TWI735950B - Printed matter, and container made of the printed matter - Google Patents

Abstract

A printed matter is formed by having a hard coat layer 2 anywhere on the substrate 1, and a glossy printing layer 3 anywhere on the hard coat layer 2, the glossy printed layer 3 includes metal flakes, and the metal flakes meet the requirements The following conditions (1) and/or (2); The average thickness of the metal flakes is 0.01~0.08μm (1) 10≦The average length of the metal flakes/the thickness of the glossy printing layer (2).

Description

Printed matter, and container made of the printed matter

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

Traditionally, in various printed materials, in order to improve the design of the pattern, it has been required to impart metallic luster.

As a means of imparting metallic luster, a film with metallic luster is used. For example, a film with metallic luster is attached to a paper substrate to produce a substrate with metallic luster, and a pattern layer or the like is printed on the substrate to produce a printed matter with metallic luster.

However, since a thin film with metallic luster is formed by forming a metal vapor-deposited film on the thin film, it requires cost and is not suitable for inexpensive printed matter. Furthermore, the substrate with a metallic luster film attached to the paper substrate is curled due to the difference in shrinkage between the paper and the film. The accuracy of the step of forming a container is reduced, and there is a problem of reduced yield. In order to solve the above-mentioned problems, Patent Document 1 is proposed. Prior art literature Patent literature

Patent Document 1 　 JP 2003-2323 A

[The problem to be solved by the invention]

Patent Document 1 discloses a paper container formed by forming a printed layer with a metallic luster region containing an adhesive resin and metal thin film flakes on a paper substrate.

The paper container of Patent Document 1 does not have the problem of cost or curling. However, although the paper container of Patent Document 1 has a certain level of metallic luster, it does not have a high level of metallic luster.

The object of the present invention is to provide a printed matter and a container with high metallic luster without using metal vapor deposition methods. [Means to Solve the Problem]

In order to solve the above problems, the present invention provides the following printed matter and containers of [1] to [18]. [1] A printed matter, which is formed by having a hard coating anywhere on a substrate, and having a glossy printing layer anywhere on the hard coating layer, the glossy printing layer comprising metal flakes, and the metal flakes Meet the following conditions (1) and/or (2); The average thickness of the metal flakes is 0.01~0.08μm (1) 10≦the average length of the metal flakes/the thickness of the glossy printing layer (2). [2] The printed matter as in [1], wherein the average length and average thickness of the aforementioned metal flakes satisfy the following condition (3); the average thickness of the metal flakes/the average length of the metal flakes≦0.010 (3). [3] The printed matter of [1] or [2], wherein the average length of the aforementioned metal flakes is 5.0 to 30.0 μm. [4] The printed matter according to any one of [1] to [3], wherein the thickness of the aforementioned glossy printing layer is 0.15 to 1.50 μm. [5] The printed matter according to any one of [1] to [4], wherein the metal flakes are eccentrically present on the upper part of the glossy printed layer. [6] The printed matter as in any one of [1] to [5], wherein the cut-off value of the surface of the glossy printed layer is 0.08mm, JIS B0601: 2001 arithmetic average roughness (Ra _0.08 ) satisfies the following conditions (4); Ra _0.08 ≦0.100μm (4). [7] The printed matter according to [6], wherein _{the cut-off value of the surface of the aforementioned Ra 0.08} and the aforementioned glossy printed layer is JIS B0601: 2001 arithmetic average roughness (Ra _0.25 ) satisfies the following condition (5); 0.300<Ra _0.08 /Ra _0.25 <0.500 (5). [8] The printed matter as in any one of [1] to [7], wherein the cut-off value of the surface of the glossy printed layer is 0.08mm, the skewness of the roughness curve of JIS B0601:2001 (Rsk _0.08 ), and The skewness _{(Rsk 0.25} ) of the roughness curve of JIS B0601:2001 when the cut-off value of the surface of the aforementioned glossy printed layer is 0.25mm, satisfies the following conditions (7) and (8); 0.200＜Rsk _{0.25 -Rsk 0.08} ＜ 0.500 (7) 0<Rsk _0.25 (8). [9] The printed matter as in any one of [1] to [8], wherein the pattern is formed by the aforementioned glossy printing layer. [10] The printed matter as in any one of [1] to [9], wherein the JIS Z8741: 1997 on the surface of the hard coat layer has a 60 degree mirror gloss of 85% or more. [11] The printed matter according to any one of [1] to [10], wherein the surface roughness PPS of JIS P8151: 2004 of the surface of the hard coat layer is less than 1 μm. [12] The printed matter according to any one of [1] to [11], wherein the hard coat layer is a cured material layer of an ionizing radiation curable resin composition. [13] The printed matter according to any one of [1] to [12], wherein the aforementioned substrate is a paper substrate. [14] The printed matter according to [13], wherein the substrate is the paper substrate, and the surface of the glossy printed layer has a 60-degree specular gloss of 150% or more in JIS Z8741: 1997. [15] The printed matter according to any one of [1] to [14], wherein a pattern layer is provided on the aforementioned glossy printing layer. [16] The printed matter according to any one of [1] to [15], wherein any part of the gloss printing layer and/or the hard coat layer where the gloss printing layer is not formed has a pattern layer and become. [17] The printed matter according to any one of [1] to [16], wherein a surface protection layer is provided on the outermost surface of the side having the aforementioned glossy printed layer. [18] A container which is formed by using a printed matter as in any one of [1] to [17] [Effects of the invention]

The printed matter and the container of the present invention do not use metal vapor deposition methods and have high metallic luster, and the cost performance ratio is extremely excellent.

