JP6988220B2 - Printed matter and containers using it - Google Patents

Description

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

Conventionally, various printed matter may be required to have a metallic luster in order to improve its design.

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

However, since a film having a metallic luster is formed by forming a metal vapor deposition film on the film, it is costly and is not suitable for inexpensive printed matter. Further, the substrate in which a film having a metallic luster is bonded on a paper substrate is curled due to the difference in shrinkage between the paper and the film, and subsequent steps (for example, a printing step on the substrate, a printed matter in a container) are generated. There is a problem that the accuracy of the processing process) is lowered and the yield is lowered.
Patent Document 1 has been proposed in order to solve the above problem.

Japanese Unexamined Patent Publication No. 2016-88098

Patent Document 1 discloses a printed matter having a hard coat layer and a glossy printed layer including a metal thin film fragment on a paper base material.

The printed matter of Patent Document 1 has no problem in terms of cost and curl, and has a certain level of metallic luster. However, since the printed matter of Patent Document 1 forms a hard coat layer from an ultraviolet curable resin composition containing a monomer and an initiator, it remains in the hard coat layer when the manufacturing process is not sufficiently controlled. In some cases, odors caused by monomers and initiators were generated. In particular, it was difficult to remove the odor when a large amount of the monomer or the initiator was infiltrated into the paper substrate.

An object of the present invention is to provide a printed matter and a container which imparts metallic luster and suppresses odor without using means of metal vapor deposition.

In order to solve the above problems, the present invention provides the following [1] to [2].
[1] A printed matter having a glossy print layer on a paper substrate, the printed matter has an anchor coat layer containing a thermoplastic resin between the paper substrate and the glossy print layer, and the glossy print layer is a metal. A printed matter containing scales and having a surface roughness on the glossy printing layer side with respect to the paper substrate of the printed matter satisfying the following condition 1.
<Condition 1>
_{The arithmetic average roughness Ra 0.25} of JIS B0601: 1994 of the surface when the cutoff value is 0.25 mm is 0.25 μm or less.
[2] A container made of the printed matter according to the above [1].

The printed matter and container of the present invention can impart metallic luster and suppress odor without using means for metal vapor deposition.

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

[Printed matter]
The printed matter of the present invention is a printed matter having a glossy printing layer on a paper substrate, and the printed matter has an anchor coat layer containing a thermoplastic resin between the paper substrate and the glossy printing layer, and the glossy printing The layer contains metal scales, and the roughness of the surface on the glossy print layer side with respect to the paper substrate of the printed matter satisfies the following condition 1.
<Condition 1>
_{The arithmetic average roughness Ra 0.25} of JIS B0601: 1994 of the surface when the cutoff value is 0.25 mm is 0.25 μm or less.

1 to 3 are cross-sectional views showing an embodiment of the printed matter 100 of the present invention. The printed matter 100 of FIGS. 1 to 3 has an anchor coat layer 20 and a glossy printed layer 30 on the paper base material 10 in this order. Further, the printed matter 100 of FIGS. 1 to 3 has a surface protective layer 40 so as to cover the surface on the glossy printing layer 20 side with respect to the paper base material 10 of the printed matter. Further, the printed matter 100 of FIGS. 2 and 3 has a pattern layer 50.

<< Base material >>
The paper base material is not particularly limited as long as it is made of paper and has shapeability, bending resistance, rigidity, waist, strength and the like. For example, it is a main strength material, and bleached or unbleached paper having a strong size property, or various types of paper such as pure white roll paper, kraft paper, paperboard, processed paper, and milk base paper can be used. Further, the paper base material may be a stack of a plurality of layers of the above-mentioned paper.

The thickness of the paper substrate is preferably 110 to 860 μm, more preferably 260 to 640 μm. The basis weight of the paper substrate is preferably 80 to 600 g / m ² , more preferably 230 to 550 g / m ² . Within the above range, the balance between the strength and processability of the printed matter can be improved.
In the present specification, the thickness of each layer constituting the printed matter is, for example, the average value of the thicknesses of 20 points measured based on the cross-sectional photograph of the cross section obtained by cutting the printed matter in the vertical direction.
In addition, in this specification, "AA-BB" means "AA or more and BB or less". The same applies hereinafter.

<< Anchor coat layer >>
The anchor coat layer is a layer formed between the paper base material and the glossy printing layer and containing a thermoplastic resin. The anchor coat layer has a role of facilitating the satisfaction of conditions 1 and 2, a role of enhancing adhesion to layers located above and below the anchor coat layer, and a role of improving the metallic luster of the glossy print layer.

