection method of printed matter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a printed matter having an antiglare property with high-class feeling, while having a metallic sheen without using metal deposition means.SOLUTION: A printed matter includes: a gloss printed layer including a metal scale on an arbitrary portion on a base material; and further, a surface protective layer on an outermost surface where the gloss printed layer is located. Arithmetic average roughness (Ra) of JIS B0601:2001 when a cutoff value on a surface of the surface protective layer is 0.08 mm, arithmetic average roughness (Ra) of JIS B0601:2001 when a cutoff value on a surface of the surface protective layer is 0.25 mm, and arithmetic average roughness (Ra) of JIS B0601:2001 when a cutoff value on a surface of the surface protective layer is 0.8 mm satisfy the following conditions (1) and (2): 0.50≤(Ra-Ra)/(Ra-Ra)≤1.50 (1); and 0.10 μm≤Ra≤0.50 μm (2).SELECTED DRAWING: Figure 1

Description

  The present invention relates to a printed matter, a container using the printed matter, a method for producing the printed matter, and a method for selecting the printed matter.

  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 layer 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, and has a certain level of metallic luster. However, a paper container pursuing a metallic luster as in Patent Document 1 has a sharp reflection of illumination and lacks antiglare properties, and does not have a calm design feeling.
In addition, when the surface is simply matted in order to impart antiglare properties to the printed matter, there are cases where the metallic luster is lowered and the high-quality feeling of the printed matter is lost.

  An object of the present invention is to provide a printed matter and a container having a metallic luster and a high-class anti-glare property. The present invention also provides a method for producing or selecting a printed matter having a high-quality anti-glare property while having a metallic luster.

In order to solve the above problems, the present invention provides the following printed materials [1] to [14], a container using the printed material, a method for producing the printed material, and a method for selecting the printed material.
[1] A printed matter having a glossy print layer containing metal scales at an arbitrary position on a substrate, and further having a surface protective layer on the outermost surface on the side having the glossy print layer, JIS B0601: 2001 arithmetic average roughness (Ra _0.08 ) when the surface cut-off value of the protective layer is 0.08 mm, and the surface cut-off value of the surface protective layer is 0.25 mm JIS B0601: 2001 arithmetic average roughness (Ra _0.25 ) and JIS B0601: 2001 arithmetic average roughness (Ra _0.8 ) when the surface cut-off value of the surface protective layer is 0.8 mm. Printed matter satisfying the following conditions (1) and (2).
0.50 ≦ (Ra _0.8 −Ra _0.25 ) / (Ra _0.25 −Ra _0.08 ) ≦ 1.50 (1)
0.10 μm ≦ Ra _0.25 ≦ 0.50 μm (2)
[2] The maximum valley depth (Rv _0.08 ) of JIS B0601: 2001 when the surface cutoff value of the surface protective layer is 0.08 mm, and the surface cutoff value of the surface protective layer is 0 The maximum valley depth (Rv _0.25 ) of JIS B0601: 2001 when _.25 mm and the maximum valley depth of JIS B0601: 2001 when the cut-off value of the surface of the surface protective layer is 0.8 mm. The printed matter of [3], wherein (Rv _0.8 ) satisfies the following conditions (3) and (4).
1.00 ≦ (Rv _0.8 −Rv _0.25 ) / (Rv _0.25 −Rv _0.08 ) ≦ 2.00 (3)
0.50 μm ≦ Rv _0.25 ≦ 1.00 μm (4)
[3] The printed matter according to [1] or [2], in which 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)
[4] The printed material 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 material 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 [1] to [5], wherein the glossy printed layer has a thickness of 0.15 to 1.50 μm.
[7] The printed matter according to any one of [1] to [6], wherein the metal scale is unevenly distributed above the glossy printed layer.
[8] The printed matter according to any one of [1] to [7], wherein a pattern is formed by the glossy printed layer.
[9] The printed material according to any one of [1] to [8], which has a hard coat layer between the substrate and the pattern layer.
[10] The printed matter according to [9], wherein the hard coat layer is a cured product layer of an ionizing radiation curable resin composition.
[11] The printed material according to any one of [1] to [10], wherein the substrate is a paper substrate.
[12] A container using the printed material according to any one of [1] to [11].
[13] A method for producing a printed matter having a glossy printed layer containing metal scales at an arbitrary location on a substrate, and further having a surface protective layer on the outermost surface on the side having the glossy printed layer. ,
By performing the step of forming the glossy printed layer from the ink for the glossy printed layer containing metal scales, the step of forming the surface protective layer from the ink for the surface protective layer,
The arithmetic average roughness (Ra _0.08 ) of JIS B0601: 2001 when the cut-off value of the surface of the surface protective layer is 0.08 mm, and the cut-off value of the surface of the surface protective layer is 0.25 mm JIS B0601: 2001 arithmetic average roughness (Ra _0.25 ) and JIS B0601: 2001 arithmetic average roughness (Ra ₀ ) when the surface cut-off value of the surface protective layer is 0.8 mm. _.8 ) satisfies the following conditions (1) and (2).
0.50 ≦ (Ra _0.8 −Ra _0.25 ) / (Ra _0.25 −Ra _0.08 ) ≦ 1.50 (1)
0.10 μm ≦ Ra _0.25 ≦ 0.50 μm (2)
[14] When selecting a printed matter having a glossy print layer containing metal scales at an arbitrary location on the substrate and further having a surface protective layer on the outermost surface on the side having the glossy print layer,
The arithmetic average roughness (Ra _0.08 ) of JIS B0601: 2001 when the cut-off value of the surface of the surface protective layer is 0.08 mm, and the cut-off value of the surface of the surface protective layer is 0.25 mm JIS B0601: 2001 arithmetic average roughness (Ra _0.25 ) and JIS B0601: 2001 arithmetic average roughness (Ra ₀ ) when the surface cut-off value of the surface protective layer is 0.8 mm. _.8 ) satisfies the following conditions (1) and (2) as a determination condition.
0.50 ≦ (Ra _0.8 −Ra _0.25 ) / (Ra _0.25 −Ra _0.08 ) ≦ 1.50 (1)
0.10 μm ≦ Ra _0.25 ≦ 0.50 μm (2)

