TW201615443A - Printed matter, container formed by using the printed matter, printed matter manufacturing method and printed matter selecting method - Google Patents

Abstract

The present invention discloses a printed matter, which is formed by providing a glossy printing layer containing metallic scales on any part of a substrate and further providing a surface protection layer on the outermost surface of the side having the glossy printing layer. When the cut-off value is set to be 0.08mm, the surface protection layer has an arithmetic average roughness degree (Ra0.08) of JIS B0601:2001. When the cut-off value is set to be 0.8mm, the surface protection layer has an arithmetic average roughness degree (Ra0.25) of JIS B0601:2001. When the cut-off value is set to be 0.8mm, the surface protection layer has an arithmetic average roughness degree (Ra0.8) of JIS B0601:2001. These arithmetic average roughness degrees satisfy the following two conditions: (1) 0.50 ≤ (Ra0.8-Ra0.25)/(Ra0.25-Ra0.08) ≤ 1.50; and (2) 0.10[mu]m ≤ Ra0.25 ≤ 0.50[mu] m.

Description

Printed matter, container using the printed matter, method for producing printed matter, and method for selecting printed matter

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

Conventionally, in order to improve the design properties of various printed materials, it is sometimes required to impart metallic luster.

As one of means for imparting metallic luster, a film having a metallic luster is used. For example, a film having a metallic luster is bonded to a paper substrate to prepare a substrate having a metallic luster, and a pattern layer or the like is printed on the substrate to prepare a printed matter having a metallic luster.

However, since the film having a metallic luster is formed by forming a metal deposited film on the film, it is expensive and is not suitable for a printed product which is inexpensive. Further, the substrate obtained by laminating a film having a metallic luster on a paper substrate has a problem that curling occurs due to a difference in shrinkage ratio between the paper and the film, resulting in a subsequent step (for example, a step of printing the substrate, The precision of the step of processing the printed matter into a container is lowered, and the yield is lowered.

In order to solve the above problem, Patent Document 1 has been proposed.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2003-2323

Patent Document 1 discloses a paper container in which a printing layer is formed on a paper substrate, and the printing layer has a bonding resin and a metallic luster layer region containing a metal thin film.

The paper container of Patent Document 1 has no problem in terms of cost or curl, and has a certain degree of metallic luster. However, in the case of a paper container which pursues metallic luster as in Patent Document 1, the illumination is strongly reflected and lacks anti-glare property, and does not have a sense of coordination.

In addition, when the surface is simply roughened in order to impart anti-glare properties to the printed matter, the metallic gloss may be lowered or the high-grade feeling of the printed matter may be lost.

An object of the present invention is to provide a printed matter and a container which have a metallic luster and have an anti-glare property of a high-grade feeling. Further, the present invention provides a method of manufacturing or selecting a printed matter having a metallic luster and having an anti-glare property of a high-grade feeling.

In order to solve the above problems, the present invention provides the printed matter of the following [1] to [6], a container using the printed matter, a method for producing a printed matter, and a method for selecting a printed matter.

[1] A printed matter having a glossy printed layer containing a metal flake at any portion on a substrate, and further having a surface protective layer on an outermost surface of the side having the gloss printed layer, the surface of the surface protective layer The arithmetic mean roughness (Ra _0.08 ) of JIS B0601:2001 when the cutoff value is set to 0.08 mm, and the arithmetic mean roughness (JIS B0601:2001) of the surface of the surface protective layer when the cutoff value is 0.25 mm _0.25 ) The arithmetic mean roughness (Ra _0.8 ) of JIS B0601:2001 when the cutoff value of the surface protective layer surface is set to 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)

0.10μm≦Ra _0.25 ≦0.50μm (2)

[2] A printed matter having a glossy printed layer at any portion on a substrate and further having a surface protective layer on an outermost surface of the side having the gloss printed layer, the glossy printed layer containing metal scales, facing When the surface on the surface protective layer side of the printed matter is irradiated with visible light at an angle of 45 degrees from the normal, the reflection intensity is measured every 0.1 degree in the range of -45 degrees to +45 degrees with respect to the regular reflection direction, and the direction of the regular reflection is displayed. The absolute value of the diffusion angle of the reflection intensity of 1/2 of the reflection intensity is α, and the absolute value of the diffusion angle indicating the reflection intensity of 1/3 of the reflection intensity in the specular reflection direction is β, and the reflection intensity of the specular reflection direction is displayed. When the absolute value of the diffusion angle of the 1/10 reflection intensity is γ, the α, β, and γ satisfy the following condition (5) in at least a part of the surface protective layer directly above the gloss printed layer. (9).

4.0 degrees ≦α≦6.0 degrees (5)

5.5 degrees ≦β≦10.0 degrees (6)

9.5 degrees ≦γ≦15.0 degrees (7)

1.2 degrees ≦β-α≦2.5 degrees (8)

4.0 degrees ≦γ-β≦8.0 degrees (9)

[3] A method of producing a printed matter, wherein the printed matter has a glossy printed layer containing a metal flake at any portion on a substrate, and further has a surface protective layer on an outermost surface of the side having the gloss printed layer, the printed matter The manufacturing method comprises the steps of forming the gloss printed layer with an ink for a glossy printed layer containing metal flakes, and forming the surface protective layer with an ink for a surface protective layer, so that the surface of the surface protective layer is cut off The arithmetic mean roughness (Ra _0.08 ) of JIS B0601:2001 when 0.08 mm is set, and the arithmetic mean roughness (Ra _0.25 ) of JIS B0601:2001 when the cutoff value of the surface protective layer surface is 0.25 mm, and The arithmetic mean roughness (Ra _0.8 ) of JIS B0601:2001 when the cutoff value of the surface protective layer was set to 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)

0.10μm≦Ra _0.25 ≦0.50μm (2)

[4] A method of producing a printed matter, comprising forming a gloss print layer on an arbitrary portion of a substrate, and further forming a surface protective layer on an outermost surface of the side having the gloss print layer, and performing a gloss print layer containing a metal scale a step of forming the glossy printed layer with an ink, and a step of forming the surface protective layer with an ink for the surface protective layer, thereby: when the surface facing the surface protective layer is irradiated with visible light at an angle of 45 degrees from the normal, The reflection intensity is measured every 0.1 degrees in the range of -45 degrees to +45 degrees in the normal reflection direction, and the absolute value of the diffusion angle indicating the reflection intensity of 1/2 of the reflection intensity in the regular reflection direction is set to α, and the display is positive. The absolute value of the diffusion angle of the reflection intensity of 1/3 of the reflection direction reflection intensity is β, and when the absolute value of the diffusion angle of the reflection intensity of 1/10 of the reflection intensity in the normal reflection direction is γ, the gloss print layer is used. In at least a part of the surface protective layer of the upper portion, the α, β, and γ satisfy the following conditions (5) to (9).

4.0 degrees ≦α≦6.0 degrees (5)

5.5 degrees ≦β≦10.0 degrees (6)

9.5 degrees ≦γ≦15.0 degrees (7)

1.2 degrees ≦β-α≦2.5 degrees (8)

4.0 degrees ≦γ-β≦8.0 degrees (9)

[5] A method of selecting a printed matter, which comprises a glossy printed layer containing a metal flake at any portion selected on a substrate, and further having a surface protective layer on the outermost surface of the side having the glossy printed layer; The following conditions are used as the determination conditions: the arithmetic mean roughness (Ra _0.08 ) of JIS B0601:2001 when the cutoff value of the surface protective layer surface is 0.08 mm, and the cutoff value of the surface of the surface protective layer is 0.25. The arithmetic mean roughness (Ra _0.25 ) of JIS B0601:2001 at mm and the arithmetic mean roughness (Ra _0.8 ) of JIS B0601:2001 when the cutoff value of the surface protective layer is set to 0.8 mm satisfy the following conditions ( 1), (2).

0.50≦(Ra _0.8 -Ra _0.25 )/(Ra _0.25 -Ra _0.08 )≦1.50 (1)

0.10μm≦Ra _0.25 ≦0.50μm (2)

[6] A method of selecting a printed matter, which comprises a glossy printed layer containing a metal flake at any portion selected on a substrate, and further having a surface protective layer on the outermost surface of the side having the glossy printed layer; The following conditions are used as the determination condition: when the visible light is irradiated at an angle of 45 degrees from the normal toward the surface on the surface protective layer side, the reflection is measured every 0.1 degree in the range of -45 degrees to +45 degrees with respect to the regular reflection direction. For the intensity, the absolute value of the diffusion angle indicating the reflection intensity of 1/2 of the reflection intensity in the normal reflection direction is α, and the absolute value of the diffusion angle indicating the reflection intensity of 1/3 of the reflection intensity in the regular reflection direction is β. When the absolute value of the diffusion angle indicating the reflection intensity of 1/10 of the reflection intensity in the normal reflection direction is γ, at least the surface protective layer directly above the gloss printed layer is provided. In a part of the region, the α, β, and γ satisfy the following conditions (5) to (9).

4.0 degrees ≦α≦6.0 degrees (5)

5.5 degrees ≦β≦10.0 degrees (6)

9.5 degrees ≦γ≦15.0 degrees (7)

1.2 degrees ≦β-α≦2.5 degrees (8)

4.0 degrees ≦γ-β≦8.0 degrees (9)

The printed matter and container of the present invention have a metallic luster and have an anti-glare property in which a high-grade feeling is present. Moreover, the printed matter and the container of the present invention can achieve this effect without using a metal vapor deposition method, and thus the cost performance is extremely excellent. Moreover, according to the method for producing a printed matter of the present invention, a printed matter having the above effects can be easily produced. Further, according to the method of selecting a printed matter of the present invention, the printed matter having the above effects can be accurately selected.

1‧‧‧Substrate

2‧‧‧hard coating

3‧‧‧Glossy print layer

31‧‧‧Metal scales are biased in the area

4‧‧‧pattern layer

5‧‧‧Surface protection layer

10‧‧‧Printed matter

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a cross-sectional view showing an embodiment of a printed matter of the present invention.

Fig. 2 is a cross-sectional view showing another embodiment of the printed matter of the present invention.

Fig. 3 is a view showing the intensity distribution of reflected light of the printed matter of Example 1.

Fig. 4 is a view showing the intensity distribution of reflected light of the printed matter of Comparative Example 1.

Fig. 5 is a view showing the intensity distribution of reflected light of the printed matter of Comparative Example 2.

Fig. 6 is a view showing the intensity distribution of reflected light of the printed matter of Comparative Example 3.

Fig. 7 is a view showing the intensity distribution of reflected light of the printed matter of Comparative Example 4.

Fig. 8 is a view showing the intensity distribution of reflected light of the printed matter of Comparative Example 5.

[printed matter]

The printed matter according to the first embodiment of the present invention has a glossy printed layer containing a metal flake on an arbitrary portion of the substrate, and a printed matter having a surface protective layer on the outermost surface on the side having the glossy printed layer, and a surface protective layer. The arithmetic mean roughness (Ra _0.08 ) of JIS B0601:2001 when the cutoff value is set to 0.08 mm, and the arithmetic mean roughness of the JIS B0601:2001 when the cutoff value of the surface of the surface protective layer is 0.25 mm (Ra) _0.25 ) and the arithmetic mean roughness (Ra _0.8 ) of JIS B0601:2001 when the cutoff value of the surface of the surface protective layer is set to 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)

0.10μm≦Ra _0.25 ≦0.50μm (2)

The printed matter according to the second embodiment of the present invention has a glossy printed layer on an arbitrary portion of the substrate, and further has a surface protective layer on the outermost surface of the side having the glossy printed layer, and the glossy printed layer contains a metal. The scale, when the visible light is irradiated toward the surface of the surface of the printed matter at an angle of 45 degrees from the normal, the reflection intensity is measured every 0.1 degree in the range of -45 degrees to +45 degrees with respect to the normal reflection direction, and the display will be displayed. The absolute value of the diffusion angle of the reflection intensity of 1/2 of the reflection intensity in the regular reflection direction is α, and the absolute value of the diffusion angle indicating the reflection intensity of 1/3 of the reflection intensity in the regular reflection direction is β, and the regular reflection is displayed. When the absolute value of the diffusion angle of the reflection intensity of 1/10 of the directional reflection intensity is γ, the α, β, and γ satisfy the following conditions in at least a part of the surface protective layer directly above the gloss printed layer ( 5)~(9).