By using a thermoplastic resin as the resin component of the anchor coat layer, the following effects (1) and (2) can be easily exerted.
(1) It is not necessary to use a monomer or an initiator, and the odor of printed matter can be suppressed.
(2) The ink for the glossy print layer easily penetrates into the anchor coat layer, and the adhesion between the anchor coat layer and the glossy print layer is improved.

The anchor coat layer can be formed by applying and drying an ink for an anchor coat layer containing components constituting the anchor coat layer such as a thermoplastic resin.
By forming the anchor coat layer by coating in this way, it is possible to easily alleviate the unevenness of the paper base material. In particular, the anchor coat layer ink containing a thermoplastic resin does not cure instantly like the ultraviolet curable resin composition, so that it not only alleviates unevenness with a large frequency (unevenness with a cutoff value of 0.08 mm), but also Unevenness with a small frequency (unevenness with a cutoff value of 0.25 mm) can be alleviated, and conditions 1 and 2 can be easily satisfied.
A general method for forming a thermoplastic resin layer on a paper substrate is a method of laminating a thermoplastic resin such as polyethylene by extrusion laminating. However, in the study by the present inventors, it was found that it is difficult to alleviate the unevenness of the paper substrate (particularly the unevenness having a small frequency) in the case of such a method. It is considered that this phenomenon is caused by the unevenness of the surface of the rubber roll (the surface unevenness originally possessed by the rubber roll, the unevenness caused by the deformation of the rubber due to the pressure at the time of laminating) being transferred to the surface of the thermoplastic resin layer.

The anchor coat layer 20 may be formed in the entire region on the paper substrate 10 as shown in FIG. 1, or may be formed in a partial region on the paper substrate 10 as shown in FIGS. 2 and 3. You may.
However, when the anchor coat layer 20 is formed in a part of the region on the paper substrate 10 as shown in FIGS. 2 and 3, the anchor coat layer 20 may be formed at least in the region directly below the glossy print layer 30. preferable. By forming the anchor coat layer in the region directly below the glossy print layer, the ink for the glossy print layer does not directly penetrate into the highly permeable paper substrate, so that when the solvent volatilizes in the process of forming the glossy print layer. In addition, the metal scales tend to rise above the glossy print layer, and the metal scales are unevenly distributed on the upper part of the glossy print layer, so that the metallic gloss of the glossy print layer can be easily improved.
Further, when the anchor coat layer 20 is formed only in the region directly under the glossy print layer 30 as shown in FIGS. 2 and 3, it is advantageous in terms of drying time and material cost, and the risk of residual solvent is reduced. It is suitable in that it can be done.

Examples of the thermoplastic resin constituting the anchor coat layer include polystyrene resin, polyolefin resin, ABS resin, AS resin, AN resin, polyphenylene oxide resin, polycarbonate resin, polyacetal resin, polyethylene terephthalate resin, and polybutylente. Examples thereof include one selected from a phthalate resin, a polysulfone resin, a polyphenylene sulfide resin, an acrylic resin and a cellulose resin, or a mixture thereof. Among these, an acrylic resin is preferable.

The proportion of the thermoplastic resin in the total resin components of the anchor coat layer is preferably 50% by mass or more, more preferably 70% by mass or more, further preferably 90% by mass or more, and 100% by mass. Is even more preferable.
The anchor coat layer may contain additives such as pigments, antioxidants and leveling agents as long as the effects of the present invention are not impaired.

The thickness of the anchor coat layer is preferably 0.5 to 10 μm, more preferably 0.7 to 8 μm, and even more preferably 0.8 to 5 μm.
By setting the thickness of the anchor coat layer to 0.5 μm or more, it is possible to easily satisfy the conditions 1 and 2. Further, by setting the thickness of the anchor coat layer to 10 μm or less, the processability of the printed matter can be improved.

_{The arithmetic average roughness Ra 0.25} of JIS B0601: 1994 on the surface of the anchor coat layer when the cutoff value is 0.25 mm is preferably 0.30 μm or less, and more preferably 0.25 μm or less. , 0.23 μm or less, and even more preferably 0.20 μm or less. _{The lower limit of Ra 0.25 on} the surface of the anchor coat layer is not particularly limited, but is preferably 0.05 μm or more, and more preferably 0.10 μm or more.

_{The arithmetic average roughness Ra 0.08} of JIS B0601: 1994 on the surface of the anchor coat layer when the cutoff value is 0.08 mm is preferably 0.17 μm or less, and more preferably 0.15 μm or less. , 0.10 μm or less is more preferable. _{The lower limit of Ra 0.08 on} the surface of the anchor coat layer is not particularly limited, but is preferably 0.03 μm or more, and more preferably 0.05 μm or more.

