JP2019018445A - Printed matter and container using the same - Google Patents

Abstract

To provide a printed matter capable of adding a metallic sheen without using means of metal deposition, while suppressing offensive odor.SOLUTION: A printed matter has a glossy print layer on a paper substrate. The printed matter includes an anchor coat layer containing a thermoplastic resin between the paper substrate and the glossy print layer. The glossy print layer includes metal flakes. With the paper substrate of the printed matter as a standard, surface roughness of the glossy print layer side satisfies a condition 1 below. <Condition 1> If a cutoff value is 0.25 mm, arithmetic average roughness Raof JIS B0601:1994 on the surface is 0.25 μm or less.SELECTED DRAWING: Figure 1

Description

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

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

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

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

Japanese Patent Laid-Open No. 2006-88098

  Patent Document 1 discloses a printed matter having a glossy print layer including a hard coat layer and metal thin film strips on a paper substrate.

  The printed matter of Patent Document 1 has no problem with respect to 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 managed. Occasionally an odor caused by a monomer or initiator may occur. In particular, when a large amount of monomer or initiator has penetrated into the paper substrate, it has been difficult to remove the odor.

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

In order to solve the above problems, the present invention provides the following [1] to [2].
[1] A printed matter having a glossy printed layer on a paper substrate, wherein the printed matter has an anchor coat layer containing a thermoplastic resin between the paper substrate and the glossy printed layer, and the glossy printed layer is a metal A printed matter comprising scales, wherein the surface of the printed material on the glossy printed layer side relative to the paper substrate satisfies the following condition 1.
<Condition 1>
JIS B0601: 1994 arithmetic average roughness Ra _{0.25 of the} surface when the cut-off value is 0.25 mm is 0.25 μm or less.
[2] A container using the printed material according to [1].

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

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

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

  1-3 is sectional drawing which shows one Embodiment of the printed matter 100 of this invention. The printed matter 100 in FIGS. 1 to 3 has an anchor coat layer 20 and a glossy printed layer 30 in this order on a paper substrate 10. Moreover, the printed matter 100 of FIGS. 1-3 has the surface protective layer 40 so that the surface by the side of the glossy printed layer 20 on the basis of the paper base material 10 of a printed matter may be covered. 2 and 3 has a pattern layer 50.

<< Base material >>
The paper substrate is not particularly limited as long as it is made of paper and has formability, flex resistance, rigidity, waist, strength, and the like. For example, it is a main strength material, and various types of paper such as strong size bleached or unbleached paper, or pure white roll paper, kraft paper, paperboard, processed paper, and milk base paper can be used. Further, the paper base material may be a laminate of the above-described 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 . By setting it within the above range, the balance between the strength and processability of the printed matter can be improved.
In this specification, the thickness of each layer constituting the printed material is, for example, an average value of 20 thicknesses measured based on the cross-sectional photograph obtained by taking a cross-sectional photograph of a cross-section obtained by cutting the printed material in the vertical direction.
In the present specification, “AA to BB” means “AA to BB”. The same applies hereinafter.

<< Anchor coat layer >>
The anchor coat layer is a layer formed between the paper substrate and the glossy print layer and containing a thermoplastic resin. The anchor coat layer has a role of making it easy to satisfy the conditions 1 and 2, and also has a role of improving adhesion with layers positioned above and below the anchor coat layer, and a role of improving the metallic luster of the glossy printing 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 the printed matter can be suppressed.
(2) The ink for the gloss printing layer can easily penetrate into the anchor coating layer, and the adhesion between the anchor coating layer and the gloss printing layer is improved.