4.0 degrees ≦α≦6.0 degrees (5)

5.5 degrees ≦β≦10.0 degrees (6)

9.5 degrees ≦γ≦15.0 degrees (7)

1.2 degrees ≦β-α≦2.5 degrees (8)

4.0 degrees ≦γ-β≦8.0 degrees (9)

Hereinafter, embodiments of the printed matter of the present invention will be described. Hereinafter, the embodiment common to the first embodiment and the second embodiment will be described unless otherwise specified.

1 and 2 are cross-sectional views showing an embodiment of a printed matter 10 of the present invention. The printed matter 10 of FIGS. 1 and 2 has a hard coat layer 2, a glossy printed layer 3, and a surface protective layer 5 on the substrate 1, and the surface protective layer 5 serves as the outermost surface of the printed matter 10. The printed matter of FIG. 2 further has a pattern layer 4 between the glossy printed layer 3 and the surface protective layer 5. Further, the glossy printed layer 3 of the printed matter 10 of FIGS. 1 and 2 has the upper metal scales biased in the region 31.

Surface condition of surface protective layer: Conditions (1), (2)

The surface of the glossy printed layer of the printed matter of the present invention satisfies the above conditions (1) and (2). Condition (1) by the Department of the cutoff value is set when 0.08mm of JIS B0601: 2001 of the arithmetic mean roughness (Ra _0.08), the cutoff value is set to 0.25mm when the JIS B0601: 2001 of the arithmetic mean roughness (Ra _0.25 And the arithmetic mean roughness (Ra _0.8 ) of JIS B0601:2001 when the cutoff value is set to 0.8 mm. The printed matter of the second embodiment of the present invention preferably satisfies the conditions (1) and (2).

The cutoff value is a value indicating a degree of cutting off the undulation component (low frequency component) from the profile curve composed of the roughness component (high frequency component) and the undulation component (low frequency component). In other words, the cutoff value is a value indicating the thickness of the filter for cutting the undulation component (low frequency component). More specifically, if the cutoff value is large, the filter is thicker, so the undulation component (low frequency component) is large. The volts were removed, but the small undulations were not removed. In other words, when the cutoff value is large, the value including the undulation component (low frequency component) is obtained. On the other hand, if the cutoff value is small, the filter is fine, and thus the undulation component (low frequency component) is almost completely cut off. In other words, when the cutoff value is small, the value of the roughness component (high frequency component) that accurately reflects the roughness component (low frequency component) is hardly included.

Hereinafter, a roughness component having a cutoff value of 0.08 mm is referred to as a high frequency component, a roughness component having a cutoff value of 0.25 mm is referred to as an intermediate frequency component, and a relief component having a cutoff value of 0.8 mm is referred to as a low frequency component.

Condition (1) (a difference between Ra Ra of the low frequency components of the middle frequency component) and Ra _0.25 -Ra _0.08 (difference Ra Ra of the intermediate frequency component and the high-frequency component) the ratio Ra _0.8 -Ra _0.25. Condition (2) means that Ra of a specific intermediate frequency component exists moderately. That is, when the conditions (1) and (2) are not satisfied, Ra of the high-frequency component, the intermediate-frequency component, and the low-frequency component does not exist moderately. Here, the Ra of the high-frequency component contributes to the diffusion of the high angle, the Ra of the intermediate frequency component contributes to the moderate diffusion, and the Ra of the low-frequency component contributes to the diffusion of the low angle. Therefore, when the Ra of the high-frequency component, the intermediate-frequency component, and the low-frequency component is not well balanced, the diffusion of the specific angle is weakened. If the diffusion of a specific angle is weakened, a singular point is generated in the diffusion change, and it becomes an anti-glare with discomfort.

When the Ra of the high-frequency component is excessively present, the diffusion of the larger angle is increased, so that the metallic luster of the gloss printed layer is largely lowered by the diffused light, and the metallic luster of the printed matter disappears. Moreover, if the spread of a large angle increases, it turns white without a high-grade feeling. Further, since the diffusion of the larger angle is increased, the proportion of the reflected light in the regular reflection direction is reduced, resulting in a decrease in glossiness.

In the case where Ra of the low-frequency component is excessively present, the diffusion of the smaller angle is increased, so that the ratio of the reflected light in the regular reflection direction is reduced, resulting in a decrease in glossiness. Ra is not moderate in the low frequency component In the case of existence, the diffusion with a small angle disappears, and the proportion of the reflected light in the direction of the regular reflection increases, and the visibility decreases.

The Ra of the intermediate frequency component functions to connect the high-frequency component and the low-frequency component in an appropriate manner, thereby ensuring a rapid change in visibility.

The condition (1) is more preferably 0.60 ≦ (Ra _{0.8 -} Ra _0.25 ) / (Ra _{0.25 -} Ra _0.08 ) ≦ 1.40, and further preferably 0.70 ≦ (Ra _{0.8 -} Ra _0.25 ) / (Ra _{0.25 -} Ra _0.08 ) ≦ 1.30.

The condition (2) more preferably satisfies 0.15 μm ≦ Ra _0.25 ≦ 0.45 μm, and further preferably satisfies 0.20 μm ≦ Ra _0.25 ≦ 0.40 μm.

The surface of the surface protective layer has a Ra of _0.08 or less, preferably 0.20 μm or less, more preferably 0.18 μm or less, still more 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.

The 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, still more preferably 0.50 μm or less. The lower limit of Ra _0.8 of the surface of the surface protective layer is about 0.30 μm.

Conditions (3), (4)

It is preferable that the printed matter of the first embodiment of the present invention has a maximum valley depth (Rv _0.08 ) of JIS B0601:2001 when the cutoff value of the surface of the surface protective layer is 0.08 mm, and a cutoff value of the surface of the surface protective layer. The maximum valley depth (Rv _0.25 ) of JIS B0601:2001 at _0.25 mm and the maximum valley depth (Rv _0.8 ) of JIS B0601:2001 when the surface of the surface protective layer is set to 0.8 mm satisfy the following conditions ( 3), (4).

_{1.00 ≦ (Rv 0.8 -Rv 0.25)} / (Rv 0.25 -Rv 0.08) ≦ 2.00 (3)

0.50μm≦Rv _0.25 ≦1.00μm (4)

The printed matter of the second embodiment of the present invention preferably satisfies the conditions (3) and (4).

The condition (3) specifies the ratio of Rv _{0.8 -} Rv _0.25 (the difference between the Rv of the low frequency component and the Rv of the intermediate frequency component) and Rv _{0.25 -} Rv _0.08 (the difference between the Rv of the intermediate frequency component and the Rv of the high frequency component). Condition (4) means that there is an Rv of a specific intermediate frequency component.

By satisfying the conditions (3) and (4), the Rv of the high-frequency component, the intermediate-frequency component, and the low-frequency component is moderately present, and there is no singularity in which the diffusion of the specific angle is weakened, which is preferable. Further, by the moderate presence of the Rv of the high-frequency component, the intermediate-frequency component, and the low-frequency component, the ratio of the reflected light in the normal reflection direction is reduced and the glossiness is lowered, and the proportion of the reflected light in the regular reflection direction is suppressed from increasing. Further, since the visibility is lowered, it is preferable because it has both metallic luster and anti-glare property with a high-grade feeling.

The condition (3) is more preferably 1.10 ≦ (Rv _{0.8 -} Rv _0.25 ) / (Rv _{0.25 -} Rv _0.08 ) ≦ 1.80, further preferably 1.20 ≦ (Rv _{0.8 -} Rv _0.25 ) / (Rv _{0.25 -} Rv _0.08 ) ≦ 1.50 .

The condition (4) is more preferably 0.55 μm ≦ Rv _0.25 ≦ 0.90 μm, and further preferably 0.60 μm ≦ Rv _0.25 ≦ 0.80 μm.

Rv _{0.08 on the} surface of the surface protective layer is preferably 0.55 μm or less, more preferably 0.45 μm or less, still more 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.

The 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, still more preferably 1.50 μm or less. The lower limit of Rv _0.8 of the surface of the surface protective layer is about 1.00 μm.

In 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, still more preferably 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.

In the surface of the surface protective layer, the maximum peak height Rp _0.25 of JIS B0601:2001 when the cutoff value is 0.25 mm is preferably 1.0 μm or less, more preferably 0.90 μm or less, still more preferably 0.80 μm or less. The lower limit of Rp _0.25 of the surface of the surface protective layer is about 0.30 μm.

In 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, still more preferably 1.40 μm or less. The lower limit of Rp _0.8 of the surface of the surface protective layer is about 1.00 μm.

The surface of the surface protective layer of the printed matter of the present invention has high smoothness, and therefore Rv and Rp of the surface of the surface protective layer are approximate. That is, in the present invention, Rp may be used instead of the Rv of the surface of the surface protective layer.

Condition (5)~(9)

In the printed matter according to the second embodiment of the present invention, when the visible light is irradiated toward the surface of the surface protective layer side of the printed matter at an angle of 45 degrees from the normal, the refractive index is in the range of -45 degrees to +45 degrees with respect to the regular reflection direction. The reflection intensity is measured, and the absolute value of the diffusion angle indicating the reflection intensity of 1/2 of the reflection intensity in the normal reflection direction is α, and the absolute value of the diffusion angle of the reflection intensity of 1/3 of the reflection intensity in the regular reflection direction is displayed. When β is set and the absolute value of the diffusion angle indicating the reflection intensity of 1/10 of the reflection intensity in the normal reflection direction is γ, the α is at least a part of the surface protective layer directly above the gloss printed layer. , β and γ satisfy the following conditions (5) to (9).

4.0 degrees ≦α≦6.0 degrees (5)

5.5 degrees ≦β≦10.0 degrees (6)

9.5 degrees ≦γ≦15.0 degrees (7)

1.2 degrees ≦β-α≦2.5 degrees (8)

4.0 degrees ≦γ-β≦8.0 degrees (9)

The printed matter according to the first embodiment of the present invention preferably satisfies the conditions (5) to (9).

First, the meanings of α, β, and γ will be described.

The "reflective direction reflection intensity" which is a reference for α, β, and γ indicates the intensity of light reflected in the regular reflection direction among the light incident on the printed matter and reflected. That is, the reflection intensity in the normal reflection direction is not the surface of the surface protective layer, the surface of the gloss printed layer, and the intensity of light which is diffused inside the layers and reflected in the direction of the regular reflection. Further, the reflection intensity in the regular reflection direction may also be referred to as a smooth portion of the surface of the surface protective layer and a light intensity of the light which is regularly reflected at the metal scale which is arranged in parallel with the substrate on the upper portion of the gloss printed layer.

On the other hand, α, β, and γ represent ranges in which light is diffused and reflected by light incident on the printed matter and reflected. More specifically, α represents a range in which the reflected light is spread by a small diffusion, β represents a range in which the reflected light is spread by moderate diffusion, and γ represents a range in which the reflected light is spread by a large diffusion.

Therefore, the conditions (5) to (9) satisfying the difference between α, β, and γ, and the like, mean that a certain amount of small diffusion, moderate diffusion, large diffusion, and diffusion are not included. Will be too small or excessive.

As described above, satisfying the conditions (5) to (9) means that a certain amount of small diffusion, moderate diffusion, and large diffusion are respectively contained. In this way, by containing a certain amount of large, medium, and small diffusion, even if the hand-held printed matter is observed from various angles, there is no sudden change in the reflection intensity, and the anti-glare property can be provided to provide a high-grade feeling without discomfort.

Moreover, when there is excessive diffusion element on the metallic luster surface, the metallic luster of the metallic luster surface is damaged, but if the conditions (5) to (9) are not excessively diffused, the The reduction in metallic gloss is suppressed to the minimum necessary. Further, if the conditions (5) to (9) are not excessively spread, the appearance of the printed matter is not whitened. Further, the upper limits of the conditions (7) and (9) are particularly effective for suppressing a decrease in metallic luster and suppressing whitening. Further, since the diffusion of the conditions (5) to (9) is not too small, it is possible to prevent the visual person from feeling uncomfortable because the reflection intensity is too strong in the regular reflection direction.