_{By setting Ra 0.25} and Ra _0.08 on the surface of the anchor coat layer to the above ranges, it is possible to easily satisfy the conditions 1 and 2.
In the present specification, the surface shape such as the arithmetic average roughness Ra is the average value of the measured values at 20 points without foreign matter or defects.

<< Glossy print layer >>
The glossy printing layer is a layer located on the anchor coat layer, and is formed by printing an ink for a glossy printing layer. By forming the layer that imparts gloss in this way by printing rather than by vapor deposition, it is possible to reduce costs and suppress curling of printed matter. The glossy print layer is preferably formed in contact with the anchor coat layer from the viewpoint of improving the metallic luster and the adhesiveness.
The glossy print layer may be formed in a desired pattern only in a part of the printed matter when the printed matter is observed from the plane direction. That is, the glossy print layer may form a pattern such as a character, a number, a figure, a symbol, a landscape, a person, an animal, or a character.
Further, the glossy print layer may be formed so as to cover the entire surface of the printed matter when the printed matter is observed from the plane direction.

It is necessary to include metal scales in the glossy print layer. By using the metal scales, the metallic luster of the glossy print layer can be improved.

When the glossy print layer has a binder resin, the metal scales are preferably unevenly distributed on the upper part of the glossy print layer (on the side opposite to the anchor coat layer of the glossy print layer). The metal scales are unevenly distributed on the upper part of the glossy printing layer to improve the metallic luster and to improve the adhesion between the glossy printing layer and the layer (anchor coat layer or paper base material) located directly under the glossy printing layer. Can be improved.

When the glossy print layer has a binder resin, the metal scales can be unevenly distributed on the upper part of the glossy print layer in the process of forming the glossy print layer. More specifically, in the process of heating and drying the glossy print layer, when the solvent of the ink for the glossy print layer volatilizes, the solvent flows upward. Then, it is considered that the metal scales emerge with the flow of the solvent, and the metal scales are unevenly distributed on the upper part of the glossy printing layer. In particular, by locating the anchor coat layer instead of the paper base material directly under the glossy printing layer, the downward flow of the solvent can be suppressed, and the metal scales can be easily unevenly distributed on the upper part of the glossy printing layer.

The degree of uneven distribution of metal scales can be confirmed by imaging the cross section of the printed matter with an electron microscope and checking the density difference in the glossy printed layer of the captured photograph. More specifically, the uneven distribution of the metal scales is observed as white because the reflection of electrons is remarkable, and the parts that do not substantially contain the metal scales are observed as gray.
The ratio of the thickness of the uneven distribution area of the metal scales in the glossy print layer [(the thickness of the uneven distribution area of the metal scales / the total thickness of the glossy print layer)] is 10 to 60% from the viewpoint of the balance between metallic luster and adhesion. It is preferably 20 to 50%, more preferably 25 to 45%, and even more preferably 25 to 45%.

The metal scales preferably satisfy the following condition A.
<Condition A>
Average thickness of metal scales / Average length of metal scales ≤ 0.010

By setting [Average thickness of metal scales / Average length of metal scales] to 0.010 or less, the horizontal direction of the glossy print layer (perpendicular to the thickness direction of the glossy print layer) when the ink for the glossy print layer is applied. The metal scales are less likely to tilt with respect to the direction in which they are printed. Therefore, when the solvent flows above the glossy printing layer in the drying process of the glossy printing, the metal scales are easily affected by the force of the solvent flow, and the metal scales are easily unevenly distributed on the upper part of the glossy printing layer. Since the scales are easily arranged in parallel, the metallic luster can be easily improved. Further, the harmful effect of tilting the metal scale increases with the increase in the content of the metal scale, but when the above condition A is satisfied, the content of the metal scale can be increased because the metal scale is difficult to tilt. , The metallic luster can be easily improved.
If the average thickness of the metal scales is too thin with respect to the average length of the metal scales, handling may become difficult and sufficient metallic luster may not be exhibited.
Therefore, the above condition A preferably satisfies 0.001 ≤ average thickness of metal scales / average length of metal scales ≤ 0.010, and 0.002 ≤ average thickness of metal scales / average length of metal scales. It is more preferable to satisfy ≤0.008, and it is further preferable to satisfy 0.002≤average thickness of metal scales / average length of metal scales ≤0.005.