The anchor coat layer can be formed by applying and drying an ink for an anchor coat layer containing a component constituting the anchor coat layer such as a thermoplastic resin.
Thus, by forming the anchor coat layer by coating (coating), the unevenness of the paper substrate can be easily relaxed. In particular, the anchor coat layer ink containing a thermoplastic resin does not cure instantaneously like an ultraviolet curable resin composition, and therefore not only relieves large frequency irregularities (unevenness with a cutoff value of 0.08 mm), Unevenness with a small frequency (unevenness with a cut-off value of 0.25 mm) can be relaxed, and conditions 1 and 2 can be easily satisfied.
A general technique for forming a thermoplastic resin layer on a paper substrate is a technique in which a thermoplastic resin such as polyethylene is laminated by extrusion lamination. However, as a result of the study by the present inventors, it has been found that it is difficult to alleviate the unevenness of the paper base material (particularly, the unevenness having a low frequency) in this method. This phenomenon is considered to be caused by the fact that the irregularities on the surface of the rubber roll (surface irregularities originally possessed by the rubber roll, irregularities caused by the deformation of the rubber by the pressure during lamination) are transferred to the surface of the thermoplastic resin layer.

As shown in FIG. 1, the anchor coat layer 20 may be formed in the entire region on the paper substrate 10, or may be formed in a partial region on the paper substrate 10 as in FIGS. 2 and 3. May be.
However, as shown in FIGS. 2 and 3, when the anchor coat layer 20 is formed in a partial region on the paper substrate 10, the anchor coat layer 20 may be formed at least in a region immediately below the glossy print layer 30. preferable. By forming an anchor coat layer directly under the glossy printing layer, the ink for the glossy printing layer does not penetrate directly into the highly permeable paper base material, so the solvent volatilizes during the process of forming the glossy printing layer. In addition, the metal scales are likely to float above the glossy printed layer, and the metal scales are unevenly distributed above the glossy printed layer, making it easy to improve the metallic gloss of the glossy printed layer.
Further, as shown in FIGS. 2 and 3, when the anchor coat layer 20 is formed only in the region immediately below the glossy printing layer 30, it is advantageous in terms of drying time and material cost, and also reduces the risk of residual solvent. It is preferable in that it can be performed.

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

The ratio of the thermoplastic resin in the total resin component 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. Even more preferably.
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 still more preferably 0.8 to 5 μm.
Condition 1 and condition 2 can be easily satisfied by setting the thickness of the anchor coat layer to 0.5 μm or more. Moreover, the processability of a printed matter can be made favorable by the thickness of an anchor coat layer being 10 micrometers or less.

JIS B0601: 1994 arithmetic average roughness Ra _0.25 of the anchor coat layer surface when the cut-off value is 0.25 mm is preferably 0.30 μm or less, more preferably 0.25 μm or less. 0.23 μm or less is more preferable, and 0.20 μm or less is even more preferable. 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. More preferably, it is 0.10 μm or less. 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 within the above ranges, Condition 1 and Condition 2 can be easily satisfied.
In the present specification, the surface shape such as the arithmetic average roughness Ra is an average value of measured values at 20 locations free from foreign matter and defects.

<< Glossy Print Layer >>
The gloss print layer is a layer located on the anchor coat layer, and is formed by printing the gloss print layer ink. Thus, by forming the gloss imparting layer by printing instead of vapor deposition, the cost can be reduced and curling of the printed matter can be suppressed. The gloss printing layer is preferably formed in contact with the anchor coat layer from the viewpoint of improving the metallic luster and the adhesiveness.
The glossy printed layer may be formed in a desired pattern only in a partial area of the printed material when the printed material is observed from the plane direction. That is, patterns such as letters, numbers, figures, symbols, landscapes, people, animals, and characters may be formed by the glossy print layer.
The glossy printed layer may be formed so as to cover the entire surface of the printed material when the printed material is observed from the plane direction.

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

  Moreover, when a glossy printed layer has binder resin, it is preferable that a metal scale is unevenly distributed in the upper part (the side opposite to the anchor coat layer of a glossy printed layer) of a glossy printed layer. The metallic scale is unevenly distributed on the upper part of the glossy printed layer, thereby improving the metallic luster and improving the adhesion between the glossy printed layer and the layer (anchor coat layer or paper substrate) located immediately below the glossy printed layer. Can be improved.