As described above, the printed matter of the present invention which satisfies the conditions (5) to (9) suppresses the decrease in the metallic luster of the gloss printed layer to the minimum necessary, thereby providing metallic luster and imparting an anti-glare property with a high-grade feeling. .

The condition (5) is preferably such that it satisfies 4.5 degrees ≦α ≦ 6.0 degrees, more preferably satisfies 4.5 degrees ≦ α ≦ 5.5 degrees.

The condition (6) is preferably such that it satisfies 5.5 degrees ≦β≦9.0 degrees, more preferably satisfies 6.0 degrees ≦β≦8.0 degrees.

The condition (7) preferably satisfies 10.5 degrees ≦γ≦15.0 degrees, more preferably 12.0 degrees ≦γ≦14.0 degrees.

The condition (8) preferably satisfies 1.4 degrees ≦β-α≦2.5 degrees, more preferably satisfies 1.4 degrees ≦β-α≦2.2 degrees.

The condition (9) preferably satisfies 4.5 degrees ≦γ-β≦7.5 degrees, more preferably satisfies 5.0 degrees ≦γ-β≦7.0 degrees.

The conditions (5) to (9) may be satisfied in at least a part of the surface protective layer of the upper portion where the gloss printed layer is located. The upper portion of the gloss printed layer refers to the range indicated by "x" in Fig. 1. That is, in the case of FIG. 1, only a part of the range indicated by "x" satisfies the conditions (5) to (9). Also, in order to make the effect of the present invention more Preferably, it is preferable to satisfy the conditions (5) to (9) in all the regions of the surface protective layer directly above the gloss printed layer.

Further, when the printed matter has a pattern layer between the gloss printed layer and the surface protective layer, the values of the conditions (5) to (9) are slightly different depending on the pattern color (more specifically, the type of the pigment constituting the pattern). Differently, it is preferable to satisfy the conditions (5) to (9) in the regions of all colors except black.

Condition (10)

Preferably, the printed matter of the present invention is measured at a distance of from -45 degrees to +45 degrees with respect to the normal reflection direction when the visible light is irradiated toward the surface of the surface of the printed matter at a surface of the surface of the printed matter at an angle of 45 degrees from the normal. In the reflection intensity, when the absolute value of the diffusion angle indicating the reflection intensity of the reflection intensity in the normal reflection direction is δ, at least a part of the surface protective layer directly above the gloss printed layer, the γ, And δ satisfy the following condition (10).

Δ-γ≦4.0 degrees (10)

The printed matter according to the first embodiment of the present invention preferably satisfies the condition (10).

As described above, γ represents the range in which the reflected light spreads due to the large diffusion, and δ represents the range in which the reflected light spreads beyond the maximum diffusion of γ. Further, the condition (10) means that a large amount of diffusion is not contained in a large amount.

By satisfying the condition (10), the reduction in the metallic luster of the gloss printed layer can be more easily suppressed. The condition (10) is preferably satisfied in the same region as the region satisfying the conditions (5) to (9).

Further, in order to more easily satisfy the effect of the condition (10), δ is preferably 19.0 degrees or less, more preferably 18.0 degrees or less, still more preferably 17.0 degrees or less. The lower limit of δ is about 14.0 degrees.

Method for measuring reflection intensity

First, the visible light (parallel light) is irradiated toward the surface of the surface of the printed matter on the surface of the surface of the printed matter at an angle of 45 degrees from the normal. Then, for the reflected light, the normal reflection direction of the illumination light is set to 0 degrees, and the photodetector is scanned every 0.1 degrees in the range of -45 degrees to +45 degrees with respect to the regular reflection direction, and is measured at each angle. Intensity (luminosity). When measuring the intensity, the brightness of the light source is fixed. Further, when the intensity (photometric) was measured, the opening angle of the photodetector detected by the pupil of the light receiver was set to 0.1 degree. Therefore, for example, the measurement of 0 degree (positive reflection) is performed within a range of ±0.05 degrees, the measurement of 1 degree is measured in the range of 0.95 degrees to 1.05 degrees, and the measurement of -1 degree is performed at -0.95 degrees - The measurement was carried out in the range of 1.05 degrees. Furthermore, the measurement of -45 degrees is measured in the range of -44.95 degrees to -45.00 degrees, and the measurement range is narrower than other angles by 0.05 degrees. Since there is almost no large diffusion of -45 degrees, the condition is not (5 ) caused an impact.

The apparatus for measuring the intensity is not particularly limited, and a general-purpose goniophotometer can be used. In the present invention, a product name GP-200 (beam diameter: about 10.5 mm, in-beam tilt angle: 0.29 degrees or less) manufactured by Murakami Color Research Laboratory Co., Ltd. was used as a goniophotometer.

3 to 8 are views showing the reflection intensity distribution of the printed materials of Example 1 and Comparative Examples 1 to 5.

Calculation of α, β, γ and δ

α, β, γ, and δ can be calculated from the reflection intensity measured in the above manner. Specifically, first, the value of the reflection intensity (positive reflection intensity) in the normal reflection direction (0 degree) is confirmed. When α is calculated, the measurement angle which is 1/2 or less of the normal reflection intensity is confirmed in both the positive direction and the negative direction, and the average value of the absolute values of the angles is α. β, γ, and δ can be calculated by changing "1/2 or less" of the above order to "1/3 or less", "1/10 or less", or "1/20 or less". Thus, α, β, γ, and δ can be calculated from the measured values of the reflection intensities. Furthermore, it is also possible to use strong reflection The degree distribution map understands the estimated values of α, β, γ, and δ. For example, in the case of Fig. 1, the specular reflection intensity is about 2.3, and the angles of the positive and negative directions of the 1/2 reflection intensity (1.15) are about +5.4 and -5.0, respectively. Then, the average value of the absolute values of the equal angles of 5.2 degrees can be read as the estimated value of α. However, the α, β, γ, and δ read from the reflection intensity distribution map are estimated values, so the accurate values should be calculated from the measured values as described above, α, β, γ, and δ.

Furthermore, when the measurement angle is farther than 0 degrees, the reflection intensity may not gradually decrease but fluctuate up and down. At this time, there is a case where after the reduction to a certain ratio of the regular reflection intensity or less, the ratio is exceeded and the ratio is lowered again. When a plurality of measurement angles which are equal to or less than a certain ratio of the normal reflection intensity are observed as described above, the measurement angle which is equal to or lower than the ratio is an intermediate value between the first measurement angle and the last measurement angle.

Substrate

The material of the substrate is not particularly limited as long as it is a material used for a conventional printed matter, and specifically, high-quality paper, medium-quality paper, coated paper, synthetic paper, impregnated paper, laminated paper, coated paper for printing, A plastic film such as paper such as coated paper, a polyethylene terephthalate film, a polyethylene film, a polypropylene film, or a polycarbonate film, or the like, or the like is used.

The thickness of the substrate is not particularly limited. 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 coating

Preferably, there is a hard coat layer between the substrate and the gloss printed layer. The metal gloss of the gloss printed layer can be easily made good by interposing the hard coat layer between the substrate and the gloss print layer. The reason is considered as follows. Further, by making the metallic luster of the gloss printed layer good, the metallic luster of the printed matter of the present invention is good.

First, it is considered that the solvent of the ink for the gloss printing layer is less likely to penetrate into the hard coat layer. Therefore, when the ink for the gloss printing layer is applied onto the hard coat layer and dried, the solvent does not easily flow below the gloss printed layer. On the other hand, when the solvent evaporates during the drying process, the solvent easily flows over the gloss printed layer. Further, as the solvent flows, the metal scales float upward above the glossy printed layer, and the metal scales are biased to the upper portion of the glossy printed layer, so that the metallic gloss of the glossy printed layer is good.

Further, it is considered that the surface of the above substrate is rough, although there is a difference in degree depending on the type. For example, paper has a rough surface due to fibers. When the surface of such a rough surface is formed into a glossy printed layer, the surface of the glossy printed layer is rough, and the metallic luster is not good. However, by using a hard coat layer to alleviate the roughness of the surface of the substrate, the surface of the glossy printed layer can be suppressed. Rough and good metal luster.

Further, when the surface of the substrate is damaged, the unevenness of the damage is reflected on the surface of the gloss printed layer, resulting in a decrease in the metallic luster of the gloss printed layer. However, since the surface of the base body composed of the base material and the hard coat layer is not easily damaged, the unevenness due to the damage can be suppressed from being reflected on the surface of the gloss printed layer, and the metallic gloss of the gloss printed layer is good.

The hard coat layer is preferably formed at a portion corresponding to a portion where the gloss printed layer described below is formed. Further, from the viewpoint of avoiding the trouble of alignment of the hard coat layer and the gloss print layer, the hard coat layer is preferably provided on the entire surface of the region of the base material where the gloss print layer is formed. Moreover, the hard coat layer is preferably formed on the entire surface of the base material from the viewpoint of uniformizing the physical properties of the base material composed of the base material and the hard coat layer and suppressing deformation of the base material.

It is preferred to smooth the surface of the hard coat layer (the surface of the hard coat layer opposite to the substrate). In the case where the surface of the hard coat layer is rough, the surface area of the hard coat layer is increased, and the solvent is easily penetrated when the gloss print layer is formed. On the other hand, if the surface of the hard coat layer is smoothed, it dissolves. The agent does not easily penetrate into the hard coat layer, so that the metal scale is easily biased on the upper portion of the gloss print layer, and the gloss of the gloss print layer is good. Further, in the case where the surface of the hard coat layer is rough, the unevenness of the hard coat layer is also reflected on the gloss print layer, resulting in a rough surface of the gloss print layer. On the other hand, if the surface of the hard coat layer is smoothed, the surface of the gloss printed layer is also smoothed, and the metallic gloss of the gloss printed layer can be made good.

Examples of the smoothing index of the surface of the hard coat layer include the specular gloss of JIS Z8741:1997 or the arithmetic mean roughness Ra of JIS B0601:2001.

The mirror gloss of the hard coat surface of JIS Z8741:1997 at 60 degrees is preferably 85% or more, more preferably 90% or more.

Further, the arithmetic mean roughness Ra (Ra _0.08HA ) of JIS B0601:2001 on the surface of the hard coat layer when the cutoff value is set to 0.08 mm is preferably 0.080 μm or less, more preferably 0.060 μm or less, still more preferably 0.040. Below μm.

Further, the cutoff value indicates the thickness of the filter for removing the fluctuation component (low frequency component) from the profile curve. More specifically, the profile curve can be divided into a undulation component (low frequency component) and a roughness component (high frequency component), and the smaller the cutoff value (the finer the filter), the lower the frequency component is removed and the higher the proportion of the high frequency component many. Therefore, Ra _0.08HA represents the unevenness of the high-frequency component of the hard coat layer, and the following Ra _0.8HA represents the unevenness of the low-frequency component of the hard coat layer. Further, an intermediate frequency component having a cutoff value of 0.25 mm may be added, and the surface shape may be managed by the three-component unevenness. The surface unevenness of the surface protective layer described below refers to the unevenness of the three components.

If the hard coat layer contains a large number of irregularities of high-frequency components, the surface area of the hard coat layer is enlarged, and the solvent is easily penetrated. Therefore, the metal scale of the gloss printed layer is hardly biased to the upper portion, and the metallic luster is easily damaged. Therefore, Ra _{0.08 is} preferable. _{HA is} set to the above range.

Further, the arithmetic mean roughness Ra (Ra _0.8HA ) of JIS B0601:2001 on the surface of the hard coat layer when the cutoff value is 0.8 mm is preferably 0.400 μm or less, more preferably 0.370 μm or less, still more preferably 0.350. Below μm.