[Best form to implement the invention] [Printed matter]

The printed matter of the present invention is formed by having a hard coating anywhere on the substrate, and having a glossy printing layer anywhere on the hard coating. The glossy printing layer contains metal flakes, and the metal flakes meet the following conditions (1 ) And/or (2). The average thickness of the metal flakes is 0.01~0.08μm (1) 10≦[Average length of metal flakes/Thickness of glossy printing layer] (2)

Hereinafter, an embodiment of the printed matter of the present invention will be described. Fig. 1 and Fig. 2 are cross-sectional views showing an embodiment of the printed matter 10 of the present invention. The printed matter 10 shown in Figure 1 and Figure 2 is on the substrate 1 and has a hard coat layer 2 and a glossy printed layer 3 in this order. The printed matter in Figure 2 further has a pattern layer 4 and a surface protection layer 5 on the glossy printing layer 3. In addition, the glossy printed layer 3 of the printed matter 10 in FIG. 1 and FIG. 2 has a region 31 where metal flakes on the upper part are biased. Substrate

The material of the base material is not particularly limited as long as it is the material used in conventional printed matter, etc., but specifically, high-quality paper, medium-quality paper, coated paper, synthetic paper, impregnated paper, laminated paper, and coating for printing can be used. Paper, paper such as coated paper for recording, plastic film such as polyethylene terephthalate film, polyethylene film, polypropylene film, polycarbonate film, etc., or composites of these, etc. In the present invention, no matter what kind of substrate is used, by having a hard coat layer described later on the substrate, high metallic luster can always be realized.

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

In the present invention, by allowing the hard coat layer to exist between the base material and the glossy printing layer, the metallic luster of the glossy printing layer can be sufficiently improved. The reason for this is judged as follows. First, the hard coat layer is difficult to permeate the solvent of the ink for the glossy printing layer. Therefore, it is difficult for the solvent to flow under the glossy printing layer when the ink for the glossy printing layer is applied to the hard coat layer and dried. On the other hand, when the solvent is volatilized during the drying process, it becomes easy to flow over the glossy printing layer. Moreover, with the flow of the solvent, the metal flakes float above the glossy printing layer, and the metal flakes tend to exist on the upper part of the glossy printing layer, which can fully improve the metallic luster of the glossy printing layer. In addition, although the above-mentioned base material differs in degree depending on the type, the surface is rough. For example, paper has a rough surface due to fibers. It is considered that when the surface of the substrate is rough like this, when the glossy printing layer is formed, the surface of the glossy printing layer will also be rough, and the metallic luster cannot be improved sufficiently. However, the hard coating can alleviate the roughness of the substrate surface and suppress The surface of the glossy printing layer is rough, which can fully improve the metallic luster. In addition, when the surface of the substrate is damaged, the unevenness of the scar is reflected on the surface of the glossy printing layer, and the metallic luster of the glossy printing layer will be reduced. However, it is believed that the substrate made of the base material and the hard coat layer is not easy to be damaged on the surface, so that the unevenness caused by scratches is suppressed from being reflected on the surface of the glossy printing layer, and the metallic luster of the glossy printing layer can be fully improved.

The hard coat layer is preferably formed at least in a place corresponding to the place where the gloss printing layer is formed as described later. In addition, from the viewpoint of eliminating the cumbersome positioning of the hard coat layer and the glossy printed layer, the hard coat layer is preferably provided on the entire surface of the substrate where the glossy printed layer is formed. In addition, from the viewpoints of making the physical properties of the substrate formed of the substrate and the hard coating layer uniform and suppressing deformation of the substrate, the hard coating layer is preferably formed on the entire surface of the substrate.

The surface of the hard coat layer (the surface of the hard coat layer opposite to the substrate) is preferably smoothed. When the surface of the hard coat layer is rough, the surface area of the hard coat layer increases, and the solvent becomes easy to permeate when the glossy printing layer is formed. On the other hand, if the surface of the hard coat layer is smoothed, it is difficult for the solvent to penetrate the hard coat layer. Therefore, it becomes easy for the metal flakes to exist on the upper part of the glossy printing layer, and the metallic luster of the glossy printing layer can be sufficiently improved. Moreover, when the surface of the hard coat layer is rough, the unevenness of the hard coat layer is also reflected in the glossy printing layer, and the surface of the glossy printing layer is also rough. On the other hand, if the surface of the hard coat layer is smoothed, the surface of the glossy printed layer is also smoothed, and the above-mentioned surface shape is easily obtained.

As an index for smoothing the surface of the hard coat layer, there may be JIS Z8741: 1997 specular gloss or JIS B0601: 2001 arithmetic average roughness Ra. The JIS Z8741: 1997 60 degree mirror gloss of the hard coat surface is preferably 85% or more, more preferably 90% or more.

In the case of the hard coat layer, the surface roughness PPS of the hard coat layer is measured in accordance with JIS P8151: 2004, and is preferably less than 1 μm, preferably 0.6 μm or less. By making the surface roughness PPS of the surface less than 1 μm, the above-mentioned effects can be more remarkably exerted.

_{In addition, the arithmetic mean roughness Ra (Ra 0.08HA} ) of the hard coat surface with a cut-off value of 0.08 mm in JIS B0601:2001 is preferably 0.080 μm or less, more preferably 0.060 μm or less, and particularly preferably 0.040 μm or less. Furthermore, the cutoff value indicates the fineness of the filter that removes undulation components (low frequency components) from the cross-sectional curve. More specifically, the cross-sectional curve system can be divided into fluctuation components (medium frequency components, low frequency components) and roughness components (high frequency components). The higher the ratio of high frequency components. _Thus, Ra 0.08HA irregularities represents high-frequency component of the hard coat _layer, Ra 0.8HA later irregularities represents the low-frequency component of the hard coat layer. In addition, Ra _{0.25HA mentioned later} represents the unevenness of the intermediate frequency component of the hard coat layer. If the hard coat layer contains a lot of unevenness of high frequency components, the surface area of the hard coat layer becomes wider and the solvent becomes easy to permeate. Therefore, the metal flakes of the glossy printing layer are difficult to be concentrated on the upper part, and the metallic luster is easily damaged. Therefore, Ra _0.08HA should be in the above range.