  The printed matter and container of the present invention have high-quality anti-glare properties while having metallic luster. Moreover, since the printed matter and the container of the present invention can achieve this effect without using metal vapor deposition means, they are extremely excellent in cost performance. Moreover, according to the printed matter manufacturing method of the present invention, a printed matter having the above-described effects can be easily manufactured. Further, according to the method for selecting a printed material of the present invention, it is possible to accurately select a printed material having the above-described effects.

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 is a printed matter having a glossy printed layer containing metal scales at an arbitrary location on the substrate and further having a surface protective layer on the outermost surface on the side having the glossy printed layer. The arithmetic average roughness (Ra _0.08 ) of JIS B0601: 2001 when the cut-off value of the surface of the surface protective layer was 0.08 mm, and the cut-off value of the surface of the surface protective layer was 0.25 mm JIS B0601: 2001 arithmetic mean roughness (Ra _0.25 ) and JIS B0601: 2001 arithmetic mean roughness (Ra _0.8 ) when the cut-off value of the surface of the surface protective layer is 0.8 mm ) Satisfies the following conditions (1) and (2).
0.50 ≦ (Ra _0.8 −Ra _0.25 ) / (Ra _0.25 −Ra _0.08 ) ≦ 1.50 (1)
0.10 μm ≦ Ra _0.25 ≦ 0.50 μm (2)

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. 1 and 2 has a hard coat layer 2, a glossy printed layer 3 and a surface protective layer 5 in this order on a substrate 1, and the surface protective layer 5 is the outermost surface of the printed product 10. . The printed matter in FIG. 2 further has a pattern layer 4 between the glossy printed layer 3 and the surface protective layer 5. 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 Surface Protective Layer In the printed matter of the present invention, the surface of the glossy printed layer satisfies the above conditions (1) and (2). Condition (1) is the arithmetic average roughness (Ra _0.08 ) of JIS B0601: 2001 when the cut-off value is 0.08 mm, and the arithmetic mean of JIS B0601: 2001 when the cut-off value is 0.25 mm. It is defined by the average roughness (Ra _0.25 ) and the arithmetic average roughness (Ra _0.8 ) of JIS B0601: 2001 when the cutoff value is 0.8 mm.
The cutoff value is a value indicating the degree to which the swell component (low frequency component) is cut from the cross-sectional curve composed of the roughness component (high frequency component) and the swell component (low frequency component). In other words, the cutoff value is a value indicating the fineness of the filter that cuts the swell 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 component (low frequency component) is cut, but a small swell is not cut. That is, when the cutoff value is large, the value includes a swell 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 (low frequency component) is cut. That is, when the cut-off value is small, the roughness component (high frequency component) that does not substantially include the swell component (low frequency component) is accurately reflected.
Hereinafter, a roughness component having a cutoff value of 0.08 mm may be referred to as a high frequency component, a roughness component having a cutoff value of 0.25 mm as an intermediate frequency component, and a swell component having a cutoff value of 0.8 mm as a low frequency component.

Condition (1) is: Ra _0.8 -Ra _0.25 (difference between Ra of low frequency component and Ra of medium frequency component) and Ra _0.25 -Ra _0.08 (Ra of medium frequency component and high frequency component) Ratio of the difference of Ra). Condition (2) means that Ra of a predetermined medium frequency component exists moderately. That is, when the conditions (1) and (2) are not satisfied, the high-frequency component, the medium-frequency component, and the low-frequency component Ra do not exist appropriately. Here, the high-frequency component Ra contributes to high-angle diffusion, the medium-frequency component Ra contributes to moderate diffusion, and the low-frequency component Ra contributes to low-angle diffusion. Therefore, when the Ra of the high frequency component, the medium frequency component, and the low frequency component does not exist in a balanced manner, the diffusion at a specific angle becomes weak. When the diffusion at a specific angle becomes weak, a singular point is generated in the change in diffusion, resulting in an anti-glare effect that is uncomfortable.
When Ra of the high-frequency component is excessively present, diffusion with a large angle increases, so that the metallic gloss of the glossy printed layer is significantly lowered by the diffused light, and the metallic gloss of the printed matter is lost. Moreover, if diffusion with a large angle increases, there is a sense of whiteness and a high-class feeling does not appear. Further, the diffusion with a large angle increases, so that the ratio of reflected light in the regular reflection direction decreases and the glossiness decreases.
When Ra of the low frequency component is excessively present, the diffusion at a small angle increases, so that the ratio of the reflected light in the regular reflection direction is reduced and the glossiness is lowered. When the low-frequency component Ra does not exist appropriately, diffusion with a small angle is lost, the ratio of reflected light in the regular reflection direction increases, and visibility decreases.
When the Ra of the medium frequency component is present appropriately, it plays a role as a link between the high frequency component and the low frequency component, and can prevent a steep visibility change.