  When the gloss printing layer has a binder resin, the metal scale can be unevenly distributed on the gloss printing layer in the process of forming the gloss printing layer. More specifically, when the solvent for the glossy printing layer ink volatilizes during the heat drying process of the glossy printing layer, the solvent flows upward. And it is thought that a metal scale floats with the flow of a solvent, and a metal scale is unevenly distributed in the upper part of a glossy printed layer. In particular, by positioning the anchor coat layer instead of the paper substrate directly under the glossy print layer, the downward flow of the solvent can be suppressed, and the metal scales can be easily unevenly distributed on the glossy print layer.

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

The metal scale preferably satisfies the following condition A.
<Condition A>
Average thickness of metal scale / average length of metal scale ≦ 0.010

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

In addition, at the time of applying the ink for the glossy printed layer, from the viewpoint of suppressing the metal scale from tilting with respect to the horizontal direction of the glossy printed layer, and suppressing the metal scale from protruding from the surface of the glossy printed layer. The average length of the metal scales and the thickness of the glossy printed layer preferably satisfy the following condition B.
<Condition B>
10 ≦ average length of metal scale / thickness of glossy printed layer

  In addition, if [average length of metal scale / thickness of glossy printed layer] is too large, metal scale may protrude from the surface of the glossy printed layer, so condition B is 12 ≦ average length of metal scale. It is more preferable to satisfy / gloss printed layer thickness ≦ 60, and it is more preferable to satisfy 14 ≦ average length of metal scale / gloss printed layer thickness ≦ 50.

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

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

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

The glossy printed layer preferably further contains a binder resin.
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 protective layer and from the viewpoint of odor suppression.
As the thermoplastic resin as the binder resin for the glossy print layer, the same thermoplastic resin as exemplified for the anchor coat layer can be used.
The ratio 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. Even more preferably.

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

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

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

The gloss printing layer can be formed by applying and drying an ink for gloss printing layer obtained by diluting a component forming the gloss printing layer with a solvent on the anchor coat layer.
When the ink for glossy printing layer contains a binder resin, from the viewpoint of coexistence of uneven distribution of metal scales and drying efficiency, 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 ink for glossy printing layer. The content is preferably 650 to 800 parts by mass. Moreover, when the ink for glossy printing layers does not contain binder resin, from a viewpoint of coexistence of the dispersibility of a metal scale, and drying efficiency, a solvent is 600-1100 mass with respect to 100 mass parts of metal scales of the ink for glossy printing layers. It is preferable to contain part, and it is more preferable to contain 650-800 mass parts.
Since the permeability of the solvent varies depending on the resin composition of the anchor coat layer, a suitable solvent type cannot be generally specified. However, a solvent having a boiling point of 1 atm of 75 to 110 ° C. is preferable, for example, ethyl acetate, isopropyl alcohol ( IPA), ethanol, n-propyl acetate, or a mixture thereof can be suitably used.

<< surface protective layer >>
The printed material 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 material when the printed material is observed from the plane direction.

The surface protective layer preferably includes a cured product of a thermosetting resin composition or a cured product layer of an ultraviolet curable resin composition, and more preferably includes a cured product of a thermosetting resin composition.
When the surface protective layer contains a cured product of the thermosetting resin, the odor of the printed material can be suppressed 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 instantaneously, not only the unevenness with a large frequency (unevenness with a cut-off value of 0.08 mm) is relaxed, but also the unevenness with a low frequency (unevenness with a cut-off value of 0.25 mm). ) Can be relaxed, 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, and silicone resin. In the thermosetting resin composition, a curing agent is added to these curable resins as necessary.

  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 easily satisfying the conditions 1 and 2. The phrase “substantially free of particles in the surface protective layer” means that the proportion of 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, and 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 to be added as necessary.

<< 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 with respect to the paper substrate of the printed matter satisfies the following condition 1.
<Condition 1>
JIS B0601: 1994 arithmetic average roughness Ra _{0.25 of the} surface when the cut-off value is 0.25 mm is 0.25 μm or less.