_{In addition, the arithmetic average roughness Ra (Ra 0.25HA} ) of the hard coat surface with a cut-off value of 0.25 mm is preferably 0.200 μm or less, more preferably 0.175 μm or less, and particularly preferably 0.150 μm or less in JIS B0601:2001. _{In addition, the arithmetic average roughness Ra (Ra 0.8HA} ) of the hard coat surface with a cutoff value of 0.8 mm in JIS B0601:2001 is preferably 0.400 μm or less, more preferably 0.370 μm or less, and particularly preferably 0.350 μm or less. The unevenness of the mid-frequency component and the low-frequency component is not as high as that of the high-frequency component, but it increases the surface area. Therefore, Ra _{0.25HA is} preferably in the above range. Moreover, if the unevenness of the intermediate frequency component and low frequency component of the hard coat layer disappears, the unevenness caused by the unevenness of the intermediate frequency component and low frequency component of the hard coat layer will not be formed on the surface of the glossy printing layer. Glossy printing The layer has a tendency to over-smooth. At this time, the reflected light in the regular reflection direction of the glossy printed layer becomes too strong, which may give a visual observer an uncomfortable feeling. Therefore, Ra _{0.25HA is} preferably 0.050 μm or more, more preferably 0.100 μm or more. Furthermore, Ra _{0.8HA is} preferably 0.100 μm or more, more preferably 0.200 μm or more.

_{Furthermore, the arithmetic average roughness Ra (Ra 0.08BA} ) of the substrate surface with a cut-off value of 0.08mm: JIS B0601:2001, and the arithmetic average roughness of the substrate surface with a cut-off value of 0.25mm: JIS B0601:2001 Ra (Ra _0.25BA ), the aforementioned Ra _0.08HA and Ra _0.8HA preferably satisfy the following condition (a ₁ ). [Ra _0.25HA /Ra _0.25BA ]>[Ra _0.08HA /Ra _0.08BA ] (a ₁ ) Also, the arithmetic average roughness Ra(Ra _{0.08 BA ), JIS B0601:2001 arithmetic average roughness Ra (Ra 0.8BA} ) of the substrate surface with a cut-off value of 0.8 mm, and the above-mentioned Ra _{0.08 HA} and Ra _{0.8 HA} preferably satisfy the following condition (a ₂ ). [Ra _0.8HA /Ra _0.8BA ]>[Ra _0.08HA /Ra _0.08BA ] (a ₂ ) The ratio of the Ra of the hard coat layer to the Ra of the base material indicates the degree to which the hard coat layer relaxes the unevenness of the base material . In addition, the aforementioned conditions (a ₁ ) and (a ₂ ) indicate that the degree of mitigating the high-frequency component is greater than the degree of mitigating the medium-frequency component and low-frequency component of the unevenness of the substrate by the hard coat layer. As mentioned above, if the surface area of the hard coat layer is increased, the unevenness of the high-frequency component has a greater influence. Therefore, the hard coat layer preferably relaxes the unevenness of the high-frequency component of the base material. On the other hand, if the unevenness of the medium and low frequency components of the substrate is excessively reduced, the texture of the substrate may be impaired, and the reflected light in the regular reflection direction of the glossy printed layer may become too strong. Therefore, it is of great significance to satisfy the above conditions (a ₁ ) and (a ₂ ). This condition means that the high frequency components are relaxed compared to the degree to which the medium and low frequency components of the unevenness of the base material are relaxed. The degree is greater.

In order to more easily exert the above-mentioned effects, the above-mentioned Ra _0.08HA , Ra _0.25HA , Ra _0.08BA, and Ra _0.25BA preferably satisfy the following condition (b ₁ ). 1.5≦[Ra _0.25HA /Ra _0.25BA ]/[Ra _0.08HA /Ra _0.08BA ] (b ₁ ) The condition (b ₁ ) is more preferably 1.5≦[Ra _0.25HA /Ra _0.25BA ]/[Ra _0.08HA /Ra _0.08BA ]≦4.0, particularly _preferably 1.5≦[Ra 0.25HA /Ra _0.25BA ]/[Ra _0.08HA /Ra _0.08BA ]≦3.5. Furthermore, in order to more easily exhibit the above-mentioned effects, the above-mentioned Ra _0.08HA , Ra _0.8HA , Ra _0.08BA, and Ra _0.8BA preferably satisfy the following condition (b ₂ ). 1.8≦[Ra _0.8HA /Ra _0.8BA ]/[Ra _0.08HA /Ra _0.08BA ] (b ₂ ) condition (b ₂ ) is more preferably 2.2≦[Ra _0.8HA /Ra _0.8BA ]/[Ra _0.08HA /Ra _0.08BA ]≦4.0, particularly _preferably 2.5≦[Ra 0.8HA /Ra _0.8BA ]/[Ra _0.08HA /Ra _0.08BA ]≦3.5.

Specific examples of the hard coat layer include the hardened layer of the ionizing radiation curable resin composition (hereinafter also referred to as the "hardened layer"), clay coating, etc., from smoothness, damage prevention, and penetration prevention. From the viewpoint of becoming more favorable, the cured product layer of the ionizing radiation curable resin composition is preferable. Furthermore, when the hard coat layer is formed from the ionizing radiation curable resin composition, the hard coat layer can be cured instantaneously by the irradiation of ionizing radiation, so that the hard coat layer can be suppressed during the formation process of the hard coat layer. The surface shape of the substrate follows the unevenness of the high-frequency component of the substrate. In other words, when the hard coat layer is formed from the ionizing radiation curable resin composition, the hard coat layer can 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 appropriately follows the unevenness of the low-frequency component of the substrate. That is, when the hard coat layer is formed from the ionizing radiation curable resin composition, the surface of the hard coat layer can be made into a shape with moderate low-frequency component unevenness while suppressing the unevenness of the high-frequency component, and the above-mentioned effect can be easily exhibited. (Suppression of solvent penetration of hard coat layer, maintenance of base material texture, etc.). Hardened layer

The ionizing radiation curable resin composition used to form the cured layer is a composition containing a compound having an ionizing radiation curable functional group (hereinafter also referred to as "ionizing radiation curable compound"). Examples of the ionizing radiation-curable functional group include ethylenic unsaturated bonding groups such as (meth)acryloyl, vinyl, and allyl groups, epoxy groups, and oxetanyl groups. As the ionizing radiation curable compound, a compound having an ethylenically unsaturated bond group is preferred, a compound having an ethylenically unsaturated bond group is more preferred, and a compound having two or more ethylenically unsaturated bonds is more preferred. Multifunctional (meth)acrylate based compound. As a polyfunctional (meth)acrylate compound, any one of monomers and oligomers can be used, but from the viewpoint that the high crosslinking density makes the damage prevention and penetration prevention better From a standpoint, it is preferably a monomer. Furthermore, the so-called ionizing radiation refers to those with energy capable of polymerizing or cross-linking molecules among electromagnetic waves or charged particle beams. Ultraviolet rays (UV) or electron rays (EB) are usually used, but they can also be used. Electromagnetic waves such as X-rays and γ-rays, and charged particle beams such as α-rays and ion beams are used.