The condition (1) more preferably satisfies 0.60 ≦ (Ra _0.8 −Ra _0.25 ) / (Ra _0.25 −Ra _0.08 ) ≦ 1.40, and 0.70 ≦ (Ra It is more preferable that _0.8− Ra _0.25 ) / (Ra _0.25 −Ra _0.08 ) ≦ 1.30.
Condition (2) more preferably satisfies 0.15 μm ≦ Ra _0.25 ≦ 0.45 μm, and more preferably satisfies 0.20 μm ≦ Ra _0.25 ≦ 0.40 μm.

Ra _0.08 of the surface of the surface protective layer is preferably 0.20 μm or less, more preferably 0.18 μm or less, and further preferably 0.15 μm or less. The lower limit of Ra _{0.08 on} the surface of the surface protective layer is about 0.05 μm.
Ra _0.8 of the surface of the surface protective layer is preferably 0.60 μm or less, more preferably 0.55 μm or less, and further preferably 0.50 μm or less. The lower limit of Ra _{0.8 on} the surface of the surface protective layer is about 0.30 μm.

The printed matter of the present invention has the maximum valley depth (Rv _0.08 ) of JIS B0601: 2001 when the cut-off value of the surface of the surface protective layer is 0.08 mm, and the cut-off value of the surface of the surface protective layer The maximum valley depth (Rv _0.25 ) of JIS B0601: 2001 when the thickness is _0.25 mm, and the maximum valley of JIS B0601: 2001 when the surface cutoff value of the surface protective layer is 0.8 mm The depth (Rv _0.8 ) preferably satisfies the following conditions (3) and (4).
1.00 ≦ (Rv _0.8 −Rv _0.25 ) / (Rv _0.25 −Rv _0.08 ) ≦ 2.00 (3)
0.50 μm ≦ Rv _0.25 ≦ 1.00 μm (4)

Condition (3) is: Rv _0.8 -Rv _0.25 (difference between Rv of low frequency component and Rv of medium frequency component) and Rv _0.25 -Rv _0.08 (Rv of medium frequency component and high frequency component) Rv difference). Condition (4) means that a predetermined medium frequency component Rv exists.
By satisfying the conditions (3) and (4), Rv of high-frequency components, medium-frequency components, and low-frequency components exist appropriately, and there is no singular point that diffusion at a specific angle becomes weak. This is preferable. In addition, since the high-frequency component, medium-frequency component, and low-frequency component Rv are appropriately present, the ratio of reflected light in the regular reflection direction is reduced and the glossiness is reduced, and the regular reflection direction is reduced. Suppressing the decrease in visibility due to an increase in the proportion of reflected light is preferable because it has a metallic luster and a high-quality anti-glare property.
The condition (3) is more preferably 1.10 ≦ (Rv _0.8 −Rv _0.25 ) / (Rv _0.25 −Rv _0.08 ) ≦ 1.80, and 1.20 ≦ (Rv _0.8− Rv _0.25 ) / (Rv _0.25 −Rv _0.08 ) ≦ 1.50 is more preferable.
Condition (4) is more preferable to satisfy the 0.55μm ≦ _{Rv 0.25} ≦ 0.90μm, it is more preferable to satisfy the 0.60μm ≦ _{Rv 0.25} ≦ 0.80μm.

Rv _0.08 of the surface of the surface protective layer is preferably 0.55 μm or less, more preferably 0.45 μm or less, and further preferably 0.35 μm or less. The lower limit of Rv _{0.08 on} the surface of the surface protective layer is about 0.10 μm.
Rv _0.8 of the surface of the surface protective layer is preferably 2.00 μm or less, more preferably 1.80 μm or less, and further preferably 1.50 μm or less. The lower limit of Rv _{0.8 on} the surface of the surface protective layer is about 1.00 μm.

As for the surface of the surface protective layer, the maximum peak height Rp _0.08 of JIS B0601: 2001 when the cutoff value is 0.08 mm is preferably 0.55 μm or less, more preferably 0.45 μm or less. Preferably, it is 0.35 μm or less. The lower limit of Rp _{0.08 on} the surface of the surface protective layer is about 0.10 μm.
As for the surface of the surface protective layer, the maximum peak height Rp _0.25 of JIS B0601: 2001 when the cut-off value is 0.25 mm is preferably 1.0 μm or less, and more preferably 0.90 μm or less. Preferably, it is 0.80 μm or less. The lower limit of Rp _{0.25 on} the surface of the surface protective layer is about 0.30 μm.
As for the surface of the surface protective layer, the maximum peak height Rp _0.8 of JIS B0601: 2001 when the cutoff value is 0.8 mm is preferably 1.90 μm or less, more preferably 1.80 μm or less. Preferably, it is 1.40 μm or less. The lower limit of Rp _{0.8 on} the surface of the surface protective layer is about 1.00 μm.
Since the printed matter of the present invention has high surface smoothness of the surface protective layer, Rv and Rp on the surface of the surface protective layer are approximate values. That is, in the present invention, Rp can be used as an alternative to Rv on the surface of the surface protective layer.

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.

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.

It is preferable to have a hard-coat layer between a hard-coat layer base material and a glossy printing layer. By interposing a hard coat layer between the substrate and the glossy printed layer, the glossy printed layer can easily have a good metallic luster. The reason is considered as follows. In addition, making the metallic gloss of the glossy printed layer good leads to making the metallic gloss of the printed matter of the present invention good.
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. And it is thought that a metal scale floats above a glossy printing layer with the flow of a solvent, metal scales are unevenly distributed on the glossy printing layer, and the glossiness of the glossy printing layer can be improved.
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 a glossy printed layer is formed on a substrate with a rough surface like this, the surface of the glossy printed layer also becomes rough, and the metallic luster cannot be improved, but the hard coat layer reduces the roughness of the substrate surface. By doing so, it is considered that the surface of the glossy printed layer is prevented from being rough and the metallic luster can be improved.
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 the surface of the glossy printed layer can be prevented from reflecting irregularities due to scratches and the metallic gloss of the glossy printed layer can be improved.