Further, from the viewpoint of further suppressing the tilting of the metal scales with respect to the horizontal direction of the glossy printing layer at the time of applying the ink for the glossy printing layer, and suppressing the protrusion of the metal scales from the surface of the glossy printing layer. It is preferable that the average length of the metal scales and the thickness of the glossy printing layer satisfy the following condition B.
<Condition B>
10 ≤ Average length of metal scales / Thickness of glossy print layer

If [the average length of the metal scales / the thickness of the glossy print layer] is too large, the metal scales may protrude from the surface of the glossy print layer. Therefore, the condition B is 12 ≦ the average length of the metal scales. It is more preferable to satisfy / the thickness of the glossy print layer ≦ 60, and further preferably 14 ≦ the average length of the metal scales / the thickness of the glossy print layer ≦ 50.

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

The average length of the metal scales is preferably 5.0 to 30.0 μm, more preferably 8.0 to 20.0 μm, from the viewpoint of dispersibility, uneven distribution and arrangement of the metal scales.
The average thickness of the metal scales is preferably 0.10 μm or less, more preferably 0.08 μm or less, still more preferably 0.06 μm or less, from the viewpoint of uneven distribution and arrangement of the metal scales. .. The average thickness of the metal scales is preferably 0.01 μm or more, more preferably 0.02 μm or more, from the viewpoint of handleability and high gloss.

The average length and the average thickness of the metal scales shall be the average value of 100 metal scales. The length and thickness of each metal scale can be measured by using a laser interferometry type three-dimensional shape analysis device with the metal scale scattered on a smooth base material. The length of each metal scale means the maximum diameter when the individual metal scale is observed from a plane in any direction, and the thickness of the individual metal scale is the thickness when the individual metal scale is observed from the cross-sectional direction. It means the maximum thickness. The maximum diameter when each metal scale is observed from a plane in an arbitrary direction is intended to unify the direction in which the maximum diameter of each metal scale is measured. For example, when the X-axis direction on the image-processed screen of the measurement result of the three-dimensional shape analysis device is an arbitrary direction (measurement direction), the maximum diameter is measured in a direction parallel to the X-axis. Even if the maximum diameter exists in a direction that is not parallel to the X-axis, it is not regarded as the maximum diameter.
Examples of the laser interference type three-dimensional shape analysis device include the trade name “Shape Analysis Laser Microscope VK-X Series” manufactured by KEYENCE CORPORATION.

The glossy print layer preferably further contains a binder resin.
As the binder resin, a thermoplastic resin, a thermosetting resin and an ultraviolet curable resin can be used. Among these, a thermoplastic resin is preferable from the viewpoint of adhesion to the anchor coat layer and the surface protection layer and from the viewpoint of suppressing odor.
As the thermoplastic resin as the binder resin of the glossy printing layer, the same thermoplastic resin as that exemplified in the anchor coat layer can be used.
The proportion of the thermoplastic resin in the total binder resin of the glossy printing layer is preferably 50% by mass or more, more preferably 70% by mass or more, further preferably 90% by mass or more, and 100% by mass. Is even more preferable.

The blending ratio of the binder resin and the metal scales is preferably 55:45 to 30:70, and more preferably 50:50 to 35:65 in terms of solid content mass ratio. By setting the number of metal scales to 45 or more with respect to the binder resin 55, it becomes easy to obtain sufficient metallic luster, and by setting the number of metal scales to 70 or less with respect to the binder resin 30, the printability of the glossy print layer and the printed matter can be obtained. It is possible to improve workability easily. In the present invention, since the anchor coat layer is provided below the glossy print layer, the metal scales can be unevenly distributed on the upper part of the glossy print layer even if a large amount of metal scales are used as described above.

The thickness of the glossy print layer is preferably 0.15 to 1.50 μm, more preferably 0.20 to 1.00 μm, from the viewpoint of uneven distribution and arrangement of metal scales and concealment. It is more preferably 0.25 to 0.75 μm.

The glossy print layer may contain a colorant such as titanium oxide, zinc flower, carbon black, iron oxide, iron yellow, ultramarine blue, metallic pigment, and pearl pigment in order to make the glossy print layer a desired color. ..

The glossy print layer can be formed by applying an ink for a glossy print layer, which is obtained by diluting the components forming the glossy print layer with a solvent, onto the anchor coat layer and drying.
When the glossy printing layer ink contains a binder resin, the solvent is contained in an amount of 600 to 1100 parts by mass with respect to 100 parts by mass of the total solid content of the glossy printing layer ink from the viewpoint of achieving both uneven distribution of metal scales and drying efficiency. It is preferably contained in an amount of 650 to 800 parts by mass, and more preferably contained in an amount of 650 to 800 parts by mass. When the glossy print layer ink does not contain a binder resin, 600 to 1100 mass of solvent is added to 100 parts by mass of the metal scales of the glossy print layer ink from the viewpoint of achieving both dispersibility and drying efficiency of the metal scales. It is preferably contained in parts, and more preferably 650 to 800 parts by mass.
Since the permeability of the solvent differs depending on the resin composition of the anchor coat layer, a suitable solvent type cannot be unequivocally determined, but a solvent having a boiling point of 75 to 110 ° C. at 1 atm is preferable, and for example, ethyl acetate and isopropyl alcohol (eg, ethyl acetate and isopropyl alcohol). IPA), ethanol, n-propyl acetate, a mixture thereof, or the like can be preferably used.