Among the polyfunctional (meth)acrylate monomers, examples of the bifunctional (meth)acrylate monomers include ethylene glycol di(meth)acrylate, bisphenol A tetraethoxydi Acrylate, bisphenol A tetrapropoxy diacrylate, 1,6-hexanediol diacrylate, etc. Examples of (meth)acrylate monomers having trifunctional or higher functionality include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, Dipentaerythritol hexa(meth)acrylate, dipentaerythritol tetra(meth)acrylate, isocyanuric acid modified (meth)acrylate, etc. In addition, the above-mentioned (meth)acrylate-based monomers may be modified by part of the molecular skeleton, and may also be used via ethylene oxide, propylene oxide, caprolactone, isocyanuric acid, alkyl, Those modified by cyclic alkyl, aromatic, bisphenol, etc. The number of functional groups of the polyfunctional (meth)acrylate monomer is preferably 2-6, more preferably 2-3.

In addition, examples of the polyfunctional (meth)acrylate oligomer include urethane (meth)acrylate, epoxy (meth)acrylate, polyester (meth)acrylate, Acrylate polymers such as polyether (meth)acrylate. Urethane (meth)acrylate is, for example, obtained by the reaction of polyol and organic diisocyanate with hydroxy (meth)acrylate. In addition, preferred epoxy (meth)acrylates are obtained by reacting trifunctional or higher aromatic epoxy resins, alicyclic epoxy resins, aliphatic epoxy resins, etc. with (meth)acrylic acid ( Meth) acrylate is a (meth)acrylate obtained by reacting a bifunctional or higher aromatic epoxy resin, alicyclic epoxy resin, aliphatic epoxy resin, etc., with a polybasic acid and (meth)acrylic acid, And (meth)acrylate obtained by reacting bifunctional or higher aromatic epoxy resin, alicyclic epoxy resin, aliphatic epoxy resin, etc., with phenols and (meth)acrylic acid. The above-mentioned ionizing radiation curable compound system can be used individually by 1 type or in combination of 2 or more types. The ionizing radiation curable compound preferably contains 50% by mass or more of the polyfunctional (meth)acrylate monomer, and more preferably contains 80% by mass or more.

When the ionizing radiation curable compound is an ultraviolet curable compound, the ionizing radiation curable composition (ultraviolet effective resin composition) preferably contains an additive such as a photopolymerization initiator or a photopolymerization accelerator. Examples of photopolymerization initiators include acetophenone, benzophenone, α-hydroxyalkylphenol, Michele ketone, benzoin, benzyl methyl ketal, and benzyl benzoic acid. One or more selected from esters, α-acetoxime esters, and thioxanthones. In addition, the photopolymerization accelerator system can reduce the polymerization hindrance caused by air during curing and can accelerate the curing speed. One or more selected such as ethyl formate. The ionizing radiation curable resin composition may also contain additives such as light stabilizers, antioxidants, and leveling agents. Furthermore, the ionizing radiation curable resin composition may contain resin components (thermoplastic resin or thermosetting resin) other than the ionizing radiation curable compound. However, in order to easily achieve the above effects, the ratio of the ionizing radiation-forming compound in the total resin components of the ionizing radiation-curable resin composition is preferably 90% by mass or more, more preferably 95% by mass or more, and particularly preferably 100 quality%.

From the viewpoint of smoothing the base material and preventing damage, the thickness of the cured product layer is preferably 2 μm or more. Furthermore, since the workability of the hardened material layer is too thick, the thickness of the hardened material layer is preferably 3-20 μm, more preferably 4-10 μm, and particularly preferably 5-7 μm.

The cured product layer can be formed by applying an ink for a cured product layer containing an ionizing radiation curable resin composition and optionally a diluent solvent on a substrate, drying, and irradiating with ionizing radiation. Furthermore, when the ink for the cured material layer does not contain a solvent, drying is not required. Clay coating

The clay coating includes clay and binder resin. As the clay, as long as it is generally referred to as clay or clay, it can be used without particular limitation. Furthermore, kaolin, talc, bentonite, smectite, vermiculite, mica, chlorite, kojiclay, and frog can be used. Mesh clay, halloysite, mica, etc.

In addition to clay, the clay coating preferably also contains pigments such as calcium carbonate, titanium dioxide, amorphous silica, foamable molybdenum sulfate, and satin white. By using calcium carbonate or titanium dioxide as a pigment, the smoothness of the surface of the clay coating can be easily improved. Furthermore, calcium carbonate is more suitable for use because it is cheap.

Examples of binder resins include latex binder resins (for example, styrene butadiene latex, acrylic latex, vinyl acetate latex), and water-soluble binder resins (for example, starch (modified starch, oxidized starch) , Hydroxyethyl etherified starch, phosphate esterified starch), polyvinyl alcohol, casein, etc.).

Clay in clay coating: Pigment: The quality of binder resin is better than 1~20:50~90:10~30. The clay coating can also contain additives such as pigment dispersant, defoamer, foam inhibitor, viscosity regulator, lubricant, water resistance agent, water retention agent, color material, printing adaptability improver, etc.

From the viewpoint of the smoothing of the substrate, the prevention of damage, and the balance of workability, the thickness of the clay coating is preferably 5-40 μm, more preferably 10-30 μm, and particularly preferably 15-25 μm.