When the Ra _0.25 of the surface on the glossy print layer side (hereinafter also referred to as “surface on the glossy print layer side”) with respect to the paper substrate of the print exceeds _0.25 μm, the surface diffusion of the print Therefore, the metallic luster cannot be improved.
Ra _0.25 on the surface of the glossy printed 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 printed layer side is not particularly limited, but is preferably 0.05 μm or more, and preferably 0.10 μm or more from the viewpoint of suppressing glare due to excessively strong metallic luster. It is more preferable.

  The surface on the side of the glossy printed layer on the basis of the paper substrate of the printed material means the outermost surface of the printed material on the side having the glossy printed layer. In the case of FIGS. That means. In addition, although the location which does not have a glossy printing layer also exists in printed matter, Ra of the surface by the side of a glossy printing layer shall be measured in the surface by the side of the glossy printing layer of the location which has a glossy printing layer.

In the printed matter of the present invention, it is preferable that the roughness of the surface on the glossy printed layer side based on the paper substrate of the printed matter satisfies the following condition 2.
<Condition 2>
When the cut-off value is 0.08 mm, the arithmetic average roughness Ra _0.08 of JIS B0601: 1994 of the surface and Ra _0.25 are “(Ra _0.25 −Ra _0.08 ) / The relationship of Ra _0.08 ≦ 1.35 ”is satisfied.

Ra having a cutoff value of 0.08 mm (Ra _0.08 ) indicates Ra based on unevenness having a large frequency. On the other hand, Ra having a cutoff value of 0.25 mm (Ra _0.25 ) indicates Ra based on the unevenness obtained by adding the unevenness having a large frequency and the unevenness having a low frequency. For this reason, “Ra _0.25 −Ra _0.08 ” indicates Ra based on unevenness having a small frequency. Then, “(Ra _0.25 −Ra _0.08 ) / Ra _0.08 ” in Condition 2 indicates the ratio of Ra based on unevenness with a small frequency and Ra based on unevenness with a high frequency.
In other words, satisfying Condition 2 means that unevenness having a low frequency and unevenness having a high frequency exist in a balanced manner. And since the unevenness | corrugation with a small frequency and the unevenness | corrugation with a high frequency exist in this way, a metallic luster can be felt smoothly and uniformly.

In condition 2, “(Ra _0.25 −Ra _0.08 ) / Ra _0.08 ” is preferably close to 1.00. In addition, when “(Ra _0.25 −Ra _0.08 ) / Ra _0.08 ” is less than 1.00, the ratio of irregularities having a large frequency increases, and the reflected light may be whitened to reduce the metallic luster. There is sex.
Therefore, the condition 2 more preferably satisfies the relationship of “1.00 ≦ (Ra _0.25 −Ra _0.08 ) / Ra _0.08 ≦ 1.35”, and “1.05 ≦ (Ra _{0 .25} −Ra _0.08 ) / Ra _0.08 ≦ 1.30 ”is more preferable.

In the printed matter of the present invention, Ra _0.08 on the surface on the glossy printing 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 printing layer side is not particularly limited, but is preferably 0.03 μm or more, and more preferably 0.05 μm or more.

The printed matter of the present invention preferably has a JIS B0601: 1994 10-point average roughness Rz _0.25 of 1.50 μm or less when the cut-off value is 0.25 mm. More preferably, it is 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 printed layer side is preferably 0.30 μm or more, and more preferably 0.50 μm or more.
The printed matter of the present invention preferably has a JIS B0601: 1994 ten-point average roughness Rz _0.08 of the surface on the glossy printed layer side when the cut-off value is 0.08 mm, which is 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 printed 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 on the glossy printed layer side within the above ranges, the effect based on Condition 1 and Condition 2 can be further improved.

From the viewpoint of metallic gloss, the specular gloss at 60 ° of JIS Z8741: 1997 on the surface of the glossy printed layer side is preferably 80% or more, more preferably 90% or more, and 100% or more. More preferably.
In addition, although the location which does not have a glossy printing layer also exists in printed matter, the specular glossiness of the surface by the side of a glossy printing layer shall be measured in the surface by the side of the glossy printing layer of the location which has a glossy printing layer. The specular gloss is an average value of 20 locations.