  The hard coat layer is preferably formed 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 etc. 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. it can. 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 metallic gloss of the glossy printed layer can be improved.

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.

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 0.08 μm or less, and 0.06 μm or less. More preferably, it is 0.04 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.

Further, the arithmetic average roughness Ra (Ra _0.8HA ) of JIS B0601: 2001 on the hard coat layer surface when the cut-off value is 0.8 mm is preferably 0.40 μm or less, and is 0.37 μm or less. More preferably, it is 0.35 μm or less.
The unevenness of the low frequency component is not as large as the unevenness of the high frequency component, but increases the surface area of the hard coat layer. For this reason, it is preferable that Ra _0.8HA is within the above 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 surface protective layer on the outermost surface is also excessively smoothed, and the reflected light in the regular reflection direction of the surface protective layer becomes too strong, which may cause discomfort to the viewer. For this reason, Ra _0.8HA is preferably 0.10 μm or more, and more preferably 0.20 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 0.8 mm It is preferable that the arithmetic average roughness Ra (Ra _0.8BA ) of B0601: 2001, the Ra _0.08HA and the Ra _0.8HA satisfy the following condition (a).
[Ra _0.8HA / Ra _0.8BA ]> [Ra _0.08HA / Ra _0.08BA ] (a)
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 condition (a) indicates 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.
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, it is significant to satisfy the above condition (a) 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 base material.

In order to make the above effects more easily _exhibited , it is preferable that the Ra _0.08HA , Ra _0.8HA , Ra _0.08BA , and Ra _0.8BA satisfy the following condition (b).
1.8 ≦ [Ra _0.8HA / Ra _0.8BA ] / [Ra _0.08HA / Ra _0.08BA ] (b)
The condition (b) more preferably satisfies 2.2 ≦ [Ra _0.8HA / Ra _0.8BA ] / [Ra _0.08HA / Ra _0.08BA ] ≦ 4.0, and 2.5 ≦ [Ra _{More preferably, 0.8HA} / _Ra0.8BA ] / [ _Ra0.08HA / _Ra0.08BA ] ≦ 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 ionized radiation curable resin composition for forming the cured product layer 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, 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 layer contains clay and a binder resin.
Any clay can be used without particular limitation as long as it is generally called clay, and further, 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 (for example, styrene butadiene latex, acrylic latex vinyl acetate latex), water-soluble binder resins (for example, 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 substrate or the hard coat layer, and is formed by printing a glossy print layer ink. Thus, by forming the gloss imparting layer by printing instead of vapor deposition, the cost can be reduced and the occurrence of curling can be suppressed. The gloss printed layer is preferably formed on the hard coat layer, more preferably in contact with the hard coat layer, from the viewpoint of uneven distribution of the metal scales.
Further, as shown in FIG. 1, the glossy printed layer is formed in a desired pattern in a partial area on the base material or the hard coat layer, and letters, numbers, figures, symbols, landscapes, people, animals, characters, etc. The pattern may be formed, or as shown in FIG. 2, it may be formed in the entire region on the base material or the hard coat layer.

  The glossy printed layer needs to contain metal scales. By using a metal scale, the metallic gloss of the glossy printed layer can be improved.

  Moreover, it is preferable that the metal scale is unevenly distributed on the upper part of the glossy printed layer (on the side opposite to the hard coat layer of the glossy printed layer). When the metal scales are unevenly distributed on the upper part of the glossy printed layer, the metal gloss can be improved and the adhesion between the glossy printed layer and the substrate or the hard coat layer can be improved.

  The metal scales can be unevenly distributed on 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, by positioning a hard coat layer in which the solvent does not easily penetrate into the lower layer of the glossy printed layer, the solvent can be prevented from flowing downward and the solvent flows almost upward. Can be easily distributed. Further, 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 14 ≦ 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 obtained by vacuum-depositing the metal or 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 μm, and more preferably 8.0 to 20 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. . Further, 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 gloss.

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 1.5 μm, more preferably 0.20 to 1.0 μm, from the viewpoints of uneven distribution and arrangement of the metal scales and concealment. 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 described 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 gloss at 60 degrees of JIS Z8741: 1997 on the surface of the glossy printed layer is preferably 150% or more, more preferably 200% or more, and further preferably 250% or more. The upper limit of the specular gloss on the surface of the glossy printed layer is about 500%. By setting the mirror glossiness of the glossy printed layer in the above range, the glossy printed layer has a good metallic gloss, and as a result, the printed product can have a good metallic gloss.

The surface of the glossy printed layer preferably has a maximum valley depth Rv (Rv _0.08GL ) of JIS B0601: 2001 when the cut-off value is 0.08 mm, which is preferably 0.25 μm or less, and is 0.15 μm or less. More preferably, it is more preferably 0.10 μm or less. The lower limit of Rv _{0.08GL on} the surface of the glossy printed layer is about 0.010 μm.

The surface of the glossy printed layer preferably has a maximum valley depth Rv (Rv _0.8GL ) of JIS B0601: 2001 when the cut-off value is 0.8 mm, which is preferably 1.00 μm or less, and 0.95 μm or less. More preferably, it is 0.90 μm or less. The lower limit of Rv _{0.8GL on} the surface of the glossy printed layer is about 0.05 μm.

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 _0.8GL ) 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 matter of the present invention has a surface protective layer on the outermost surface on the side having the glossy printed layer. By forming the surface protective layer on the outermost surface, 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. Moreover, when it has a hard-coat layer, it is more preferable to form a surface protective layer so that the whole area | region of a hard-coat layer may be covered further.