<< Surface protection layer >>
The printed matter preferably has a surface protective layer on the glossy printed layer from the viewpoint of improving scratch resistance and weather resistance. For this effect, it is preferable to form the surface protective layer so as to cover the entire surface of the printed matter when the printed matter is observed from the plane direction.

The surface protective layer preferably contains a cured product of the thermosetting resin composition or a cured product layer of the ultraviolet curable resin composition, and more preferably contains a cured product of the thermosetting resin composition.
Since the surface protective layer contains a cured product of a thermosetting resin, it is possible to suppress the odor of printed matter while improving the scratch resistance and weather resistance of the surface protective layer. In addition, since the cured product of the thermosetting resin does not cure instantly, not only the unevenness with a large frequency (unevenness with a cutoff value of 0.08 mm) is alleviated, but also the unevenness with a small frequency (unevenness with a cutoff value of 0.25 mm) is alleviated. ) Can be alleviated, and conditions 1 and 2 can be easily satisfied.

The thermosetting resin composition is a composition containing at least a thermosetting resin, and is a resin composition that is cured by heating.
Examples of the thermosetting resin include acrylic resin, urethane resin, phenol resin, urea melamine resin, epoxy resin, unsaturated polyester resin, silicone resin and the like. To the thermosetting resin composition, a curing agent is added to these curable resins as needed.

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

It is preferable that the surface protective layer does not substantially contain particles from the viewpoint of facilitating the satisfaction of conditions 1 and 2. The fact that the surface protective layer contains substantially no particles means that the proportion of the particles in the total solid content of the surface protective layer is 0.5% by mass or less, preferably 0.1% by mass or less. , More preferably, it means 0% by mass.

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

The surface protective layer can be formed by applying and drying an ink for a surface protective layer containing a thermosetting resin composition, a solvent, and an additive added as needed.

<< Surface shape and physical properties of printed matter >>
The printed matter of the present invention requires that the surface roughness on the glossy printed layer side of the printed matter with respect to the paper substrate satisfies the following condition 1.
<Condition 1>
_{The arithmetic average roughness Ra 0.25} of JIS B0601: 1994 of the surface when the cutoff value is 0.25 mm is 0.25 μm or less.

_{When Ra 0.25} of the surface on the glossy print layer side (hereinafter, also referred to as "the surface on the glossy print layer side") based on the paper substrate of the printed matter exceeds 0.25 μm, the surface diffusion of the printed matter The proportion of the metal becomes large, and the metallic luster cannot be improved.
_{Ra 0.25} on the surface of the glossy print layer side is preferably 0.23 μm or less, more preferably 0.20 μm or less, and further preferably 0.17 μm or less.
_{The lower limit of Ra 0.25} on the surface on the glossy print layer side is not particularly limited, but is preferably 0.05 μm or more, preferably 0.10 μm or more, from the viewpoint of suppressing glare due to excessively strong metallic luster. Is more preferable.

The surface on the glossy print layer side based on the paper substrate of the printed matter means the outermost surface on the side of the printed matter having the glossy print layer, and in the case of FIGS. 1 to 3, the surface of the surface protective layer. That means. Although some printed matter does not have a glossy print layer, Ra on the surface on the glossy print layer side shall be measured on the surface on the glossy print layer side of the portion having the glossy print layer.

In the printed matter of the present invention, it is preferable that the surface roughness on the glossy printed layer side of the printed matter with respect to the paper base material satisfies the following condition 2.
<Condition 2>
_{The arithmetic average roughness Ra 0.08} of JIS B0601: 1994 and the Ra _{0.25 of the} surface when the cutoff value is 0.08 mm are "(Ra _{0.25- Ra 0.08} ) /. The relationship of "Ra _0.08 ≤ 1.35" is satisfied.