Although the unevenness of the low-frequency component is not as high as that of the high-frequency component, the surface area of the hard coat layer is enlarged. Therefore, it is preferred to set Ra _0.8HA to the above range. In addition, when the unevenness of the low-frequency component of the hard coat layer disappears, irregularities caused by the unevenness of the low-frequency component of the hard coat layer cannot be formed on the surface of the gloss printed layer, and the gloss printed layer tends to be excessively smoothed. In this case, the surface protective layer on the outermost surface may be excessively smoothed, and the reflected light in the direction of the regular reflection of the surface protective layer is too strong, causing discomfort to the viewer. Therefore, Ra _{0.8HA is} preferably 0.100 μm or more, more preferably 0.200 μm or more.

Further, the unevenness of the low-frequency component of the hard coat layer is also related to the unevenness of the low-frequency component of the surface protective layer, which contributes to the adjustment of the above α.

Further, it is preferable to set the arithmetic mean roughness Ra (Ra _0.08BA ) of JIS B0601:2001 on the surface of the substrate when the cutoff value is 0.08 mm, and JIS B0601 of the surface of the substrate when the cutoff value is 0.8 mm: The arithmetic mean roughness Ra (Ra _0.8BA ) of 2001, the above Ra _0.08HA , and 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 to Ra of the substrate indicates the extent to which the hard coat layer moderates the unevenness of the substrate. Further, the above condition (a) indicates that the hard coat layer moderates the high-frequency component of the unevenness of the substrate to a greater extent than the low-frequency component.

As described above, the enlargement of the surface area of the hard coat layer has a large influence on the unevenness of the high-frequency component. Therefore, the hard coat layer preferably relaxes the unevenness of the high frequency component of the substrate. On the other hand, if excessively moderated to the substrate The unevenness of the low-frequency component may not only impair the texture of the substrate, but also the reflected light of the glossy printed layer in the direction of normal reflection becomes too strong. Therefore, it is of great significance to satisfy the above condition (a) which indicates that the degree of the high-frequency component of the unevenness of the substrate is more than the degree of the relaxation of the low-frequency component.

In order to more easily exhibit the above effects, it is preferable that the above-mentioned conditions (b) satisfy the following conditions of Ra _0.08HA , Ra _0.8HA , Ra _0.08BA , and Ra _0.8BA .

_{1.8 ≦ [Ra 0.8HA / Ra 0.8BA} ] / [Ra 0.08HA / Ra 0.08BA] (b)

The condition (b) is more preferably such that it satisfies 2.2 ≦ [Ra _0.8HA / Ra _0.8BA ] / [Ra _0.08HA / Ra _0.08BA ] ≦ 4.0, and further preferably satisfies 2.5 ≦ [Ra _0.8HA / Ra _0.8BA ] / [ Ra _0.08HA /Ra _0.08BA ]≦3.5.

Specific examples of the hard coat layer include a cured layer of a free radiation curable resin composition (hereinafter sometimes referred to as a "hardened layer"), a clay coating layer, etc., and smoothness, damage resistance, and penetration resistance are provided. From a more preferable viewpoint, a cured layer of the composition of the free radiation curable resin is preferred.

Further, in the case where the hard coat layer is formed of the free radiation curable resin composition, the hard coat layer can be hardened instantaneously by irradiation with free radiation, so that the surface of the hard coat layer can be suppressed during the formation of the hard coat layer. The shape follows the unevenness of the high frequency component of the substrate. In other words, in the case where the hard coat layer is formed of the composition of the free radiation curable resin, the hard coat layer can be used to alleviate the unevenness of the high frequency component of the substrate. On the other hand, during the period before the hard coat layer is hardened (during the drying process), the surface shape of the hard coat layer moderately follows the unevenness of the low-frequency component of the substrate. In other words, when the hard coat layer is formed of the composition of the free-radiation-curable resin, the surface of the hard coat layer can be made to have irregularities of high-frequency components and have a shape of irregularities of a moderately low-frequency component, and the above effects can be easily exerted. (Inhibiting the penetration of the solvent into the hard coat layer, maintaining the texture of the substrate, etc.).

Hardened layer

The composition of the free-radiation curable resin for forming a cured layer is a composition of a compound containing an exoradiating curable functional group (hereinafter also referred to as "free-radiation curable compound"). Examples of the radical radiation-curable functional group include an ethylenically unsaturated bond group such as a (meth)acryl fluorenyl group, a vinyl group, and an allyl group, and an epoxy group or an oxetanyl group. The free radiation curable compound is preferably a compound having an ethylenically unsaturated bond group, more preferably a compound having two or more ethylenically unsaturated bond groups, and further preferably having two or more ethylenically unsaturated groups. A polyfunctional (meth) acrylate compound having a bond group. As the polyfunctional (meth)acrylate compound, any of a monomer and an oligomer can be used, and from the viewpoint of improving the damage resistance and the barrier property by using a high crosslinking density, it is preferably a single one. body.

In addition, the term "free radiation" refers to radiation in an electromagnetic wave or a charged particle beam having an energy quantum capable of polymerizing or crosslinking a molecule, usually using ultraviolet (UV) or electron beam (EB), and further, X-ray may be used. Charged particle beams such as electromagnetic waves such as γ rays, α rays, and ion beams.

Among the polyfunctional (meth) acrylate monomers, examples of the difunctional (meth) acrylate monomer include ethylene glycol di(meth)acrylate and bisphenol A tetraethoxy diacrylate. , bisphenol A tetrapropoxy diacrylate, 1,6-hexanediol diacrylate, and the like.

Examples of the trifunctional or higher (meth)acrylate monomer include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, and pentaerythritol IV ( Methyl) acrylate, dipentaerythritol hexa(meth) acrylate, dipentaerythritol tetra(meth) acrylate, iso-cyanuric acid modified tri(meth) acrylate, and the like.

Further, the (meth) acrylate monomer may be a monomer which partially reforms one of the molecular skeletons, and may also be used through ethylene oxide, propylene oxide, caprolactone, iso-cyanuric acid or an alkane. A monomer which has been modified with a base, a cyclic alkyl group, an aromatic group, or a bisphenol.

The number of functional groups of the polyfunctional (meth) acrylate monomer is preferably from 2 to 6, more preferably from 2 to 3.

Moreover, examples of the polyfunctional (meth)acrylate oligomer include (meth)acrylic acid amide, epoxy (meth) acrylate, polyester (meth) acrylate, and polyether (A). An acrylate polymer such as acrylate.

The (meth) acrylate can be obtained, for example, by the reaction of a polyol and an organic diisocyanate with a hydroxy (meth) acrylate.

Further, a preferred epoxy (meth) acrylate is obtained by reacting a trifunctional or higher aromatic epoxy resin, an alicyclic epoxy resin, an aliphatic epoxy resin, or the like with (meth)acrylic acid (A). (meth) acrylate obtained by reacting a polybasic or higher aromatic epoxy resin, an alicyclic epoxy resin, an aliphatic epoxy resin, etc. with a polybasic acid and (meth)acrylic acid, And a (meth) acrylate obtained by reacting a difunctional or higher aromatic epoxy resin, an alicyclic epoxy resin, or an aliphatic epoxy resin with a phenol or a (meth)acrylic acid.

The above-mentioned free radiation curable compounds may be used singly or in combination of two or more. The free radiation curable compound preferably contains 50% by mass or more of a polyfunctional (meth) acrylate monomer, and more preferably contains 80% by mass or more.

When the free radiation curable compound is an ultraviolet curable compound, the free radiation curable composition (ultraviolet curable resin composition) preferably contains an additive such as a photopolymerization initiator or a photopolymerization accelerator.

The photopolymerization initiator may, for example, be selected from the group consisting of acetophenone, benzophenone, α-hydroxyalkylphenone, mischrone, benzoin, benzil methyl ketal, and benzene. Benzoyl benzoate, α-mercaptopurine, 9-oxosulfur One or more of the classes.

Moreover, the photopolymerization accelerator can reduce the polymerization hindrance caused by air during hardening and increase the hardening speed. For example, one or more selected from the group consisting of isoamyl p-dimethylaminobenzoate and ethyl p-dimethylaminobenzoate may be mentioned.

The free radiation curable resin composition may also contain additives such as a light stabilizer, an antioxidant, and a leveling agent.

Further, the free radiation curable resin composition may contain a resin component (thermoplastic resin or thermosetting resin) other than the radical radiation curable compound. However, in order to easily achieve the above effects, the ratio of the free radiation curable compound to the total resin component of the free radiation curable resin composition is preferably 90% by mass or more, more preferably 95% by mass or more, and still more preferably 100% by mass.

The thickness of the cured layer is preferably 2 μm or more from the viewpoint of smoothing and preventing damage of the substrate. Further, when the cured layer is too thick, the workability is lowered. Therefore, the thickness of the cured layer is more preferably 3 to 20 μm, further preferably 4 to 10 μm, still more preferably 5 to 7 μm.

The cured layer can be formed by applying a cured layer containing a free radiation curable resin composition and a diluent solvent to be added as needed to a substrate, followed by drying and irradiation with free radiation. Further, in the case where the ink for the cured layer does not contain a solvent, drying is not required.

Clay coating

The clay layer contains clay and binder resin.

As the clay, as long as it is commonly called clay, it can be used without particular limitation. Further, kaolin, talc, bentonite, bentonite, vermiculite, mica, chlorite, wood, and frog can be used. Gailome clay, watery kaolin, etc.

The clay coating preferably contains calcium carbonate, titanium dioxide, and amorphous in addition to clay. Pigments such as enamel, sparkling barium sulfate, satin white. The smoothness of the surface of the clay coating can be easily improved by using calcium carbonate or titanium dioxide as a pigment. Further, calcium carbonate can be suitably used because of its low price.

Examples of the binder resin include latex-based binder resins (for example, styrene butadiene latex, acrylic latex, vinyl acetate emulsion), and water-soluble binder resins (for example, starch (modified starch, oxidized starch, and hydroxyl). Ethyl etherified starch, phosphated starch), polyvinyl alcohol, casein, etc.).

Clay in clay coating: Pigment: The quality of the binder resin is preferably 1~20:50~90:10~30.

The clay coating may also contain additives such as a pigment dispersant, an antifoaming agent, an antifoaming agent, a viscosity modifier, a lubricant, a water resistance agent, a water retaining agent, a colorant, and a printing suitability improver.

The thickness of the clay coating layer is preferably from 5 to 40 μm, more preferably from 10 to 30 μm, even more preferably from 15 to 25 μm, from the viewpoint of balance between smoothing, damage prevention and workability of the substrate.

The clay coating can be formed by applying a clay coating ink which is obtained by diluting a material constituting a clay coating in a solvent onto a substrate and drying it.

Glossy print layer

The glossy printed layer is a layer on a substrate or a hard coat layer and is formed by printing an ink for a glossy printed layer. By thus forming the gloss imparting layer by printing instead of vapor deposition, the cost can be reduced and the generation of curl 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 biasing the metal flakes.

Moreover, the glossy printed layer can be formed in a part of the substrate or the hard coat layer by using a desired pattern as shown in FIG. 1 to form characters, figures, figures, symbols, landscapes, figures, animals, A pattern such as an icon may be formed on all areas of the substrate or the hard coat layer as shown in FIG.

Metal scales are required in the glossy printed layer. By using metal flakes, the gloss of the glossy printed layer can be made good.

Further, the metal flakes are preferably formed on the upper portion of the glossy printed layer (the opposite side of the gloss printed layer from the hard coat layer). By the metal flakes being biased on the upper portion of the glossy printed layer, the metallic luster can be made good and the adhesion of the glossy printed layer to the substrate or hard coat layer can be improved.

The metal flakes may be biased over the upper portion of the gloss print layer during the formation of the glossy print layer. More specifically, it is considered that when the solvent of the gloss printing layer is volatilized during the heating and drying of the gloss printing layer, the solvent flows upward. Moreover, as the solvent flows, the metal scales float upward and the metal scales are biased over the upper portion of the glossy printed layer. In particular, by allowing the underlying layer of the glossy printed layer to be in a hard coat layer which is not easily permeable to the solvent, the solvent can be prevented from flowing downward, and the solvent flows almost upward, so that the metal scale can be easily biased to the upper portion of the glossy printed layer. Further, it is considered that when the hard coat layer is a cured layer of the free radiation curable resin composition, the metal flakes can be made more conspicuous.