In order to provide the surface of the surface protective layer with low-frequency component irregularities, medium-frequency component irregularities, and high-frequency component irregularities, the surface protective layer is a lower layer (glossy printed layer, pattern layer, etc.) when the surface protective layer is formed. It is preferable to follow the unevenness of From this point of view, the resin component of the surface protective layer ink preferably includes a thermoplastic resin and / or a thermosetting resin. Moreover, it is preferable from the said viewpoint that the ink for surface protective layers contains a solvent.
The thermoplastic resin and / or thermosetting resin is preferably contained in an amount of 5 to 60% by mass, and more preferably 10 to 30% by mass of the total resin component of the ink for the surface protective layer. In addition, from the viewpoint of improving the scratch resistance and weather resistance of the printed matter, it is preferable that the remainder of all resin components of the ink for the surface protective layer is an ultraviolet curable compound.
As the thermoplastic resin and / or thermosetting resin, a general-purpose resin such as an acrylic resin, a urethane resin, or a polyester resin can be used. The thing similar to what was illustrated in the hardened | cured material layer can be used for an ultraviolet curable compound.

Moreover, in order to increase moderate diffusion and large diffusion, it is preferable that the surface protective layer has internal squeezes. If you try to secure a certain amount of moderate or large diffusion only by the surface unevenness of the surface protective layer, the surface of the surface protective layer may become excessively uneven, and the appearance of the printed matter may deteriorate. By using together, it is easy to ensure moderate diffusion or large diffusion while maintaining the appearance of the printed matter.
The internal haze can be expressed by a difference in refractive index between materials constituting the surface protective layer. For example, when the surface protective layer contains a resin component and particles, if the refractive index of the resin component is different from the refractive index of the particles, it is possible to develop noise inside. Further, blending resins having poor compatibility and different refractive indexes, and causing phase separation of the resins within the surface protective layer can also generate noise.

The particles include polymethyl methacrylate, polyacryl-styrene copolymer, melamine resin, polycarbonate, polystyrene, polyvinyl chloride, benzoguanamine-melamine-formaldehyde condensate, silicone, organic resin such as fluorine resin and polyester resin, silica, Examples include inorganic particles such as alumina, zirconia, and titania.
From the viewpoint of developing squeezing inside, it is preferable to select particles having a refractive index difference of 0.01 to 0.10 with respect to the resin component.

The average particle diameter of the particles is preferably smaller than the thickness of the surface protective layer. The specific average particle size varies depending on the thickness of the surface protective layer and cannot be generally specified, but is preferably about 0.10 to 1.0 μm.
The content of the particles is preferably 2 to 20% by mass, more preferably 5 to 15% by mass, based on the total solid content of the surface protective layer.

  The thickness of the surface protective layer is preferably 0.50 to 5.0 μm, and more preferably 0.80 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.

[Method for producing printed matter]
The method for producing a printed material according to the present invention is a printed material having a glossy printed layer containing metal scales at an arbitrary location on a substrate, and further having a surface protective layer on the outermost surface on the side having the glossy printed layer. Cut-off of the surface of the surface protective layer by performing a step of forming a glossy printed layer from the ink for the glossy printed layer containing metal scales and a step of forming the surface protective layer from the ink for the surface protective layer. JIS B0601: 2001 arithmetic average roughness (Ra _0.08 ) when the value is 0.08 mm, and JIS B0601: 2001 arithmetic average when the surface cut-off value of the surface protective layer is 0.25 mm The roughness (Ra _0.25 ) and the arithmetic average roughness (Ra _0.8 ) of JIS B0601: 2001 when the cut-off value of the surface protective layer surface is 0.8 mm are as follows: ), Satisfy (2) It is intended to Suyo.
0.50 ≦ (Ra _0.8 −Ra _0.25 ) / (Ra _0.25 −Ra _0.08 ) ≦ 1.50 (1)
0.10 μm ≦ Ra _0.25 ≦ 0.50 μm (2)

As an index for evaluating the antiglare property, the specular gloss of JIS Z8741: 1997 may be used. Specifically, it is used on the basis of having anti-glare properties if the specular gloss is small (≈regular reflection intensity is small). However, even if the specular reflection intensity is small, if the difference between the specular reflection intensity and the reflection intensity of the peripheral region outside the vicinity of the specular reflection direction is too large, if you hold the printed matter in your hand and observe it from various angles, An angle at which the reflection intensity changes suddenly occurs. The fact that there is a portion where the reflection intensity changes suddenly means that there is a difference in the antiglare level depending on the observation angle. Due to the difference in the level of antiglare property, the viewer feels uncomfortable and lowers the quality of the printed matter.
The reason why the reflection intensity suddenly changes even though it has anti-glare properties is that the value of regular reflection intensity is small to some extent even if it contains even small diffusion, even if it does not include moderate or large diffusion. It is.
By satisfying the conditions (1) and (2) of the present invention, Ra of a high frequency component, a medium frequency component, and a low frequency component is appropriately present on the surface of the surface protective layer. It means that the reflection contains a certain amount of small diffusion, moderate diffusion and large diffusion, respectively. Therefore, the printed matter produced by the production method of the present invention has a high-class feeling that does not give a sense of incongruity without having an angle at which the reflection intensity changes suddenly even if the printed matter is held in hand and observed from various angles. It can provide glare.
Moreover, since the diffusion in the surface protective layer satisfying the conditions (1) and (2) is not excessive, the reduction of the metallic gloss of the glossy print layer can be suppressed to the minimum necessary. For this reason, the printed matter manufactured by the manufacturing method of the present invention has a metallic luster.
Furthermore, according to the manufacturing method of the present invention, it is possible to easily and stably manufacture a printed matter that has the above-described effects and is standardized with high quality.