_{Ra (Ra 0.08} ) with a cutoff value of 0.08 mm indicates Ra based on high frequency unevenness. On the other hand, Ra (Ra _0.25 ) having a cutoff value of 0.25 mm indicates Ra based on the unevenness obtained by adding the unevenness having a large frequency and the unevenness having a small frequency. Therefore, "Ra _{0.25- Ra 0.08} " indicates Ra based on the unevenness with a small frequency. Then, the condition 2 "(Ra _{0.25- Ra 0.08} ) / Ra _0.08 " indicates the ratio of Ra based on the unevenness having a low frequency to Ra based on the unevenness having a high frequency.
That is, satisfying the condition 2 means that the unevenness having a small frequency and the unevenness having a large frequency exist in a well-balanced manner. The unevenness having a small frequency and the unevenness having a high frequency are present in a well-balanced manner, so that the metallic luster can be felt smoothly and uniformly.

Condition 2 "(Ra _{0.25- Ra 0.08} ) / Ra _0.08 " preferably approaches 1.00. If "(Ra _{0.25- Ra 0.08} ) / Ra _0.08 " is less than 1.00, the proportion of unevenness with a large frequency increases, the reflected light may be whitened, and the metallic luster may decrease. There is sex.
Therefore, condition 2 more preferably satisfies the relationship of "1.00 ≤ (Ra _{0.25- Ra 0.08} ) / Ra _0.08 ≤ 1.35", and more preferably "1.05 ≤ (Ra _0). It is more preferable to satisfy the relationship of _.25 −Ra _0.08 ) / Ra _{0.08 ≦ 1.30 ”.}

In the printed matter of the present invention, Ra _0.08 on the surface of the glossy print layer side is preferably 0.17 μm or less, more preferably 0.15 μm or less, and further preferably 0.10 μm or less. _{The lower limit of Ra 0.08} on the surface on the glossy print layer side is not particularly limited, but is preferably 0.03 μm or more, and more preferably 0.05 μm or more.

In the printed matter of the present invention, when the cutoff value is 0.25 mm, the ten-point average roughness Rz _0.25 of JIS B0601: 1994 on the surface on the glossy printed layer side is preferably 1.50 μm or less. It is more preferably 1.25 μm or less, and further preferably 1.00 μm or less. _{The lower limit of Rz 0.25} on the surface on the glossy print layer side is preferably 0.30 μm or more, and more preferably 0.50 μm or more.
In the printed matter of the present invention, when the cutoff value is 0.08 mm, the ten-point average roughness Rz _0.08 of JIS B0601: 1994 on the surface on the glossy printed layer side is preferably 1.00 μm or less. It is more preferably 0.75 μm or less, and further preferably 0.50 μm or less. _{The lower limit of Rz 0.08} on the surface on the glossy print layer side is preferably 0.15 μm or more, and more preferably 0.25 μm or more.
_{By setting Rz 0.25} and Rz _0.08 on the surface of the glossy print layer side in the above ranges, the effect based on the conditions 1 and 2 can be further improved.

The mirror glossiness of the surface on the glossy print layer side at 60 degrees of JIS Z8741: 1997 is preferably 80% or more, more preferably 90% or more, and more preferably 100% or more from the viewpoint of metallic luster. Is even more preferable.
Although some printed matter does not have a glossy print layer, the mirror glossiness of the surface on the glossy print layer side shall be measured on the surface on the glossy print layer side of the portion having the glossy print layer. The mirror glossiness is the average value of the values at 20 points.

<< Picture layer >>
The printed matter preferably has a pattern layer at an arbitrary position for the purpose of enhancing the design of the printed matter. The location where the pattern layer is formed is not particularly limited, and as shown in FIG. 2, there is no anchor layer 20 on the paper base material 10 between the paper base material 10 and the anchor layer 20 as shown in FIG. The place is mentioned. When the printed matter has a surface protective layer, it is preferable to form the pattern layer on the paper substrate side rather than the surface protective layer from the viewpoint of protecting the pattern layer.

The pattern layer can be formed by printing or the like. The pattern layer may be a colored layer that covers the entire surface (so-called solid colored layer), or may be a pattern layer such as letters, numbers, figures, symbols, landscapes, people, animals, and characters. May be a combination of.

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

The thickness of the pattern layer can be appropriately adjusted in the range of about 0.1 to 20 μm in consideration of the form of the pattern layer and the desired design. Additives such as antioxidants and ultraviolet absorbers may be contained in the pattern layer as long as the effects of the present invention are not impaired.

[container]
The container of the present invention is made by using the above-mentioned printed matter of the present invention.
Examples of the container include a chemical container, a cosmetic container, a food container and the like without particular limitation. The container of the present invention has an excellent glossiness and is excellent in design. Further, since the curl of the printed matter is suppressed, it is possible to prevent troubles caused by the curl in the manufacturing process of the container. Moreover, since the container of the present invention can suppress the odor, it is extremely suitable for a food container.