The degree of deflection of the metal scale can be determined by photographing the cross section of the printed matter with an electron microscope and based on the difference in density within the glossy printed layer of the photograph taken. More specifically, the electrons of the metal scales were significantly reflected at the portions, so that white color was observed, and a gray tone was observed in the portion which was substantially free of metal scales.

From the viewpoint of the balance between the metallic luster and the adhesion, the ratio of the thickness of the metal flakes in the gloss printed layer to the region [(the thickness of the metal flakes in the region/the total thickness of the gloss printed layer)] is preferably 10 to 60%. More preferably, it is 20 to 50%, and further preferably 25 to 45%.

The metal flakes preferably satisfy the following condition (11).

Average thickness of metal scales / average length of metal scales ≦0.010 (11)

By setting the [average thickness of the metal flakes/the average length of the metal flakes] to 0.010 or less, the metal flakes are not easily horizontal with respect to the gloss print layer at the time of applying the ink for the gloss print layer (with the gloss print layer) The direction in which the thickness direction is orthogonal is inclined. Therefore, in the drying process of the gloss printing, when the solvent flows over the gloss printing layer, the metal scales are easily subjected to the force of the solvent flow, the metal scales are easily biased to the upper portion of the gloss printed layer, and the metal scales are easily arranged in parallel, so that It is easy to make the metal luster good. Moreover, the disadvantage caused by the inclination of the metal scale increases as the content of the metal scale increases, but when the above condition (11) is satisfied, since the metal scale is not easily inclined, the content of the metal scale can be increased, and the content can be easily made. Good metal luster.

Furthermore, if the average thickness of the metal flakes is too thin relative to the average length of the metal flakes, it may be difficult to handle and may not exhibit sufficient metallic luster.

Therefore, the condition (11) preferably satisfies the average thickness of the 0.001 ≦ metal flakes/the average length of the metal flakes ≦0.01, more preferably satisfies the average thickness of the 0.002 ≦ metal flakes/the average length of the metal flakes ≦0.008, and further preferably The average thickness of the 0.002 inch metal flakes/the average length of the metal flakes is ≦0.005.

Further, from the viewpoint of further suppressing the inclination of the metal flakes in the horizontal direction with respect to the gloss print layer at the time of applying the ink for the gloss print layer, and suppressing the protrusion of the metal flakes from the surface of the gloss print layer, metal is preferable. The average length of the scale and the thickness of the glossy printed layer satisfy the following condition (12). When the inclination of the metal flakes is suppressed, the conditions (5) to (9) are easily satisfied, and if the protrusion of the metal flakes is suppressed, the conditions (1) and (2) are easily satisfied.

Average length of 10 inch metal scales / thickness of gloss printed layer (12)

Further, if the [average length of the metal flakes/thickness of the gloss printed layer] is too large, the metal flakes may protrude from the surface of the gloss printed layer, and the condition (12) is more preferably to satisfy the average length of the 12-inch metal flakes/ The gloss printed layer has a thickness of ≦60, and further preferably satisfies the average length of the 14-inch metal scale/thickness of the gloss printed layer ≦30.

Examples of the material of the metal flakes include metals or alloys such as aluminum, gold, silver, brass, titanium, chromium, nickel, nickel-chromium alloy, and stainless steel.

The metal flakes can be obtained, for example, by peeling off the metal film obtained by vacuum-depositing the above-mentioned metal or alloy on a plastic film from a plastic film, and pulverizing and stirring the peeled metal film.

The average length of the metal flakes is preferably from 5.0 to 30 μm, more preferably from 8.0 to 20.0 μm, from the viewpoint of dispersion suitability, orientation and alignment of the metal flakes.

Further, the average thickness of the metal flakes is preferably 0.10 μm or less, more preferably 0.08 μm or less, and still more preferably 0.06 μm or less from the viewpoint of the orientation and arrangement of the metal flakes. Further, the average thickness of the metal flakes is preferably 0.01 μm or more, and more preferably 0.02 μm or more from the viewpoint of workability and high gloss.

The average length and average thickness of the metal scales are set to the average of 100 metal scales. Further, the length and thickness of each of the metal flakes can be measured by using a laser interference type three-dimensional shape analyzing device in a state in which the metal flakes are spread on a smooth substrate. The length of each metal scale refers to the maximum diameter when each metal scale is observed from a plane in any direction, and the thickness of each metal scale refers to the maximum thickness when each metal scale is observed from the cross-sectional direction. Furthermore, the maximum diameter when observing each metal scale from a plane in any direction means that the direction of the largest diameter of each metal scale is measured. For example, when the X-axis direction on the screen after the image processing of the measurement result of the three-dimensional shape analysis device is set to an arbitrary direction (measurement direction), The maximum diameter was measured in a direction parallel to the X axis. Even if it is assumed that there is a maximum diameter in a direction not parallel to the X-axis, it is not regarded as the maximum diameter.

As the laser interference type three-dimensional shape analysis device, for example, a product name "shape analysis laser microscope VK-X series" manufactured by KEYENCE Corporation can be cited.

The gloss printed layer preferably further contains a binder resin.

Examples of the binder resin include a thermoplastic resin such as a polyester resin, an urethane resin, an epoxy resin, a melamine resin, an alkyd resin, a phenol resin, an acrylic resin, or a cellulose resin, and a thermosetting resin. Further, as the binder resin, a cured product of the above ultraviolet curable resin composition can also be used.

The blending ratio of the binder resin to the metal flakes is preferably 55:45 to 30:70, more preferably 50:50 to 35:65 by mass ratio of the solid content. By setting the metal flakes to 45 parts or more with respect to 55 parts of the binder resin, it is easy to obtain sufficient metallic luster, and by setting the metal flakes to 70 parts or less with respect to 30 parts of the binder resin, the gloss printed layer can be easily obtained. The printability and the printability of the printed matter are good. Further, in the present invention, since the hard coat layer is provided under the gloss printed layer, as described above, even if a large number of metal flakes are used, the metal flakes can be biased to the upper portion of the gloss print layer.

The thickness of the gloss printed layer is preferably from 0.15 to 1.50 μm, more preferably from 0.20 to 1.00 μm, still more preferably from 0.25 to 0.75 μm, from the viewpoints of the orientation and arrangement of the metal scales and the concealability.

Furthermore, the thickness of the glossy printed layer can be, for example, the thickness of 20 portions in the cross-sectional image taken using a scanning electron microscope (SEM), a transmission electron microscope (TEM) or a scanning transmission electron microscope (STEM). The measurement was performed and calculated from the average of the values of the 20 sites. to When the film thickness to be measured is on the order of micrometer (μm), it is preferable to use SEM, and in the case of nanometer (nm) grade, it is preferable to use TEM or STEM. In the case of using SEM, the acceleration voltage is preferably set to 1 kV to 10 kV, and the magnification is preferably set to 1000 to 7000 times. In the case of using TEM or STEM, the acceleration voltage is preferably set to 10 kV to 30 kV, and the magnification is preferably 10 kV to 30 kV. Preferably, it is set to 50,000 to 300,000 times.

The thickness of the layer other than the glossy printed layer can also be measured by the same method as described above.

In order to make the gloss printed layer a desired color, the gloss printed layer may also contain titanium oxide, zinc flower, carbon black, iron oxide, yellow iron oxide, ultramarine blue, metallic pigment, pearl pigment, etc. Colorant.

The mirror gloss of the surface of the gloss printed layer of JIS Z8741:1997 at 60 degrees is preferably 150% or more, more preferably 200% or more, and still more preferably 250% or more. The upper limit of the specular gloss of the surface of the glossy printed layer is about 500%. By setting the specular gloss of the gloss printed layer to the above range, the metallic luster of the gloss printed layer becomes good, and the metallic luster of the printed matter can be made good.

The surface shape of the glossy printed layer is related to the conditions (5) to (10) and the specular gloss of the glossy printed layer. Therefore, the glossy printed layer preferably has a specific surface shape.

In the surface of the gloss printed layer, the maximum valley depth Rv (Rv _{0.08 GL} ) of JIS B0601:2001 when the cutoff value is 0.08 mm is preferably 0.25 μm or less, more preferably 0.15 μm or less, still more preferably 0.10 μm. the following. The lower limit of Rv _{0.08GL on} the surface of the gloss printed layer is about 0.010 μm.

In the surface of the gloss printed layer, the maximum valley depth Rv (Rv _0.8GL ) of JIS B0601:2001 when the cutoff value is 0.8 mm is preferably _1.00 μm or less, more preferably 0.95 μm or less, still more preferably 0.90 μm. the following. The lower limit of Rv _{0.8GL on} the surface of the gloss printed layer is about 0.05 μm.

Further, from the viewpoint of the metallic luster, the arithmetic mean roughness Ra (Ra _{0.08 GL} ) of JIS B0601:2001 on the surface of the gloss printed layer when the cutoff value is 0.08 mm is preferably 0.100 μm or less. Further, from the viewpoint of suppressing the reflection in the normal reflection direction and _{improving the visibility} , Ra _{0.08 GL is} preferably not too small. Therefore, Ra _{0.08GL is more} preferably 0.010 μm ≦ Ra _{0.08 GL} ≦ 0.070 μm, further preferably 0.020 μm ≦ Ra _0.08 GL ≦ _{0.050 μm} .

Further, from the viewpoint of the metallic luster, the arithmetic mean roughness Ra (Ra _0.8GL ) of JIS B0601:2001 on the surface of the gloss printed layer when the cutoff value is 0.8 mm is preferably 0.500 μm or less, more preferably 0.450. It is not more than μm, and more preferably 0.400 μm or less. Further, from the viewpoint of suppressing the reflection in the normal reflection direction and _{improving the visibility} , Ra _{0.8GL is} preferably 0.250 μm or more.

The glossy printed layer can be formed by applying a gloss printed layer ink obtained by diluting a component of a glossy printed layer with a solvent to a hard coat layer, drying it, and irradiating it with ultraviolet rays as necessary.

In the ink for a glossy printing layer, it is preferable to contain 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 the balance of the metal flakes and the drying efficiency.

Depending on the resin composition of the hard coat layer, the permeability of the solvent varies, so the suitable solvent type cannot be generalized, but for example, ethyl acetate, isopropyl alcohol (IPA), ethanol, n-propyl acetate (NPAC) or A solvent obtained by mixing such solvents.

Pattern layer

In order to improve the design of the printed matter, the printed matter of the present invention is preferably on the substrate and the above surface. Any portion between the protective layers has a patterned layer. For example, the pattern layer may be formed on the glossy printed layer and/or at any portion of the substrate where the portion of the gloss printed layer is not formed.

The pattern layer is formed by printing or the like. The pattern layer can be formed by multi-color printing using process colors of usual yellow, red, blue, and black, and can also be utilized by preparing a version of each color constituting the pattern. Multicolor printing of color is formed. The pattern of the pattern layer can be used without any particular limitation as long as it is a pattern (for example, characters, numerals, figures, symbols, landscapes, figures, animals, icons, and the like) used in normal printing.

As the ink used for forming the pattern layer, an ink obtained by appropriately mixing a colorant such as a pigment or a dye, an extender pigment, a solvent, a stabilizer, a plasticizer, a catalyst, a curing agent, or the like with a binder resin is used.

The binder resin is not particularly limited, and examples thereof include an acrylic resin, a styrene resin, a polyester resin, an amine ester resin, a chlorinated polyolefin resin, and a vinyl chloride-vinyl acetate copolymer resin. A polyvinyl butyral resin, an alkyd resin, a petroleum resin, a ketone resin, an epoxy resin, a melamine resin, a fluorine resin, a polyoxyn resin, a cellulose derivative, a rubber resin, or the like. These resins may be used singly or in combination of two or more.

The thickness of the pattern layer can be appropriately adjusted within a range of about 0.1 to 20 μm in consideration of the shape of the pattern layer and the target design. The pattern layer may contain an additive such as an antioxidant or an ultraviolet absorber insofar as the effect of the present invention is not impaired.