In order to obtain a printed matter satisfying the conditions (1) and (2), it is preferable to form a hard coat layer before forming the glossy printed layer. Moreover, in order to obtain a printed matter that satisfies the conditions (1) and (2), it is preferable that the surface shape of the surface protective layer is in the above-described range, and that the surface protective layer is internally distorted.
In order to improve the design, it is preferable to form the pattern layer after forming the glossy print layer.

  In the method for producing a printed material of the present invention, it is further preferable to obtain the printed material so as to satisfy the conditions (3) and (4) described above. Moreover, it is preferable to obtain a printed matter so as to satisfy suitable conditions (for example, mirror glossiness of the glossy print layer) such as the hard coat layer, the glossy print layer, the pattern layer, and the surface protective layer.

  Embodiments of a base material, a hard coat layer, a glossy printed layer, a picture layer, and a surface protective layer used in the method for producing a printed matter of the present invention are the base material, hard coat layer, glossy printed layer, and picture layer of the printed matter of the present invention. This is the same as the embodiment of the surface protective layer.

[How to select printed materials]
The method for selecting a printed material according to the present invention is to select a printed material having a glossy printed layer containing metal scales and further having a surface protective layer on the outermost surface on the side having the glossy printed layer. JIS B0601: 2001 arithmetic average roughness (Ra _0.08 ) when the surface cut-off value is 0.08 mm and JIS B0601: when the surface cut-off value of the surface protective layer is 0.25 mm The arithmetic average roughness (Ra _0.25 ) of 2001 and the arithmetic average roughness (Ra _0.8 ) of JIS B0601: 2001 when the cut-off value of the surface of the surface protective layer is 0.8 mm are as follows: Satisfying conditions (1) and (2) are used as determination conditions.
0.50 ≦ (Ra _0.8 −Ra _0.25 ) / (Ra _0.25 −Ra _0.08 ) ≦ 1.50 (1)
0.10 μm ≦ Ra _0.25 ≦ 0.50 μm (2)

  As described above, even if the specular gloss is used as a criterion for anti-glare property, the difference in the degree of anti-glare property for each angle is small, and the anti-glare property with a high-class feeling and the metallic gloss of the glossy printed layer is reduced In some cases, it is not possible to select a printed matter having suppressed antiglare properties. In addition, the quality of printed matter cannot be standardized only by evaluation by human eyes, depending on the individual's visual acuity, color vision, physical condition, and the like. According to the method for selecting a printed material of the present invention, it is possible to accurately select a printed material that has both metallic luster and high-quality anti-glare properties, and the quality of the printed material can be standardized.

  The printed matter to be selected in the present invention may have a layer other than the glossy printed layer and the surface protective layer. For example, you may have a hard-coat layer between a base material and a glossy printing layer, and you may have a pattern layer between a glossy printing layer and a surface protective layer.

  In the method for selecting a printed material according to the present invention, it is preferable that the conditions (3) and (4) described above are set as the determination conditions. Moreover, it is also preferable to add suitable conditions (for example, the mirror glossiness of the glossy printed layer) such as the hard coat layer, glossy printed layer, picture layer, and surface protective layer described above as determination conditions.

  Embodiments of a substrate, a hard coat layer, a glossy printed layer, a pattern layer, and a surface protective layer of a printed material selected by the method for selecting a printed material of the present invention are the base material, hard coat layer, and glossy printed layer of the printed material of the present invention. This is the same as the embodiment of the pattern layer and the surface protective layer.

  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. The results are shown in Table 1.

1-1. Specular Glossiness According to JIS Z8741: 1997, using BYK Gardner's micro-TRI-gloss as a measuring device, the printed matter of Examples 1-4 and Comparative Examples 1-6, or the glossy printed layer of the intermediate of the printed matter or The 60 degree specular glossiness of the deposited film was measured.

1-2. Arithmetic mean roughness Ra and maximum valley depth Rv
For the printed materials of Examples 1 to 4 and Comparative Examples 1 to 6, JIS B0601: 2001 arithmetic average roughness Ra and maximum valley depth Rv when the cutoff value is 0.08 mm, and the cutoff value is 0.25 mm. JIS B0601: 2001 arithmetic average roughness Ra and maximum valley depth Rv, and JIS B0601: 2001 arithmetic average roughness Ra and maximum valley depth Rv when the cutoff value is 0.8 mm Was measured. In addition, Ra and Rv were measured using the trade name SE-340 manufactured by Kosaka Laboratory Ltd. under the following measurement conditions.
[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 cut-off value λc ・ Feeding speed of stylus: 0.5 mm / s
・ Preliminary length: (cutoff value λc) × 2
・ Vertical magnification: 2000 times ・ Horizontal magnification: 10 times

1-3. Metallic luster Using the printed matter of Comparative Example 1 as a reference, the metallic luster of the printed matter of Examples 1 to 4 and Comparative Examples 2 to 6 was visually evaluated. As a result, “A” indicates a metal luster equivalent to that of the reference, “B” indicates a metal luster that is inferior to the reference, but “C”.

1-4. Antiglare property The printed materials of Examples 1 to 4 and Comparative Examples 1 to 6 were held in hand, and were shaken at various angles under the illumination of a fluorescent lamp, and the antiglare property for each angle was visually evaluated. As a result, “A” indicates that it has excellent anti-glare properties at all angles and does not feel the difference in anti-glare property for each angle, but it can be felt that it has a certain anti-glare property, but it is anti-glare property for each angle. “B” indicates that there is a difference between the two, and “C” indicates that there is little antiglare property.