The clay coating can be formed by applying a clay coating ink that is diluted in a solvent with the material constituting the clay coating on the substrate and then drying. Glossy printing layer

The gloss printing layer is a layer located on the hard coat layer and is formed by printing ink for the gloss printing layer. In this way, by printing and forming the layer that imparts metallic luster without vapor deposition, the cost can be reduced while suppressing the occurrence of curling. The glossy printing layer is preferably formed by being attached to the hard coat layer. In addition, the glossy printing layer can be formed with a desired pattern on a part of the hard coat layer as shown in Figure 1, to form a pattern of characters, numbers, graphics, signs, landscapes, people, animals, characters, etc., or As shown in Figure 2, all areas are formed on the hard coat layer.

Furthermore, in the present invention, it is necessary to include metal flakes in the glossy print layer. The metal flakes are preferably present biased on the upper part of the glossy printed layer (the opposite side of the glossy printed layer from the hard coat layer). Since the metal flakes are present on the upper part of the gloss printing layer, the metallic gloss can be improved, and the adhesion between the gloss printing layer and the hard coating can be improved.

The metal flakes can be biased in the upper part of the glossy printing layer during the process of forming the glossy printing layer. In more detail, during the heating and drying process of the glossy printing layer, when the solvent of the ink for the glossy printing layer evaporates, the solvent system flows upward. Furthermore, it was judged that the metal flakes floated with the flow of the solvent, and the metal flakes were eccentrically present on the upper part of the glossy printing layer. In particular, in the present invention, it is judged that the hard coat layer which is difficult to penetrate by the solvent is located under the gloss printing layer, so that the solvent can be prevented from flowing downward. Since almost all the solvent flows upward, the metal flakes tend to exist in the gloss printing. The upper part of the layer. In particular, it is considered that when the hard coat layer is a cured layer of an ionizing radiation curable resin composition, the deflection of the metal flakes becomes more noticeable.

The degree of deflection of the metal flakes can be confirmed by taking the cross-section of the printed matter with an electron microscope, and confirming the density difference in the glossy printing layer of the photograph taken. In more detail, where the deflection of the metal flakes exists, white is seen due to the significant reflection of electrons, and a gray tone is seen where the metal flakes are not substantially contained. The ratio of the thickness of the area where the metal flakes are biased in the glossy print layer [(the thickness of the area where the metal flakes are biased/the total thickness of the glossy print layer), from the viewpoint of the balance of metallic luster and adhesion, is preferably 10~60%, more preferably 20~50%, particularly preferably 25~45%.

From the viewpoint of the deviated existence and arrangement of the metal flakes, the average thickness of the metal flakes satisfies the following condition (1). The average thickness of the metal flakes is 0.01~0.08μm (1) Furthermore, from the viewpoint of handleability and high metallic luster, the average thickness of the metal flakes is more preferably 0.02 to 0.06 μm.

From the viewpoints of the dispersibility, the presence and arrangement of the metal flakes, the average length of the metal flakes is preferably 5.0 to 30.0 μm, more preferably 8.0 to 20.0 μm.

The average length and average thickness of the metal flakes are taken as the average value of 100 metal flakes. Furthermore, the length and thickness of each metal flake can be measured using a laser interference type three-dimensional shape analysis device in a state where the metal flakes have been spread on a smooth substrate. The length of each metal flake means the maximum diameter when viewing each metal flake from a plane in any direction, and the thickness of each metal flake means the maximum thickness when viewing each metal flake from the cross-sectional direction. In addition, the so-called maximum diameter when each metal flake is viewed from a plane in an arbitrary direction is to unify the direction in which the maximum diameter of each metal flake is measured. For example, when the X-axis direction on the screen on which the measurement result of the three-dimensional shape analysis device is image-processed is regarded as an arbitrary direction (measurement direction), the maximum diameter is measured in a direction parallel to the X-axis. It is assumed that there is a maximum diameter in a direction that is not parallel to the X axis, and it is not regarded as the maximum diameter. As a laser interference type three-dimensional shape analysis device, for example, the product name "Shape Analysis Laser Microscope VK-X Series" manufactured by KEYENCE can be cited.

At the time of applying the ink for the glossy printing layer, from the viewpoint of further suppressing the tilt of the metal flakes in the horizontal direction of the glossy print layer, and from the viewpoint of suppressing the protrusion of the metal flakes from the surface of the glossy printing layer, the average length and gloss of the metal flakes The thickness of the printed layer must meet the following condition (2). 10≦The average length of the metal flakes/the thickness of the glossy printing layer (2) Furthermore, if [the average length of the metal flakes/the thickness of the glossy printing layer] is too large, the metal flakes may protrude from the surface of the glossy print layer. Therefore, the condition (2) is more preferably to satisfy 15≦the average length of the metal flakes/ The thickness of the glossy printing layer is less than or equal to 60, and it is particularly preferable to satisfy 25≦the average length of the metal flakes/the thickness of the glossy printing layer≦50.

In addition, the metal flakes preferably satisfy the following condition (3). The average thickness of the metal flakes/the average length of the metal flakes≦0.010 (3) By setting [Average thickness of metal flakes/Average length of metal flakes] to be 0.010 or less, when the ink for the glossy printing layer is applied, the horizontal direction of the glossy printing layer (orthogonal to the thickness direction of the glossy printing layer) Direction), the metal scales are not easy to tilt. Therefore, in the drying process of glossy printing, when the solvent flows above the glossy printing layer, the metal flakes are easily affected by the flowing force of the solvent, and the metal flakes tend to exist on the upper part of the glossy printing layer, and the metal flakes are easily arranged in parallel. , It can easily make the metallic luster good. In addition, the disadvantages caused by the inclination of metal flakes increase as the content of metal flakes increases. However, when the above condition (3) is satisfied, since the metal flakes are not easily inclined, the content of metal flakes can be increased, and the metallic luster can be easily changed. good. Furthermore, if the average thickness of the metal flakes is too thin with respect to the average length of the metal flakes, the operability becomes difficult, and there is a possibility that sufficient metallic luster cannot be exhibited. Therefore, the condition (3) preferably satisfies 0.001≦the average thickness of the metal flakes/the average length of the metal flakes≦0.01, more preferably satisfies 0.002≦the average thickness of the metal flakes/the average length of the metal flakes≦0.008, and particularly preferably satisfies 0.002≦average thickness of metal flakes/average length of metal flakes≦0.005.