Surface protection layer

The printed matter of the present invention has a surface protective layer on the outermost surface of the side having the glossy printed layer. By forming a surface protective layer on the outermost surface, the scratch resistance and weather resistance of the printed matter can be improved. In order to achieve this effect, the surface protective layer is preferably provided to cover the glossy printed layer and the pattern as needed. The entire area of the layer is formed. Further, in the case of having a hard coat layer, it is more preferable to form the surface protective layer in such a manner as to cover the entire region of the hard coat layer.

The surface protective layer can be formed by applying an ink for a surface protective layer containing a resin component, particles to be added, and the like as needed, and drying and hardening as necessary.

The printed matter of the present invention must satisfy the conditions (5) to (9), and preferably further satisfy the condition (10). Further, in order to satisfy the conditions (5) to (10), as described above, it is important to balance the small diffusion, the moderate diffusion, and the large diffusion. Therefore, the surface protective layer must be configured such that the printed matter as a whole has a small diffusion, a moderate degree of diffusion, and a large diffusion balance.

Specifically, the surface protective layer preferably has the following surface shape.

The surface protective layer is preferably, the cutoff is set to 0.08mm when the JIS B0601: 2001 of the arithmetic mean roughness (Ra _0.08), the cutoff value is set to 0.25mm when the JIS B0601: 2001 of the arithmetic mean roughness (Ra _0.25 ) and the arithmetic mean roughness (Ra _0.8 ) of JIS B0601:2001 when the cutoff value is set to 0.8 mm satisfy the following conditions (c) and (d).

0.50 ≦ (Ra _{0.8 -} Ra _0.25 ) / (Ra _{0.25 -} Ra _0.08 ) ≦ 1.50 (c)

0.10μm≦Ra _0.25 ≦0.50μm (d)

The condition (c) is more preferably 0.60 ≦ (Ra _{0.8 -} Ra _0.25 ) / (Ra _{0.25 -} Ra _0.08 ) ≦ 1.40, and further preferably 0.70 ≦ (Ra _{0.8 -} Ra _0.25 ) / (Ra _{0.25 -} Ra _0.08 ) ≦ 1.30.

Condition (d) more preferably satisfies the 0.15μm ≦ Ra _0.25 ≦ 0.45μm, and further preferably satisfy 0.20μm ≦ Ra _0.25 ≦ 0.40μm.

The surface of the surface protective layer has a Ra of _0.08 or less, preferably 0.20 μm or less, more preferably 0.18 μm or less, still more 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.

The 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, still more preferably 0.50 μm or less. The lower limit of Ra _0.8 of the surface of the surface protective layer is about 0.30 μm.

Further, the surface protective layer is preferably a maximum valley depth (Rv _0.08 ) of JIS B0601:2001 when the cutoff value is set to 0.08 mm, and a maximum valley depth (Rv of JIS B0601:2001 when the cutoff value is 0.25 mm). _0.25 ) and the maximum valley depth (Rv _0.8 ) of JIS B0601:2001 when the cutoff value is set to 0.8 mm satisfy the following conditions (e) and (f).

1.00≦(Rv _0.8 -Rv _0.25 )/(Rv _0.25 -Rv _0.08 )≦2.00 (e)

0.50μm≦Rv _0.25 ≦1.00μm (f)

The condition (e) is more preferably 1.10 ≦ (Rv _{0.8 -} Rv _0.25 ) / (Rv _{0.25 -} Rv _0.08 ) ≦ 1.80, further preferably 1.20 ≦ (Rv _{0.8 -} Rv _0.25 ) / (Rv _{0.25 -} Rv _0.08 ) ≦ 1.50 .

The condition (f) is more preferably 0.55 μm ≦ Rv _0.25 ≦ 0.90 μm, and further preferably 0.60 μm ≦ Rv _0.25 ≦ 0.80 μm.

Rv _{0.08 on the} surface of the surface protective layer is preferably 0.55 μm or less, more preferably 0.45 μm or less, still more 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.

The 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, still more preferably 1.50 μm or less. The lower limit of Rv _0.8 of the surface of the surface protective layer is about 1.00 μm.

In order to impart unevenness of a low-frequency component, irregularities of an intermediate frequency component, and irregularities of a high-frequency component to the surface of the surface protective layer, the surface protective layer is preferably a lower layer (gloss printing layer, pattern layer, etc.) when the surface protective layer is formed. Bumps have followability. From this point of view, the resin component of the ink for the surface protective layer preferably contains a thermoplastic resin and/or a thermosetting resin. also, From this point of view, the ink for the surface protective layer preferably contains a solvent.

It is preferably a thermoplastic resin and/or a thermosetting resin containing 5 to 60% by mass of the total resin component of the ink for a surface protective layer, more preferably 10 to 30% by mass. In addition, from the viewpoint of improving the scratch resistance and weather resistance of the printed matter, the remainder of the total resin component of the ink for the surface protective layer is preferably an ultraviolet curable compound.

As the thermoplastic resin and/or the thermosetting resin, a general-purpose resin such as an acrylic resin, an amine ester resin, or a polyester resin can be used. As the ultraviolet curable compound, the same compound as that exemplified in the cured layer can be used.

Further, in order to increase moderate diffusion and large diffusion, the surface protective layer preferably has an internal haze. If only a certain amount of diffusion or large diffusion is ensured by the surface unevenness of the surface protective layer, the surface of the surface protective layer may be excessively uneven, and the appearance of the printed matter may be deteriorated, and the internal haze may be used together. It maintains the appearance of the printed matter and is easy to ensure a moderate spread or a large spread.

The internal haze can be expressed by the difference in refractive index between the materials constituting the surface protective layer. For example, when the surface protective layer contains a resin component and particles, the internal haze can be expressed by making the refractive index of the resin component different from the refractive index of the particles. Further, the internal haze can also be expressed by blending resins having poor compatibility and different refractive indices and phase-separating the resins in the surface protective layer.

Examples of the particles include polymethyl methacrylate, polyacrylic acid-styrene copolymer, melamine resin, polycarbonate, polystyrene, polyvinyl chloride, and benzoquinone. - Organic particles such as melamine-formaldehyde condensate, polyfluorene oxide, fluorine resin, and polyester resin, and inorganic particles such as silica, alumina, zirconia, and titania.

From the viewpoint of exhibiting internal haze, it is preferred to select a refractive index difference of 0.01 from the resin component. ~0.10 particles.

The average particle diameter of the particles is preferably smaller than the thickness of the surface protective layer. The specific average particle diameter varies depending on the thickness of the surface protective layer, and therefore cannot be generalized, and is preferably about 0.10 to 1.0 μm.

The content of the particles is preferably from 2 to 20% by mass, more preferably from 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 from 0.50 to 5.0 μm, more preferably from 0.80 to 1.5 μm.

In order to improve weather resistance, the surface protective layer preferably contains an ultraviolet absorber and/or a light stabilizer.

[container]

The container of the present invention is obtained by using the above-described printed matter of the present invention.

The container is not particularly limited, and examples thereof include a beverage container, a food container, and the like. The container of the present invention has an excellent gloss and is excellent in design. Further, since the curl of the printed matter is suppressed, the problem caused by the curling can be prevented during the manufacture of the container.

[Manufacturing method of printed matter]

In the method for producing a printed matter according to the first embodiment of the present invention, the printed matter has a glossy printed layer containing metal flakes at any portion on the substrate, and further has a surface protective layer on the outermost surface on the side having the glossy printed layer. In the method of producing a printed matter, the step of forming a glossy printed layer by using an ink for a glossy printed layer containing a metal scale, and the step of forming a surface protective layer by using a surface protective layer to form a surface protective layer When the cutoff value is set to 0.08 mm, the arithmetic mean roughness (Ra _0.08 ) of JIS B0601:2001, and the arithmetic mean roughness (Ra _0.25 ) of JIS B0601:2001 when the cutoff value of the surface protective layer surface is 0.25 mm, The arithmetic mean roughness (Ra _0.8 ) of JIS B0601:2001 when the cutoff value of the surface protective layer surface is set to 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)

0.10μm≦Ra _0.25 ≦0.50μm (2)

In the method for producing a printed matter according to the second embodiment of the present invention, a gloss printed layer is formed on an arbitrary portion of the substrate, and a surface protective layer is formed on the outermost surface of the side having the gloss printed layer, and the metal scale is contained. a step of forming the glossy printed layer with an ink and a step of forming the surface protective layer with an ink for a surface protective layer, whereby the surface facing the surface protective layer is irradiated at an angle of 45 degrees from the normal In the case of visible light, the reflection intensity is measured every 0.1 degrees with respect to the normal reflection direction in the range of -45 degrees to +45 degrees, and the absolute value of the diffusion angle of the reflection intensity showing 1/2 of the reflection intensity in the regular reflection direction is set to α. The absolute value of the diffusion angle indicating the reflection intensity of 1/3 of the reflection intensity in the normal reflection direction is β, and the absolute value of the diffusion angle indicating the reflection intensity of 1/10 of the reflection intensity in the regular reflection direction is γ. In at least a part of the surface protective layer of the upper portion where the glossy printed layer is located, the α, β, and γ satisfy the following conditions (5) to (9).

4.0 degrees ≦α≦6.0 degrees (5)

5.5 degrees ≦β≦10.0 degrees (6)

9.5 degrees ≦γ≦15.0 degrees (7)

1.2 degrees ≦β-α≦2.5 degrees (8)

4.0 degrees ≦γ-β≦8.0 degrees (9)

Hereinafter, the embodiment common to the first embodiment and the second embodiment will be described unless otherwise specified.

As an evaluation index of anti-glare property, the specular gloss of JIS Z8741:1997 is sometimes used. Specifically, if the specular gloss is small (if the regular reflection intensity is small), it is used in the reference having anti-glare properties. However, even if the intensity of the regular reflection is small, if the difference between the intensity of the regular reflection and the reflection intensity of the peripheral region in the vicinity of the direction of the regular reflection is too large, the angle of the reflection intensity suddenly changes when the hand-held printed matter is observed from various angles. . The portion where the reflection intensity suddenly changes means that there is a difference in the level of the anti-glare property depending on the observation angle. The difference in the level of the anti-glare property causes the visual person to feel uncomfortable, and the high-grade feeling of the printed matter is lowered.

The reason for having an anti-glare property but causing a sudden change in the reflection intensity is that if the value of the regular reflection intensity even contains a small diffusion, it will be reduced to some extent even if it does not contain moderate diffusion or large diffusion.

By satisfying the conditions (1) and (2), or (5) to (9) of the present invention, Ra of the high-frequency component, the intermediate-frequency component, and the low-frequency component is moderately present on the surface of the surface protective layer, meaning surface protection The reflections on the surface of the layer contain a certain amount of smaller diffusion, moderate diffusion, and greater diffusion, respectively. Therefore, with respect to the printed matter produced by the manufacturing method of the present invention, even if the hand-held printed matter is observed from various angles, there is no sharp change in the reflection intensity, and it is possible to impart an anti-glare property having a high-grade feeling without feeling uncomfortable.

Further, since the diffusion on the surface protective layer satisfying the conditions (1) and (2) or (5) to (9) is not excessive, the reduction in the metallic luster of the gloss printed layer can be suppressed to the minimum necessary. Therefore, the printed matter produced by the manufacturing method of the present invention has a metallic luster.

Further, according to the manufacturing method of the present invention, the above effects can be easily and stably produced. Standardized as high quality prints.

In order to obtain a printed matter satisfying the conditions (1) and (2), or (5) to (9), it is preferred to form a hard coat layer before forming the gloss printed layer. Moreover, in order to obtain a printed matter satisfying the conditions (1) and (2) or (5) to (9), it is preferable to set the surface shape of the surface protective layer to the above range and to cause the internal protective layer to have an internal haze.

Further, in order to improve the design, it is preferred to form a pattern layer after forming a glossy printed layer.

In the method for producing a printed matter according to the first embodiment of the present invention, it is preferable to obtain a printed matter such that the above conditions (3) and (4) are satisfied. In the method for producing a printed matter according to the second embodiment of the present invention, it is preferable to obtain a printed matter so as to satisfy the above condition (10). Moreover, it is preferable to obtain a printed matter so as to satisfy appropriate conditions (for example, specular glossiness of a gloss printed layer) of the hard coat layer, the gloss print layer, the pattern layer, and the surface protective layer.