1-5. Curl About the printed matter of Examples 1-4 and Comparative Examples 1-6, 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.

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, the gloss printing layer ink 2 having the following formulation was applied on the entire surface of the hard coat layer so that the thickness after drying was 0.50 μm and dried to form a gloss printing layer. The thickness of the gloss print layer in which the metal scales were not substantially present was 0.30 μm, and the thickness of the metal scale unevenly distributed region was 0.20 μm.
Next, an amber pattern layer was formed by offset printing at an arbitrary position on the glossy printed layer. Next, the surface protective layer ink 3 having the following formulation is applied so that the thickness after drying is 1.0 μm so as to cover the entire surface of the pattern layer and the glossy printed layer, and the surface protective layer is formed by irradiation with ultraviolet rays. A printed matter of Example 1 was obtained.

<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 2>
・ 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

<Ink for surface protective layer 3>
・ 100 parts of UV curable resin composition (manufactured by DIC Graphics, trade name: UV Carton ACT OP Varnish)
(Mixture containing 55 to 65% by mass of UV curable monomer, 10 to 20% by mass of synthetic resin, 5 to 15% by mass of particles, and 5 to 15% by mass of auxiliary agent as main components)

In Example 1, the arithmetic average roughness Ra of JIS B0601: 2001 when the cut-off value on the substrate surface was 0.08 mm was 0.129 μm. Moreover, arithmetic mean roughness Ra of JIS B0601: 2001 when the cut-off value of the substrate surface was 0.8 mm was 0.524 μm.
In Example 1, the arithmetic average roughness Ra of JIS B0601: 2001 when the cut-off value on the hard coat layer surface was 0.08 mm was 0.026 μm. The arithmetic average roughness Ra of JIS B0601: 2001 when the cut-off value on the hard coat layer surface was 0.8 mm was 0.305 μm.
In Example 1, the arithmetic average roughness Ra of JIS B0601: 2001 when the cut-off value on the glossy printed layer surface was 0.08 mm was 0.036 μm. The arithmetic average roughness Ra of JIS B0601: 2001 when the cut-off value on the glossy printed layer surface was 0.8 mm was 0.359 μm.

[Example 2]
A printed matter of Example 2 was obtained in the same manner as Example 1 except that the glossy printing layer ink 2 was applied and dried so that the thickness after drying was 0.35 μm to form a glossy printing layer. .

[Example 3]
The printed matter of Example 3 was obtained in the same manner as in Example 1 except that the glossy printing layer ink 2 was applied and dried so that the thickness after drying was 0.70 μm to form a glossy printing layer. .

[Example 4]
The printed matter of Example 4 was obtained in the same manner as in Example 1 except that the glossy printing layer ink 2 was applied and dried so that the thickness after drying was 1.00 μm to form a glossy printing layer. .

[Comparative Example 1]
A printed material of Comparative Example 1 was obtained in the same manner as in Example 1 except that the pattern layer and the surface protective layer were not formed on the glossy printed layer.

[Comparative Example 2]
A printed matter of Comparative Example 2 was obtained in the same manner as in Example 1 except that the surface protective layer was not formed on the pattern layer.

[Comparative Example 3]
A printed matter of Comparative Example 3 was obtained in the same manner as in Example 1 except that the surface protective layer ink 3 was changed to the following surface protective layer ink 4.

<Ink for surface protective layer 4>
・ 100 parts of UV curable compound (manufactured by DIC Graphics, trade name: UV low odor coat varnish S)

[Comparative Example 4]
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. Next, 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) using a sand laminating method. Bonding was performed while extruding to 15 μm to obtain a laminate substrate.
Next, an amber pattern layer was formed on the laminated base film by gravure printing. Next, the surface protective layer ink 5 having the following formulation was applied and dried so that the thickness after drying was 1.0 μm so as to cover the entire surface of the pattern layer and the deposited film, and a surface protective layer was formed. The printed matter of Example 4 was obtained.

<Surface protective layer ink 5>
70 parts thermosetting resin (manufactured by DIC Graphics, trade name: Dick Safe G-310 OP Varnish)
・ Solvent (water / IPA = 2/8) 30 parts

  In Comparative Example 4, the arithmetic average roughness Ra of JIS B0601: 2001 when the cutoff value of the deposited film was 0.08 mm was 0.048 μm. The arithmetic average roughness Ra of JIS B0601: 2001 when the cutoff value of the deposited film was 0.8 mm was 0.301 μm.

[Comparative Example 5]
Glossy printing layer ink 6 having the following prescription is applied to the entire surface of the substrate (single-sided ivory paper with a basis weight of 235 g / m ² ) so that the thickness after drying is 1.5 μm, and dried to give a gloss. A printed layer was formed. Next, a scarlet pattern layer was formed on the glossy printed layer in the same manner as in Example 1. Next, the surface protective layer ink 7 having the following formulation is applied so that the thickness after drying is 1.0 μm so as to cover the entire surface of the pattern layer and the glossy printed layer, dried, and irradiated with ultraviolet rays to form a surface protective layer. The printed matter of Comparative Example 5 was obtained.

<Glossy printing layer ink 6>
・ 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

<Surface protective layer ink 7>
・ 100 parts of UV curable resin composition (trade name: FD OLP multicolor OP varnish M1-B, manufactured by Toyo Ink Co., Ltd.)
(As a main component, a mixture containing 35 to 45 mass% of an ultraviolet curable monomer, 35 to 45 mass% of a synthetic resin, 1 to 10 mass% of particles, and 5 to 15 mass% of an auxiliary agent)

  In Comparative Example 5, the arithmetic average roughness Ra of JIS B0601: 2001 when the cutoff value of the glossy printed layer was 0.08 mm was 0.15 μm.