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

1. 1. Measurement and Evaluation The following measurements and evaluations were performed on the printed matter produced in Examples and Comparative Examples. The results are shown in Table 1.

1-1. Arithmetic mean roughness Ra and ten-point average roughness Rz
_{Arithmetic mean roughness Ra 0.25} and ten-point average roughness of JIS B0601: 1994 when the cutoff value is 0.25 mm for the surfaces of the printed matter of Examples 1 and 2 and Comparative Example 1 on the glossy printed layer side. Rz _{0.25 and the arithmetic mean roughness Ra 0.08} and the ten-point average roughness Rz _0.08 of JIS B0601: 1994 when the cutoff value was 0.08 mm were measured. For the measurement of Ra and Rz, the trade name SE-340 manufactured by Kosaka Research Institute Co., Ltd. was used, and the following measurement conditions were used.
[Needle of surface roughness detector]
Product name SE2555N manufactured by Kosaka Research Institute (tip radius of curvature: 2 μm, apex angle: 90 degrees, material: diamond)
[Measurement conditions of surface roughness measuring instrument]
・ Evaluation length (reference length): 5 times the cutoff value λc ・ Needle feed speed: 0.25 mm / s
-Preliminary length: (cutoff value λc) x 2
・ Vertical magnification: 2000 times ・ Horizontal magnification: 10 times

1-2. Mirror glossiness According to JIS Z8741: 1997, the 60-degree mirror glossiness of the surface of the printed matter of Examples 1 and 2 on the glossy print layer side was measured using a micro-TRI-gloss of BYK Gardener Co., Ltd. as a measuring instrument.

1-3. Metallic luster (1)
<Strength of metallic luster>
The printed matter of Examples 1 and 2 and Comparative Example 1 were observed from the glossy printing layer side under the illumination of a fluorescent lamp, and it was visually evaluated whether or not the metallic luster was good with respect to the following reference. 3 points have a metallic luster that is extremely better than the reference, 2 points have a metallic luster that is superior to the reference but do not feel a noticeable difference, and 1 point has a metallic luster that is equal to or less than the reference. As points, 20 subjects evaluated and calculated the average score. As a result, those with an average score of 2.5 or more were designated as "A", those with an average score of 1.5 or more and less than 2.5 were designated as "B", and those with an average score of less than 1.5 were designated as "C". ..
<Reference printed matter>
Silver ink (manufactured by DIC Graphics, trade name: CHG chip base silver) was applied to the entire surface of the anchor coat layer of the laminate A of Example 1 and dried to form a silver layer having an average thickness of 3.0 μm. .. Next, a surface protective layer similar to that in Example 1 was formed on the silver layer to obtain a reference printed matter.

1-4. Metallic luster (2)
<Uniformity of metallic luster>
The printed matter of Examples 1 and 2 and Comparative Example 1 were observed from the glossy printing layer side under the illumination of a fluorescent lamp, and it was visually evaluated whether or not the metallic luster was felt smoothly and uniformly. Twenty subjects evaluated the average score as 3 points for the smooth and uniform metallic luster, 2 points for the indescribable one, and 1 point for the smooth and non-uniform metallic luster. Calculated. As a result, those with an average score of 2.5 or more were designated as "A", those with an average score of 1.5 or more and less than 2.5 were designated as "B", and those with an average score of less than 1.5 were designated as "C". ..

1-5. Odor An odor-free printed matter was designated as "A", and an odor-sensitive printed matter was designated as "C".

2. 2. Preparation of printed matter [Example 1]
The anchor coat layer ink 1 of the following formulation is applied and dried on the entire surface of the coated surface side of the paper substrate (single-sided ivory paper having a basis weight of 235 g / m ^{2) so that the average thickness after drying is 1.0 μm.} , An anchor coat layer was formed to obtain a laminated body A.
Next, the glossy printing layer ink 2 of the following formulation was applied to the entire surface of the anchor coat layer of the laminate A so that the average thickness after drying was 0.50 μm, and dried to form a glossy printing layer. The thickness of the region where the metal scales of the glossy print layer were substantially absent was 0.30 μm, and the thickness of the region where the metal scales were unevenly distributed was 0.20 μm.
Next, the surface protective layer ink 3 of the following formulation was applied by gravure printing so as to cover the entire surface of the glossy print layer side of the printed matter so that the average thickness after drying would be 1.0 μm, and the surface protective layer ( A cured product layer of the thermosetting resin composition) was formed, and a printed matter of Example 1 was obtained.