The substrate, the hard coat layer, the gloss printed layer, the pattern layer, and the surface protective layer used in the method for producing a printed matter of the present invention, and the substrate, hard coat layer, gloss printed layer, and patterned layer of the printed matter of the present invention, The embodiment of the surface protective layer is the same.

[Selection method of printed matter]

In the method of selecting a printed matter according to the first embodiment of the present invention, when a printed matter having a surface-protected layer on the outermost surface of the side having the glossy printed layer is selected, the following is set as Judgment conditions: JIS B0601:2001 arithmetic mean roughness (Ra _0.08 ) when the cutoff value of the surface protective layer surface is set to 0.08 mm, and JIS B0601:2001 when the surface protective layer surface has a cutoff value of 0.25 mm The arithmetic mean roughness (Ra _0.25 ) and the arithmetic mean roughness (Ra _0.8 ) of JIS B0601:2001 when the cutoff value of the surface protective layer surface is 0.8 mm satisfy the following conditions (1) and (2).

0.50≦(Ra _0.8 -Ra _0.25 )/(Ra _0.25 -Ra _0.08 )≦1.50 (1)

0.10μm≦Ra _0.25 ≦0.50μm (2)

The method for selecting a printed matter according to the second embodiment of the present invention has a glossy printed layer containing a metal flake selected at any portion on the substrate, and further having a surface protective layer on the outermost surface on the side having the gloss printed layer. In the case of printing, the following conditions are used as the determination condition: when the visible light is irradiated at an angle of 45 degrees from the normal to the surface on the surface protective layer side, every 0.1 degree in the range of -45 degrees to +45 degrees with respect to the regular reflection direction. The reflection intensity is measured, and the absolute value of the diffusion angle indicating the reflection intensity of 1/2 of the reflection intensity in the normal reflection direction is α, and the absolute value of the diffusion angle indicating the reflection intensity of 1/3 of the reflection intensity in the regular reflection direction is set to β, when the absolute value of the diffusion angle indicating the reflection intensity of 1/10 of the reflection intensity in the normal reflection direction is γ, the α, β is at least a part of the surface protective layer directly above the gloss printed layer. And γ satisfy the following conditions (5) to (9).

4.0 degrees ≦α≦6.0 degrees (5)

5.5 degrees ≦β≦10.0 degrees (6)

9.5 degrees ≦γ≦15.0 degrees (7)

1.2 degrees ≦β-α≦2.5 degrees (8)

4.0 degrees ≦γ-β≦8.0 degrees (9)

As described above, even if the specular gloss is used as the criterion for determining the anti-glare property, it is sometimes impossible to select an anti-glare property having a high-grade feeling with a small difference in the degree of anti-glare of each angle, and suppressing the gloss printed layer. A printed matter having reduced anti-glare properties of metallic luster. Moreover, if the evaluation is performed only by the human eye, it will be affected by the individual's vision, color vision, physical condition, etc., and the quality of the printed matter cannot be standardized. According to the method for selecting a printed matter of the present invention, it can be accurately selected A printed matter having a metallic luster and an anti-glare property with a high-grade feel can be selected, and the quality of the printed matter can be standardized.

The printed matter of the object selected in the present invention may also have a layer other than the gloss printed layer and the surface protective layer. For example, a hard coat layer may be provided between the substrate and the gloss print layer, or a pattern layer may be provided between the gloss print layer and the surface protective layer.

In the method of selecting a printed matter according to the first embodiment of the present invention, it is preferable that the conditions (3) and (4) are further determined as determination conditions. In the method of selecting a printed matter according to the second embodiment of the present invention, it is preferable that the above condition (10) is a determination condition. Further, it is preferable to add appropriate conditions (for example, specular gloss of the gloss printed layer) such as the hard coat layer, the gloss print layer, the pattern layer, and the surface protective layer as the determination conditions.

The substrate, the hard coat layer, the gloss print layer, the pattern layer, and the surface protective layer of the printed matter selected in the method for selecting a printed matter of the present invention, and the substrate, hard coat layer, gloss printed layer, and pattern of the printed matter of the present invention. The embodiment of the layer and the surface protective layer is the same.

[Examples]

Next, the present invention will be described in more detail by way of examples, but the invention is not limited by the examples.

1. Determination and evaluation

The following measurements and evaluations were performed on the printed materials produced in the examples and comparative examples. The results are shown in Table 1.

1-1. Specular gloss

According to JIS Z8741:1997, the printed matter of Examples 1 to 4 and Comparative Examples 1 to 6 or the intermediate of the printed matter was measured using a micro-TRI-gloss of BYK Gardner Co., Ltd. as a measuring device. 60 degree specular gloss of glossy printed or vapor deposited film.

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, the arithmetic mean roughness Ra and the maximum valley depth Rv of JIS B0601:2001 when the cutoff value was 0.08 mm were measured, and the cutoff value was 0.25 mm. The arithmetic mean roughness Ra and the maximum valley depth Rv of JIS B0601:2001 and the arithmetic mean roughness Ra and the maximum valley depth Rv of JIS B0601:2001 when the cutoff value is set to 0.8 mm. In addition, the measurement of Ra and Rv was carried out using the trade name SE-340 manufactured by Otaru Research Co., Ltd., and the following measurement conditions were used.

[The stylus of the surface roughness detecting section]

The trade name SE2555N manufactured by Otaru Research Institute Co., Ltd. (front end radius of curvature: 2μm, apex angle: 90 degrees, material: diamond)

[Measurement Conditions of Surface Roughness Tester]

‧ Evaluation length (reference length): 5 times the cutoff value λ c

‧Before the stylus delivery speed: 0.5mm/s

‧Prepared length: (cutoff value λ c) × 2

‧ Vertical magnification: 2000 times

‧ Horizontal magnification: 10 times

1-3. Reflection intensity distribution

Using a goniophotometer (manufactured by Murakami Color Research Co., Ltd., trade name GP-200), visible light (parallel light) was irradiated toward the outermost surface of the printed matter at an angle of 45 degrees from the normal. For the reflected light, the photoreceptor is scanned every 0.1 degrees with respect to the normal reflection direction of the illumination light in the range of -45 degrees to +45 degrees, thereby measuring the intensity (luminosity) at each angle. Measuring intensity (light In the measurement, the opening angle of the photodetector detected by the pupil of the photoreceiver was set to 0.1 degree. Based on the measurement results, α, β, γ, and δ were calculated.

1-4. Metallic luster

The printed matter of Comparative Example 1 was used as a reference material, and the metallic luster of the printed materials of Examples 1 to 4 and Comparative Examples 2 to 6 was evaluated by visual observation. As a result, it is assumed that the metallic gloss equivalent to the reference material is "A", and the metallic gloss is set to "B" even though the metallic gloss is worse than the reference material, and the metallic gloss is not set to " C".

1-5. Anti-glare

The printed materials of Examples 1 to 4 and Comparative Examples 1 to 6 were placed under various illuminations under the illumination of a fluorescent lamp, and the anti-glare properties of the respective angles were evaluated by visual observation. As a result, the difference in anti-glare property at all angles and the difference in the anti-glare property of each angle are not set to "A", and the anti-glare property is felt to be constant, but the anti-glare property of each angle is different. For "B", it is set to "C" for those who have almost no anti-glare.

1-6. Curling

For the printed materials of Examples 1 to 4 and Comparative Examples 1 to 6, the crimp depth was measured under the conditions of a temperature of 25 ° C and a humidity of 75% RH based on the "curl depth measuring method" of JAPAN TAPPI No. 15-1.

2. Production of printed matter [Example 1]

On the entire surface of the coated surface of the substrate (single-sided ivory paper having a basis weight of 235 g/m ² ), the ink for hard coat layer 1 of the following formulation was applied and dried to have a thickness of 6 μm after drying. The ultraviolet ray is irradiated to form a hard coat layer (a cured layer of the composition of the free radiation curable resin).

Then, on the entire surface of the hard coat layer, the thickness after drying is 0.50 μm. The glossy printed layer of the following formulation was inked 2 and dried to form a glossy printed layer. The thickness of the region of the glossy printed layer in which the metal flakes are substantially absent is 0.30 μm, and the thickness of the metal flakes in the region is 0.20 μm.

Then, a dark blue pattern layer is formed by lithographic printing on any portion of the glossy printed layer. Then, the surface protective layer ink 3 of the following formulation was applied so as to cover the entire surface of the pattern layer and the gloss printed layer and the thickness after drying was 1.0 μm, and ultraviolet irradiation was performed to form a surface protective layer. The printed matter of Example 1.

<Ink for hard coating 1>

‧Free radiation hardening compound 70 parts

(Manufactured by BASF JAPAN, trade name: Lumogen OVD Primer301)

(a mixture of a difunctional acrylate monomer and a trifunctional acrylate monomer)

‧ solvent (ethyl acetate) 30 parts

<Gloss printing layer ink 2>

‧Binder resin (nitrocellulose) 4.8 parts

(Manufactured by DIC GRAPHICS)

(trade name: XS-763 Medium NT-No.1)

‧ Aluminum scales 7.2

(average length 14 μm, average thickness 0.04 μm)

‧ Solvent (ethyl acetate, IPA, ethanol, NPAC) 88 parts

<Ink for surface protective layer 3>

‧ UV curable resin composition 100 parts

(Manufactured by DIC GRAPHICS, trade name: UV CARTON ACT OP VARNISH)

(mixture containing 55 to 65 mass% of ultraviolet curable monomer, 10 to 20 mass% of synthetic resin, 5 to 15 mass% of particles, and 5 to 15 mass% of auxiliary agent as main components)

Further, in Example 1, the arithmetic mean roughness Ra of JIS B0601:2001 when the cutoff value of the surface of the substrate was set to 0.08 mm was 0.129 μm. Further, the arithmetic mean roughness Ra of JIS B0601:2001 when the cutoff value of the substrate surface was 0.8 mm was 0.524 μm.

Further, in the first embodiment, the arithmetic mean roughness Ra of JIS B0601:2001 when the cutoff value of the surface of the hard coat layer was 0.08 mm was 0.026 μm. Further, the arithmetic mean roughness Ra of JIS B0601:2001 when the cutoff value of the surface of the hard coat layer was 0.8 mm was 0.305 μm.

Further, in the first embodiment, the arithmetic mean roughness Ra of JIS B0601:2001 when the cutoff value of the surface of the gloss printed layer was 0.08 mm was 0.036 μm. Further, the arithmetic mean roughness Ra of JIS B0601:2001 when the cutoff value of the surface of the gloss printed layer was 0.8 mm was 0.359 μm.

[Embodiment 2]

The printed matter of Example 2 was obtained in the same manner as in Example 1 except that the ink for the gloss printing layer 2 was applied and dried to a thickness of 0.35 μm to form a gloss printed layer.

[Example 3]

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

[Example 4]

Example 4 was obtained in the same manner as in Example 1 except that the gloss printing layer ink 2 was applied and dried to a thickness of 1.00 μm to form a gloss printed layer. Printed matter.

[Comparative Example 1]

The printed matter 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 formed on the non-gloss printed layer.

[Comparative Example 2]

The 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]

The 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 surface protective layer ink 4 described below.

<Ink for surface protective layer 4>

‧ UV curable compound 100 parts

(Manufactured by DIC GRAPHICS, trade name: UV low odor paint S)

[Comparative Example 4]

A vapor deposited film having an aluminum deposited film having a thickness of 50 nm was prepared on a biaxially stretched PET film having a thickness of 12 μm. Then, the surface of the coated surface of the substrate (single-sided ivory paper having a basis weight of 235 g/m ² ) and the deposited film were extruded while using a sandwich lamination method to extrude low-density polyethylene (LDPE) to a thickness of 15 μm. The surface of the PET film side was bonded to each other to obtain a laminated substrate.

Then, a dark blue pattern layer is formed by gravure printing on the deposited film of the laminated substrate. Then, the surface protective layer ink 5 of the following formulation was applied and dried to cover the entire surface of the pattern layer and the vapor-deposited film so as to have a thickness of 1.0 μm after drying, thereby forming a surface protective layer and obtaining a comparison. The printed matter of Example 4.