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

The glossy printing layer preferably further contains a binder resin. Examples of the binder resin include thermoplastic resins and thermosetting resins such as polyester resins, urethane resins, epoxy resins, melamine resins, alkyd resins, phenol resins, acrylic resins, and cellulose resins. In addition, as the binder resin, a cured product of the aforementioned ultraviolet curable resin composition can also be used.

The blending ratio of the binder resin and the metal flakes is preferably 55:45 to 30:70, more preferably 50:50 to 35:65 in terms of solid content mass ratio. With the binder resin of 55, the metal flakes can be made 45 or more, and sufficient metallic luster can be easily obtained. With the binder resin of 30, the metal flakes can be made 70 or less, and the gloss of the printed layer can be easily changed. Printability and processability of printed matter became good. Furthermore, in the present invention, since the hard coat layer is provided under the glossy printed layer, even if a large amount of metal flakes are used as described above, the metal flakes can be eccentrically present on the upper part of the glossy printed layer.

From the viewpoint of the orientation and arrangement of the metal flakes, and from the viewpoint of concealment, the thickness of the glossy printing layer is preferably 0.15 to 1.50 μm, more preferably 0.20 to 1.00 μm, and particularly preferably 0.25 to 0.75 μm. Furthermore, the thickness of the glossy printing layer can be measured using a scanning electron microscope (SEM), a transmission electron microscope (TEM), or a scanning transmission electron microscope (STEM), for example, from the cross-sectional image taken. The thickness of 20 places is calculated from the average of the values of 20 places. When the measured film thickness is on the order of μm, it is preferable to use SEM, and when it is on the order of nm, it is preferable to use TEM or STEM. In SEM, the accelerating voltage is preferably 1kV~10kV, and the magnification is 1000~7000 times. In TEM or STEM, the accelerating voltage is preferably 10kV~30kV, and the magnification is 50,000~300,000 times. The thickness of layers other than the glossy printed layer can also be measured by the same method as described above.

In the gloss printing layer, in order to make the gloss printing layer the desired color, coloring agents such as titanium oxide, zinc bloom, carbon black, iron oxide, iron yellow, ultramarine blue, metallic pigments, pearlescent pigments, etc. may also be contained.

The surface of the glossy printing layer (the surface of the glossy printing layer on the opposite side of the hard coat layer) is JIS Z8741: 1997. The mirror gloss at 60 degrees is preferably 150% or more, more preferably 200% or more, and particularly preferably 250 %above. The upper limit of the mirror gloss on the surface of the glossy printing layer is about 500%.

The glossy printing layer can be formed by applying an ink for a glossy printing layer formed by diluting the components forming the glossy printing layer with a solvent, coating it on the hard coat layer, drying, and irradiating ultraviolet rays as necessary. From the viewpoint of the coexistence of the orientation of the metal flakes and the coexistence of the drying efficiency, the ink for the glossy printing layer preferably contains 600 to 1100 parts by mass of the solvent relative to 100 parts by mass of the total solid content. Since the permeability of the solvent varies with the resin composition of the hard coat layer, the type of suitable solvent cannot be generalized, but for example, ethyl acetate, isopropanol (IPA), ethanol, and n-propyl acetate (NPAC) can be used. Or a mixture of these, etc. Surface condition of glossy printing layer

_{The printed matter of the present invention is a JIS B0601:2001 arithmetic average roughness (Ra 0.08} ) when the cut-off value of the surface of the glossy printed layer is 0.08 mm, which satisfies the following condition (1). Ra _0.08 ≦0.100μm (4)

The cutoff value is a value indicating the degree to which the roughness component (high-frequency component) and the undulating component (mid-frequency component, low-frequency component) are cut from the cross-sectional curve formed by the roughness component (high-frequency component) and the undulating component (mid-frequency component, low-frequency component). In other words, the cutoff value is a value indicating the fineness of the filter that cuts undulating components (mid-frequency components, low-frequency components). More specifically, since the larger the cutoff value, the thicker the filter, the large fluctuations in the fluctuation components (mid-frequency components, low-frequency components) are cut, but the small fluctuations are not cut. That is, if the cutoff value is large, it becomes a value including fluctuation components (medium frequency components, low frequency components). On the other hand, since the cutoff value is smaller, the filter becomes finer, and most of the fluctuation components (mid-frequency components, low-frequency components) are cut. That is, if the cutoff value is small, there is almost no fluctuation component (mid-frequency component, low-frequency component), and it becomes a value that accurately reflects the roughness component (high-frequency component). Hereinafter, the roughness component with a cut-off value of 0.08 mm is also referred to as a high-frequency component, and the fluctuation component with a cut-off value of 0.25 mm is also referred to as an intermediate frequency component.

Condition (4) requires Ra _0.08 (Ra of high frequency components) to be 0.100 μm or less. When the condition (4) is not satisfied, among the reflected light on the surface of the glossy printed layer, the proportion of the reflected light in the regular reflection direction will decrease, and the metallic luster will decrease. In the condition (4), _{the lower limit of Ra 0.08} is not particularly limited, but when Ra _0.08 is greater than the specified value, the reduction in visibility due to excessively strong reflected light in the regular reflection direction can be suppressed. Based on such viewpoint, the condition (4) is preferably satisfied 0.010μm ≦ Ra _0.08 ≦ 0.070μm, more preferably satisfies the 0.020μm ≦ Ra _0.08 ≦ 0.050μm, particularly preferably satisfies 0.025μm ≦ Ra _0.08 ≦ 0.040μm.