<< Pattern layer >>
The printed material preferably has a pattern layer at an arbitrary position for the purpose of improving the design of the printed material. The location where the pattern layer is formed is not particularly limited, and does not include the anchor layer 20 on the paper substrate 10 as shown in FIG. 3 between the paper substrate 10 and the anchor layer 20 as shown in FIG. A place is mentioned. In addition, when printed matter has a surface protective layer, it is preferable to form a pattern layer in the paper base material side rather than a surface protective layer from a viewpoint of protection of a pattern layer.

  The pattern layer can be formed by printing or the like. The pattern layer may be a colored layer (so-called solid colored layer) covering the entire surface, or may be a pattern layer of characters, numbers, figures, symbols, landscapes, people, animals, characters, etc. May be combined.

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

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

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

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

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

1-1. Arithmetic average roughness Ra and ten-point average roughness Rz
JIS B0601: 1994 arithmetic average roughness Ra _0.25 and ten-point average roughness when the cut-off value is 0.25 mm for the gloss printed layer side surfaces of the printed materials of Examples 1 and 2 and Comparative Example 1. Rz _0.25 and arithmetic average roughness Ra _0.08 and ten-point average roughness Rz _0.08 of JIS B0601: 1994 when the cut-off value was 0.08 mm were measured. In addition, Ra and Rz were measured using the trade name SE-340 manufactured by Kosaka Laboratory Ltd. under the following measurement conditions.
[Surface probe for surface roughness detection]
Product name SE2555N manufactured by Kosaka Laboratory Ltd. (tip radius of curvature: 2 μm, apex angle: 90 degrees, material: diamond)
[Measurement conditions of surface roughness measuring instrument]
・ Evaluation length (reference length): 5 times the cutoff value λc ・ Feeding speed of stylus: 0.25 mm / s
・ Preliminary length: (cutoff value λc) × 2
・ Vertical magnification: 2000 times ・ Horizontal magnification: 10 times

1-2. Specular Glossiness According to JIS Z8741: 1997, by using BYK Gardner's micro-TRI-gloss as a measuring device, the 60-degree specular glossiness of the surface on the glossy printing layer side of the printed materials of Examples 1-2 was measured.

1-3. Metal luster (1)
<Strength of metallic luster>
Under the illumination of a fluorescent lamp, the printed materials of Examples 1 and 2 and Comparative Example 1 were observed from the glossy printed layer side, and it was visually evaluated whether or not the metallic gloss was good with respect to the following reference. 3 points where the metallic luster is much better than the reference, 2 points where the metallic luster is superior to the reference, but 2 points where there is no noticeable difference, and 1 where the metallic luster is less than or equal to the reference Twenty subjects evaluated and scored the average score. As a result, those having an average score of 2.5 or more were designated as “A”, those having an average score of 1.5 or more and less than 2.5 as “B”, and those having an average score of less than 1.5 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 of Example 1 was formed on the silver layer to obtain a printed reference material.

1-4. Metal luster (2)
<Uniformity of metallic luster>
Under the illumination of the fluorescent lamp, the printed materials of Examples 1 and 2 and Comparative Example 1 were observed from the glossy printed layer side, 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 a metallic luster that feels smooth and uniform, 2 for those that cannot be said to be either, and 1 for those that do not feel smooth and even. Calculated. As a result, those having an average score of 2.5 or more were designated as “A”, those having an average score of 1.5 or more and less than 2.5 as “B”, and those having an average score of less than 1.5 as “C”. .

1-5. Odor The prints that did not feel odor were designated as “A”, and those that felt odor were designated as “C”.