<Ink 1 for anchor coat layer>
An ink composition obtained by diluting a thermoplastic resin with a solvent (a 4: 4: 2 mixed solvent of ethyl acetate, methyl ethyl ketone and n-propyl acetate).
<Ink 2 for glossy print layer>
-Binder resin (nitrated cotton) 4.8 parts by mass (manufactured by DIC Graphics)
(Product name: XS-763 Medium NT-No.1)
-Aluminum scale 7.2 parts by mass (average length 14 μm, average thickness 0.04 μm)
-Diluting solvent 88 parts by mass (7: 3 mixed solvent of ethyl acetate and n-propyl acetate)
<Ink 3 for surface protection layer (thermosetting type)>
An ink composition obtained by dispersing an acrylic thermosetting resin composition in an aqueous solvent (a 3: 7 mixed solvent of water and isopropyl alcohol).

[Example 2]
The anchor coat layer ink 4 of the following formulation is applied and dried on the entire surface of the coated surface side of the paper substrate (single-sided ivory paper having a basis weight of 235 g / m ^{2) so that the average thickness after drying is 1.0 μm.} , An anchor coat layer was formed to obtain a laminated body B.
Next, the glossy printing layer ink 5 of the following formulation was applied to the entire surface of the anchor coat layer of the laminate B so that the average thickness after drying was 0.50 μm, and dried to form a glossy printing layer.
Next, the surface protective layer ink 6 of the following formulation was applied and dried so as to have an average thickness of 1.0 μm after drying so as to cover the entire surface of the glossy print layer side of the printed matter by gravure printing. A cured product layer of the thermosetting resin composition) was formed, and a printed matter of Example 2 was obtained.

<Ink 4 for anchor coat layer>
Ethanol dispersion of thermoplastic acrylic resin with a solid content of 40.3% <Ink 5 for glossy printing layer>
100 parts by mass of dispersion of aluminum scales (mass ratio of aluminum scales to dispersion medium is 15:85)
(The dispersion medium is a 14: 3: 3 mixed solvent of ethyl acetate, IPA, and n-propyl acetate).
・ 25 parts by mass of diluting solvent (n-propyl acetate alone)
<Ink 6 for surface protection layer (thermosetting type)>
An ink composition obtained by dispersing an acrylic thermosetting resin composition in ethanol.

[Comparative Example 1]
Using a melt extrusion method, low-density polyethylene (LDPE) is extruded to a thickness of 15 μm over the entire surface of the coated surface of a paper substrate (single-sided ivory paper with a basis weight of 235 g / m ^{2), and a metal roll and a rubber roll are used.} A thermoplastic resin layer was formed through the space between the two, and a laminated body C was obtained. At the time of extrusion, the paper base material was on the metal roll side and the molten resin was on the rubber roll side.
Next, a glossy printed layer and a surface protective layer similar to those in Example 1 were formed on the thermoplastic resin layer of the laminated body C to obtain a printed matter of Comparative Example 1.

From the results in Table 1, it can be confirmed that the printed matter of Examples 1 and 2 exhibits good metallic luster and can suppress odor without using the means of metal vapor deposition.

The printed matter and container of the present invention are useful in that they can impart metallic luster and suppress odors without using means for metal vapor deposition.

10: Paper substrate 20: Anchor coat layer 30: Glossy print layer 40: Surface protection layer 50: Picture layer 100: Printed matter

Claims (5)

A printed matter having a glossy printed matter on a paper substrate, wherein the printed matter has an anchor coat layer containing a thermoplastic resin between the paper substrate and the glossy print layer, and the glossy print layer is the anchor coat layer. A printed matter which is provided in contact with the glossy printed matter, contains metal scales, and has a surface roughness on the glossy printed layer side with respect to the paper substrate of the printed matter satisfying the following condition 1.
<Condition 1>
_{The arithmetic average roughness Ra 0.25} of JIS B0601: 1994 of the surface when the cutoff value is 0.25 mm is 0.25 μm or less. The printed matter according to claim 1, wherein the surface roughness satisfies the following condition 2.
<Condition 2>
_{The arithmetic average roughness Ra 0.08} of JIS B0601: 1994 and the Ra _{0.25 of the} surface when the cutoff value is 0.08 mm are "(Ra _{0.25- Ra 0.08} ) /. The relationship of "Ra _0.08 ≤ 1.35" is satisfied. The printed matter according to claim 1 or 2, wherein the thickness of the anchor coat layer is 0.5 to 10 μm. The printed matter according to any one of claims 1 to 3, which has a surface protective layer on the glossy printed layer. A container made of the printed matter according to any one of claims 1 to 4.

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