<Ink for surface protective layer 5>

‧ Thermosetting resin 70 parts

(Manufactured by DIC GRAPHICS, trade name: DIC SAFE G-310 OP VARNISH)

‧Solvent (water/IPA=2/8) 30 parts

Further, in Comparative Example 4, the arithmetic mean roughness Ra of JIS B0601:2001 when the vapor-deposited film had a cutoff value of 0.08 mm was 0.048 μm. Further, the arithmetic mean roughness Ra of JIS B0601:2001 when the cutoff value of the vapor deposited film was 0.8 mm was 0.301 μm.

[Comparative Example 5]

The entire surface of the coated surface of the substrate (single-sided ivory paper having a basis weight of 235 g/m ² ) was coated with the ink 6 for the gloss printing layer of the following formulation so that the thickness after drying became 1.5 μm. Dry to form a glossy printed layer. Then, a dark blue pattern layer was formed on the gloss printed layer by the same method as in Example 1. Then, the surface protective layer ink 7 of the following formulation was applied so as to cover the entire surface of the pattern layer and the gloss printed layer and the thickness after drying was 1.0 μm, and ultraviolet irradiation was performed to form a surface protective layer. Comparative Example 5 printed matter.

<Gloss printing layer ink 6>

‧Binder resin (nitrocellulose) 6 parts

(Manufactured by DIC GRAPHICS)

(trade name: XS-763 Medium NT-No.1)

‧Aluminum sheet 6 parts

(Manufactured by TOYO ALUMINIUM K.K., trade name: TD-180T)

(average length 15μm, average thickness over 0.2μm)

‧Solvent (ethyl acetate, IPA, ethanol, NPAC) 88

<Ink for surface protective layer 7>

‧ UV curable resin composition 100 parts

(Manufactured by TOYO INK, trade name: FD OLP MULTICOLOR OP VARNISH M1-B)

(mixture containing 35 to 45 mass% of ultraviolet curable monomer, 35 to 45 mass% of synthetic resin, 1 to 10 mass% of particles, and 5 to 15 mass% of auxiliary agent as main components)

Further, in Comparative Example 5, the arithmetic mean roughness Ra of JIS B0601:2001 when the cut-off value of the gloss printed layer was 0.08 mm was 0.15 μm.

[Comparative Example 6]

On the entire coated side of the substrate (single-sided ivory paper having a basis weight of 235 g/m ² ), a low-density polyethylene (LDPE) was extruded by a melt extrusion method to a thickness of 15 μm to form a thermoplastic resin. Floor.

Then, the gloss printing layer ink 2 of the above formulation was applied to the entire surface of the thermoplastic resin layer so as to have a thickness of 0.70 μm after drying, and dried to form a glossy printed layer.

Then, a yellow pattern layer is formed by lithographic printing on any portion of the glossy printed layer. Then, the surface protective layer ink 3 of the above-described formulation was applied so as to cover the entire surface of the pattern layer and the gloss printed layer and the thickness after drying was 1.0 μm, and ultraviolet irradiation was performed to form a surface protective layer (solvent free). A printed matter of Comparative Example 6 was obtained as a cured layer of a UV curable resin composition.

According to the results of Table 1, it was found that the printed matter of Example 1 had a metallic luster and had an anti-glare property with a high-grade feeling.

[Industrial availability]

The printed matter and the container of the present invention are useful in that they have a metallic luster without using a metal vapor deposition method and have an anti-glare property with a high-grade feeling.

1‧‧‧Substrate

2‧‧‧hard coating

3‧‧‧Glossy print layer

5‧‧‧Surface protection layer

10‧‧‧Printed matter

31‧‧‧Metal scales are biased in the area

Claims (20)

A printed matter having a glossy printed layer containing a metal scale at any portion on a substrate, and further having a surface protective layer on an outermost surface of the side having the glossy printed layer, the surface of the surface protective layer being cut off when the value is set to 0.08mm of JIS B0601: 2001 of the arithmetic mean roughness (Ra _0.08), the cut-off value of the surface of the surface protective layer is set to 0.25mm when the JIS B0601: 2001 of the arithmetic mean roughness (Ra _0.25), And the arithmetic mean roughness (Ra _0.8 ) of JIS B0601:2001 when the cutoff value of the surface protective layer is set to 0.8 mm satisfies the following conditions (1), (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 printed matter of the first aspect of the invention, wherein the surface of the surface protective layer has a maximum valley depth (Rv _0.08 ) of JIS B0601:2001 when the cutoff value is set to 0.08 mm, and a cutoff value of the surface of the surface protective layer is set. The maximum valley depth (Rv _0.25 ) of JIS B0601:2001 at _0.25 mm and the maximum valley depth (Rv _0.8 ) of JIS B0601:2001 when the surface of the surface protective layer is set to 0.8 mm satisfy the following conditions ( 3), (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). A printed matter having a glossy printed layer at any portion on a substrate and further having a surface protective layer on an outermost surface of the side having the glossy printed layer, the glossy printed layer containing metal scales facing the printed matter When the surface of the surface protective layer is irradiated with visible light at an angle of 45 degrees from the normal, the reflection intensity is measured every 0.1 degrees in the range of -45 degrees to +45 degrees with respect to the regular reflection direction, and the reflection intensity in the forward reflection direction is displayed. Expansion of 1/2 reflection intensity The absolute value of the scattered angle is set to α, and the absolute value of the diffusion angle indicating the reflection intensity of 1/3 of the reflection intensity in the normal reflection direction is β, and the diffusion angle of the reflection intensity of 1/10 of the reflection intensity in the regular reflection direction is displayed. When the absolute value is γ, the α, β, and γ satisfy at least a part of the surface protective layer of the upper portion of the gloss printed layer satisfying the following conditions (5) to (9): 4.0 degrees ≦ α ≦ 6.0 Degree (5) 5.5 degrees ≦β≦10.0 degrees (6) 9.5 degrees ≦γ≦15.0 degrees (7) 1.2 degrees ≦β-α≦2.5 degrees (8) 4.0 degrees ≦γ-β≦8.0 degrees (9). The printed matter of claim 3, wherein the surface facing the surface of the printed matter on the surface of the surface of the printed matter is irradiated with visible light at an angle of 45 degrees from the normal, and is in the range of -45 degrees to +45 degrees with respect to the direction of the regular reflection. When the reflection intensity is measured at 0.1 degree, and the absolute value of the diffusion angle indicating the reflection intensity of 1/20 of the reflection intensity in the normal reflection direction is δ, at least a part of the surface protective layer directly above the gloss printed layer is present. γ, and δ satisfy the following condition (10): δ-γ ≦ 4.0 degrees (10). The printed matter according to any one of claims 1 to 4, wherein the average length and the average thickness of the metal flakes satisfy the following condition (11): the average thickness of the metal flakes/the average length of the metal flakes ≦0.010 (11) . The printed matter according to any one of claims 1 to 5, wherein the average length of the metal flakes and the thickness of the gloss printed layer satisfy the following condition (12): 10 ≦ [average length of metal scales / thickness of gloss printed layer] (12). The printed matter according to any one of claims 1 to 6, wherein the metal scale has an average length of 5.0 to 30.0 μm. The printed matter according to any one of claims 1 to 7, wherein the metal flakes have an average thickness of 0.10 μm or less. The printed matter according to any one of claims 1 to 8, wherein the gloss printed layer has a thickness of 0.15 to 1.50 μm. The printed matter of any one of claims 1 to 9, wherein the metal scale is biased over the glossy printed layer. The printed matter according to any one of claims 1 to 10, which is formed by patterning the glossy printed layer. A printed matter according to any one of claims 1 to 11, which has a hard coat layer between the substrate and the gloss printed layer. The printed matter of claim 12, wherein the hard coat layer is a hardened layer of the free radiation curable resin composition. The printed matter of any one of claims 1 to 13, wherein the substrate is a paper substrate. The printed matter according to any one of claims 1 to 14, which has a patterned layer at any portion between the substrate and the surface protective layer. A container obtained by using the printed matter of any one of claims 1 to 15. A method for producing a printed matter, wherein the printed matter has a glossy printed layer containing a metal scale at any portion of the substrate, and further has a surface protective layer on an outermost surface of the side having the glossy printed layer, and a method of producing the printed matter The step of forming the glossy printed layer with an ink containing a metallic scale-containing glossy printing layer and the step of forming the surface protective layer with an ink for a surface protective layer are used to set a cutoff value of 0.08 on the surface of the surface protective layer. The arithmetic mean roughness (Ra _0.08 ) of JIS B0601:2001 at mm, the arithmetic mean roughness (Ra _0.25 ) of JIS B0601:2001 when the cutoff value of the surface protective layer is 0.25 mm, and the surface protection the cutoff value of the surface layer is set to 0.8mm when the JIS B0601: 2001 of the arithmetic mean roughness (Ra _0.8) satisfies the following condition (1), (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). A method for producing a printed matter, comprising forming a gloss printed layer on an arbitrary portion of a substrate, and further forming a surface protective layer on an outermost surface of the side having the glossy printed layer, and forming an ink by a gloss printed layer containing a metal scale a step of forming the glossy printed layer and a step of forming the surface protective layer with an ink for the surface protective layer, whereby the surface facing the surface protective layer is irradiated with visible light at an angle of 45 degrees from the normal, relative to the regular reflection The direction of the reflection is measured every 0.1 degrees in the range of -45 degrees to +45 degrees, and the absolute value of the diffusion angle of the reflection intensity showing 1/2 of the reflection intensity in the regular reflection direction is set to α, and the reflection in the regular reflection direction is displayed. The absolute value of the diffusion angle of the reflection intensity of 1/3 of the intensity is β, and when the absolute value of the diffusion angle of the reflection intensity of 1/10 of the reflection intensity in the normal reflection direction is γ, the gloss printed layer is placed. In at least a part of the surface protective layer of the upper portion, the α, β, and γ satisfy the following conditions (5) to (9): 4.0 degrees ≦α≦6.0 degrees (5) 5.5 degrees ≦β≦10.0 degrees (6) 9.5 degrees ≦γ≦15.0 degrees (7) 1.2 degrees ≦β-α≦2.5 degrees (8) 4.0 degrees ≦γ-β≦8.0 Degree (9). A method for selecting a printed matter, which comprises a glossy printed layer containing a metal flake at any portion selected on a substrate, and further comprising a surface protective layer on an outermost surface of the side having the glossy printed layer, In the case where the surface of the surface protective layer has a cutoff value of 0.08 mm, the arithmetic mean roughness (Ra _0.08 ) of JIS B0601:2001 and the surface of the surface protective layer are set to 0.25 mm. The arithmetic mean roughness (Ra _0.25 ) of JIS B0601:2001 and the arithmetic mean roughness (Ra _0.8 ) of JIS B0601:2001 when the cutoff value of the surface protective layer is set to 0.8 mm satisfy the following condition (1), (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). A method for selecting a printed matter, which comprises a glossy printed layer containing a metal flake at any portion selected on a substrate, and further comprising a surface protective layer on an outermost surface of the side having the glossy printed layer, The case is judged as follows: When the visible light is irradiated at an angle of 45 degrees from the normal to the surface on the side of the surface protective layer, the reflection intensity is measured every 0.1 degrees in the range of -45 degrees to +45 degrees with respect to the normal reflection direction. The absolute value of the diffusion angle showing the reflection intensity of 1/2 of the reflection intensity in the specular reflection direction is set to α, which will show the inverse of the reflection intensity of the specular reflection direction. The absolute value of the diffusion angle of the incident intensity is β, and when the absolute value of the diffusion angle indicating the reflection intensity of 1/10 of the reflection intensity in the normal reflection direction is γ, the surface protective layer is located directly above the gloss printed layer. In at least a part of the region, the α, β, and γ satisfy the following conditions (5) to (9): 4.0 degrees ≦ α ≦ 6.0 degrees (5) 5.5 degrees ≦ β ≦ 10.0 degrees (6) 9.5 degrees ≦ γ ≦ 15.0 degrees (7) 1.2 degrees ≦β-α≦2.5 degrees (8) 4.0 degrees ≦γ-β≦8.0 degrees (9).