[Comparative Example 6]
A thermoplastic resin layer is formed by extruding low-density polyethylene (LDPE) to a thickness of 15 μm using a melt extrusion method on the entire coated surface side of the base material (single-sided ivory paper having a basis weight of 235 g / m ² ). Formed.
Next, the gloss printing layer ink 2 having the above formulation was applied on the entire surface of the thermoplastic resin layer so that the thickness after drying was 0.70 μm, and dried to form a gloss printing layer.
Next, a yellow pattern layer was formed by offset printing at an arbitrary position on the glossy printed layer. Next, the surface protective layer ink 3 having the above formulation was applied so that the thickness after drying was 1.0 μm so as to cover the entire surface of the pattern layer and the glossy printed layer, and the surface protective layer (solvent-free) was applied. The cured product layer of the ultraviolet curable resin composition of the mold was formed, and the printed matter of Comparative Example 6 was obtained.

  From the results in Table 1, it can be seen that the printed materials of Examples 1 to 4 have metallic luster and high-quality anti-glare properties.

  The printed matter and container of the present invention are useful in that they have a metallic luster and a high-quality anti-glare property without using a 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 (14)

A printed matter having a glossy printed layer containing metal scales at an arbitrary location on the substrate, and further having a surface protective layer on the outermost surface on the side having the glossy printed layer, JIS B0601: 2001 arithmetic average roughness (Ra _0.08 ) when the surface cut-off value is 0.08 mm, and JIS B0601 when the surface cut-off value of the surface protective layer is 0.25 mm : Arithmetic mean roughness (Ra _0.25 ) of 2001 and arithmetic mean roughness (Ra _0.8 ) of JIS B0601: 2001 when the cut-off value of the surface of the surface protective layer is 0.8 mm A printed matter satisfying the following conditions (1) and (2).
0.50 ≦ (Ra _0.8 −Ra _0.25 ) / (Ra _0.25 −Ra _0.08 ) ≦ 1.50 (1)
0.10 μm ≦ Ra _0.25 ≦ 0.50 μm (2) The maximum valley depth (Rv _0.08 ) of JIS B0601: 2001 when the cut-off value of the surface of the surface protective layer is 0.08 mm, and the cut-off value of the surface of the surface protective layer is 0.25 mm JIS B0601: 2001 maximum valley depth (Rv _0.25 ) and JIS B0601: 2001 maximum valley depth (Rv ₀ ) when the cut-off value of the surface of the surface protective layer is 0.8 mm. _.8 ) satisfies the following conditions (3) and (4).
1.00 ≦ (Rv _0.8 −Rv _0.25 ) / (Rv _0.25 −Rv _0.08 ) ≦ 2.00 (3)
0.50 μm ≦ Rv _0.25 ≦ 1.00 μm (4) The printed matter according to claim 1 or 2, 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 claim 1, wherein an 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 claim 1, 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 6, wherein the metal scale is unevenly distributed above the glossy printed layer.   The printed matter according to claim 1, wherein a pattern is formed by the glossy printed layer.   The printed matter according to any one of claims 1 to 8, further comprising a hard coat layer between the substrate and the pattern layer.   The printed matter according to claim 9, wherein the hard coat layer is a cured product layer of an ionizing radiation curable resin composition.   The printed material according to claim 1, wherein the substrate is a paper substrate.   A container using the printed matter according to any one of claims 1 to 11. A method for producing a printed matter having a glossy printed layer containing metal scales at an arbitrary location on a substrate, and further having a surface protective layer on the outermost surface on the side having the glossy printed layer,
By performing the step of forming the glossy printed layer from the ink for the glossy printed layer containing metal scales, the step of forming the surface protective layer from the ink for the surface protective layer,
The arithmetic average roughness (Ra _0.08 ) of JIS B0601: 2001 when the cut-off value of the surface of the surface protective layer is 0.08 mm, and the cut-off value of the surface of the surface protective layer is 0.25 mm JIS B0601: 2001 arithmetic average roughness (Ra _0.25 ) and JIS B0601: 2001 arithmetic average roughness (Ra ₀ ) when the surface cut-off value of the surface protective layer is 0.8 mm. _.8 ) satisfies the following conditions (1) and (2).
0.50 ≦ (Ra _0.8 −Ra _0.25 ) / (Ra _0.25 −Ra _0.08 ) ≦ 1.50 (1)
0.10 μm ≦ Ra _0.25 ≦ 0.50 μm (2) When selecting a printed matter having a glossy printed layer containing metal scales at an arbitrary location on the substrate and further having a surface protective layer on the outermost surface on the side having the glossy printed layer,
The arithmetic average roughness (Ra _0.08 ) of JIS B0601: 2001 when the cut-off value of the surface of the surface protective layer is 0.08 mm, and the cut-off value of the surface of the surface protective layer is 0.25 mm JIS B0601: 2001 arithmetic average roughness (Ra _0.25 ) and JIS B0601: 2001 arithmetic average roughness (Ra ₀ ) when the surface cut-off value of the surface protective layer is 0.8 mm. _.8 ) satisfies the following conditions (1) and (2) as a determination condition.
0.50 ≦ (Ra _0.8 −Ra _0.25 ) / (Ra _0.25 −Ra _0.08 ) ≦ 1.50 (1)
0.10 μm ≦ Ra _0.25 ≦ 0.50 μm (2)