2. Production of printed matter [Example 1]
The anchor coat layer ink 1 having the following prescription is applied to the entire surface of the paper substrate (single-sided ivory paper with a basis weight of 235 g / m ² ) so that the average thickness after drying is 1.0 μm and dried. An anchor coat layer was formed to obtain a laminate A.
Next, the gloss printing layer ink 2 having the following formulation was applied on the entire surface of the anchor coat layer of the laminate A so as to have an average thickness after drying of 0.50 μm, and dried to form a gloss printing layer. The thickness of the gloss print layer in which the metal scales were not substantially present was 0.30 μm, and the thickness of the metal scale unevenly distributed region was 0.20 μm.
Next, the surface protective layer ink 3 having 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 glossy printed layer side of the printed matter, and the surface protective layer ( The cured product layer of the thermosetting resin composition was formed, and the printed matter of Example 1 was obtained.

<Ink for anchor coat layer 1>
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).
<Glossy printing layer ink 2>
-Binder resin (nitrified cotton) 4.8 parts by mass (manufactured by DIC Graphics)
(Product name: XS-763 Medium NT-No. 1)
・ 7.2 parts by mass of aluminum scale (average length 14 μm, average thickness 0.04 μm)
・ Diluted solvent 88 parts by mass (7: 3 mixed solvent of ethyl acetate and n-propyl acetate)
<Ink for surface protective layer 3 (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 having the following prescription is applied to the entire surface of the paper substrate (single-sided ivory paper with a basis weight of 235 g / m ² ) so that the average thickness after drying is 1.0 μm and dried. An anchor coat layer was formed to obtain a laminate B.
Next, the gloss printing layer ink 5 having the following formulation was applied on 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 gloss printing layer.
Next, the surface protective layer ink 6 having the following formulation is applied and dried by gravure printing so that the average thickness after drying is 1.0 μm so as to cover the entire glossy printed layer side of the printed matter, and the surface protective layer ( A cured product layer of a thermosetting resin composition was formed, and a printed material of Example 2 was obtained.

<Ink for anchor coat layer 4>
Ethanol dispersion of thermoplastic acrylic resin having a solid content of 40.3% <Glossy printing layer ink 5>
-Aluminum scale dispersion 100 parts by mass (mass ratio of aluminum scale 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 weight of diluting solvent (n-propyl acetate alone)
<Ink 6 for surface protective layer (thermosetting type)>
An ink composition obtained by dispersing an acrylic thermosetting resin composition in ethanol.

[Comparative Example 1]
A metal roll and a rubber roll are extruded on the entire coated surface side of a paper substrate (basis weight: 235 g / m ² single-sided ivory paper) using a melt extrusion method so that the thickness is 15 μm. A thermoplastic resin layer was formed between the two and a laminate C was obtained. When extruding, the paper base was on the metal roll side and the molten resin was on the rubber roll side.
Next, the same glossy printed layer and surface protective layer as in Example 1 were formed on the thermoplastic resin layer of the laminate C, and the printed matter of Comparative Example 1 was obtained.

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

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

10: Paper base material 20: Anchor coat layer 30: Glossy print layer 40: Surface protective layer 50: Picture layer 100: Printed matter

Claims (5)

A printed matter having a glossy printed layer on a paper substrate, wherein the printed matter has an anchor coat layer containing a thermoplastic resin between the paper substrate and the glossy printed layer, and the glossy printed layer contains metal scales. The printed matter has a surface roughness on the glossy printed layer side based on the paper substrate of the printed matter that satisfies the following condition 1.
<Condition 1>
JIS B0601: 1994 arithmetic average roughness Ra _{0.25 of the} surface when the cut-off value is 0.25 mm is 0.25 μm or less. The printed matter according to claim 1, wherein the roughness of the surface satisfies the following condition 2.
<Condition 2>
When the cut-off value is 0.08 mm, the arithmetic average roughness Ra _0.08 of JIS B0601: 1994 of the surface and Ra _0.25 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 anchor coat layer has a thickness of 0.5 to 10 µm.   The printed matter according to claim 1, further comprising a surface protective layer on the glossy printed layer.   A container formed using the printed matter according to claim 1.