_{The arithmetic average roughness (Ra 0.25} ) of JIS B0601:2001 when the cut-off value of the surface of the printed matter of the present invention is Ra _0.08 and the glossy printed layer is 0.25 mm, preferably satisfies the following condition (5). 0.300＜Ra _0.08 /Ra _0.25 ＜0.500 (5)

Condition (5) specifies the _{ratio of Ra 0.08} (Ra of high frequency components) to Ra _0.25 (Ra of intermediate frequency components). That is, the condition (5) means that not only the Ra of the high frequency component but also the Ra of the specified intermediate frequency component exists on the surface of the glossy printing layer. By satisfying the condition (5), the Ra system of the intermediate frequency component is moderately present, and the reflection intensity of the regular reflection light is suppressed from becoming too strong, which is preferable because it can prevent the viewer from being uncomfortable. The condition (5) is more preferably 0.325<Ra _0.08 /Ra _0.25 <0.500, and particularly _{preferably 0.350<Ra 0.08} /Ra _0.25 <0.450.

_{The arithmetic average roughness (Ra 0.8} ) of JIS B0601:2001 when the cutoff value of the surface of the printed matter of the present invention is Ra _0.08 and the glossy printed layer is 0.8 mm, and preferably satisfies the following condition (6). 0.050＜Ra _0.08 /Ra _0.8 ＜0.200 (6)

Condition (6) specifies the _{ratio of Ra 0.08} (Ra for high frequency components) to Ra _0.8 (Ra for low frequency components). That is, the condition (6) means that not only the Ra of the high-frequency component, but also the Ra of the specified low-frequency component exists on the surface of the glossy printing layer. By satisfying the condition (6), the Ra system of the intermediate frequency component is moderately present, and the reflection intensity of the regular reflection light is suppressed from becoming too strong, which is preferable because it can prevent the viewer from being uncomfortable. The condition (6) is more preferably 0.075<Ra _0.08 /Ra _0.8 <0.180, and particularly _{preferably 0.100<Ra 0.08} /Ra _0.8 <0.160.

The printed matter of the present invention is JIS B0601 when the cut-off value of the surface of the glossy printed layer is 0.08mm: The skewness of the roughness curve of 2001 (Rsk _0.08 ), and the cut-off value of the surface of the glossy printed layer is JIS B0601 when the cut-off value is 0.25mm: _{The skewness (Rsk 0.25} ) of the roughness curve in 2001 preferably satisfies the following conditions (7) and (8). 0.200＜Rsk _0.25 -Rsk _0.08 ＜0.500 (7) 0＜Rsk _0.25 (8)

The printed matter of the present invention is JIS B0601 when the cut-off value of the surface of the glossy printed layer is 0.08mm: The skewness of the roughness curve of 2001 (Rsk _0.08 ), and JIS B0601 when the cut-off value of the surface of the glossy printed layer is 0.8mm: _{The skewness (Rsk 0.8} ) of the roughness curve in 2001 is preferably to satisfy the following conditions (9) and (10). 0.100＜Rsk _0.25 －Rsk _0.08 ＜0.300 (9) 0＜Rsk _0.5 (10)

The skewness (Rsk) of the roughness curve is an index indicating how much the height distribution of the surface formed by the convex part (mountain) and the concave part (valley) deviates from the normal distribution. If the height distribution is a normal distribution, the value is 0 , The concave part has a negative value in the dominant surface, and the convex part has a positive non-dimensional value in the dominant surface. By satisfying the conditions (7) to (10), the convex parts are moderately dominant intermediate frequency components and low frequency components, and there is no overlap of high frequency components that do not have extremely convex parts. Therefore, it has a metallic luster and becomes a good visual recognition. Has a moderately diffused surface.

Furthermore, in the present invention, conditions (4) to (10) are the average values of 10 measurements. Pattern layer

The printed matter of the present invention is for the purpose of improving the pattern design of the printed matter, and it is preferable to have a pattern layer on any part of the glossy printed layer and/or on the hard coat layer where the glossy printed layer is not formed. For example, the pattern layer can be formed anywhere on the glossy printing layer and/or on the substrate where the glossy printing layer is not formed. The pattern layer is formed by printing or the like. The pattern layer can be formed by multi-color printing with normal yellow, red, blue, and black processing colors, and can also prepare plates of each color that constitutes the pattern, which can be formed by special multi-color printing, etc. . As long as the pattern of the pattern layer is a pattern used in normal printing (for example, characters, numbers, graphics, signs, landscapes, people, animals, characters, etc.), it can be used without particular limitation.

As the ink used for the formation of the pattern layer, a binder resin may be suitably mixed with coloring agents such as pigments and dyes, extender pigments, solvents, stabilizers, plasticizers, catalysts, hardeners, and the like. The binder resin is not particularly limited, and examples include acrylic resins, styrene resins, polyester resins, urethane resins, chlorinated polyolefin resins, and vinyl chloride-vinyl acetate. Copolymer resins, polyvinyl butyral resins, alkyd resins, petroleum resins, ketone resins, epoxy resins, melamine resins, fluorine resins, silicone resins, cellulose derivatives, rubber resins Wait. These resin systems can be used alone or in combination of two or more kinds.

The thickness of the pattern layer can be adjusted appropriately within the range of about 0.1-20μm, considering the shape and purpose of the pattern design. The pattern layer may contain additives such as antioxidants and ultraviolet absorbers within a range that does not hinder the effects of the present invention. Surface protection layer

The printed matter of the present invention preferably has a surface protection layer on the outermost surface on the side with the glossy printed layer. By forming a surface protective layer, the scratch resistance and weather resistance of the printed matter can be improved. For this effect, the surface protection layer is preferably formed to cover the entire area of the glossy printing layer and the pattern layer provided as needed, and more preferably to further cover the entire area of the hard coat layer.

The surface protection layer is preferably formed of a curable resin. Surface protective layer The surface protective layer is preferably a cured layer of a thermosetting resin composition, but is preferably a cured layer of an ultraviolet curable resin composition. When the surface protective layer is formed with an ultraviolet curable resin composition, the surface protective layer can be cured instantaneously by ultraviolet radiation. Therefore, during the formation of the surface protective layer, the surface shape of the surface protective layer can be prevented from following the lower layer ( For example, the unevenness of the high-frequency component of the pattern layer, etc., can improve the metallic luster of the surface of the surface protection layer. On the other hand, during the period before the ultraviolet curable resin composition is irradiated with ultraviolet rays (the period before the ultraviolet curable resin composition starts to harden), the surface shape of the surface protective layer appropriately follows the low-frequency components of the lower layer (such as the gloss printing layer, etc.) The bumps. Therefore, although there is a small amount in the surface protection layer, the low-frequency component of the unevenness is maintained, and the surface of the surface protection layer is prevented from being excessively smoothed, and the reflected light in the regular reflection direction becomes too high, which gives the viewer a sense of discomfort. . Furthermore, in order to achieve the aforementioned effects more easily, the ultraviolet curable resin composition preferably does not contain a solvent.

The ultraviolet curable resin composition forming the surface protective layer can be the same as the ultraviolet curable resin composition exemplified for the glossy printing layer. In order to improve weather resistance, the surface protective layer preferably contains an ultraviolet absorber and/or a light stabilizer. Furthermore, the ultraviolet curable resin composition may contain resin components (thermoplastic resin or thermosetting resin) other than the ultraviolet curable compound. However, in order to easily achieve the above effect, the proportion of the ultraviolet curable compound in the total resin components of the ultraviolet curable resin composition is preferably 90% by mass or more, more preferably 95% by mass or more, and particularly preferably 100% by mass .

The surface protective layer can be formed by coating an ink for a surface protective layer containing an ultraviolet curable resin composition and an optionally added solvent on a substrate, drying, and irradiating with ionizing radiation. Furthermore, when the ink for the surface protective layer does not contain a solvent, drying is not required.

The thickness of the surface protection layer is preferably 0.5 to 5.0 μm, more preferably 0.8 to 1.5 μm. [container]

The container of the present invention is formed by using the above-mentioned printed matter of the present invention. The container is not particularly limited, and examples include beverage containers, food containers, and the like. The container of the present invention has an excellent gloss and has excellent pattern design. In addition, since the curling of the printed matter is suppressed, the trouble caused by curling can be prevented during the manufacturing process of the container. [Example]

Secondly, the present invention is explained in more detail through examples, but the present invention is not limited by this example at all. 1. Measurement and evaluation

The following measurements and evaluations were performed on the printed matter produced in the examples and comparative examples and the printed matter of the reference example. The results are shown in Table 1 to Table 3. 1-1. Mirror gloss

For the printed matter of Examples 1 to 4, Comparative Examples 1 to 4, and intermediates of the printed matter, the micro-TRI-gloss of BYK Gardner was used as a measuring instrument to measure the 60 degree specular gloss in JIS Z8741:1997. 1-2. Surface roughness PPS

For the printed matter of Examples 1 to 4 and the intermediates of the printed matter, the Parker Print-Surf Ver. 58-06-00 of TESTING MACHINES INC. was used as the measuring instrument, and the surface of the hard coat layer was measured according to JIS P8151: 2004. Surface roughness PPS. 1-3. Curl

For the printed matter of Examples 1 to 4 and Comparative Examples 1 to 4, according to the "Curl Depth Measurement Method" of JAPAN TAPPI No. 15-1, the curl depth was measured under the conditions of a temperature of 25° C. and a humidity of 75% RH. 1-4. Surface roughness measurement (cutoff value 0.08mm, 0.25mm, 0.8mm)

For the surface of the glossy printed layer or vapor-deposited film of the printed matter of Examples 1 to 4 and Comparative Examples 1 to 3, a surface roughness tester (model: SE2555N/manufactured by Kosaka Laboratory Co., Ltd.) was used under the following measurement conditions Measure the surface roughness according to JIS B0601:2001 when the cutoff values are 0.08mm, 0.25mm, 0.8mm. [The stylus of the surface roughness detection department] Product name SE2555N manufactured by Kosaka Research Institute (front end curvature radius: 2μm, vertex angle: 90 degrees, material: diamond) [Measurement conditions of surface roughness tester] ・Evaluation length (reference length): 5 times the cutoff value λc ・Moving speed of stylus: 0.5mm/s ・Preparation length: (cutoff value λc)×2 ・Longitudinal magnification: 2000 times ・Horizontal magnification: 10 times 2. Production of printed matter [Example 1]

On the entire surface of the substrate (single-sided ivory paper with a basis weight of 235g/m ² ) on the coated side, the hard coat ink 1 of the following formulation was applied so that the thickness after drying became 6 μm, dried, and irradiated with ultraviolet rays , To form a hard coat layer (cured layer of ionizing radiation curable resin composition). Next, on the entire surface of the hard coat layer, the gloss printing layer ink 1 of the following formulation was applied so that the thickness after drying became 0.30 μm, and dried to form a gloss printing layer. The printed matter of Example 1 was obtained. Furthermore, the thickness of the region where the metal flakes of the glossy printing layer of Example 1 are substantially absent is 0.20 μm, and the thickness of the region where the metal flakes are biased is 0.10 μm. ＜Ink for hard coat 1＞

・Ionizing radiation hardening compound 70 copies (Made by BASF Japan, trade name: Lumogen OVD Primer301) (Mixture of 2-functional acrylate monomer and 3-functional acrylate monomer) ・Solvent (ethyl acetate) 30 copies ＜Ink for glossy printing layer 1＞

・Binder resin (nitrocellulose) 4.8 copies (Manufactured by DIC Graphics) (Trade name: XS-763 Mejiyume NT-No.1) ・Aluminum flakes 7.2 copies (The average length is 14μm, the average thickness is 0.04μm) ・Solvents (ethyl acetate, IPA, ethanol, NPAC) 88 copies [Example 2]

Except that the thickness of the glossy printed layer was changed to 0.50 μm, the printed matter of Example 2 was obtained in the same manner as in Example 1. Furthermore, the thickness of the region where the metal flakes of the glossy printing layer of Example 2 are substantially absent is 0.30 μm, and the thickness of the region where the metal flakes are biased is 0.20 μm. [Example 3]

Except that the thickness of the glossy printed layer was changed to 0.70 μm, in the same manner as in Example 1, a printed matter of Example 3 was obtained. Furthermore, the thickness of the region where the metal flakes of the glossy printing layer are substantially absent is 0.42 μm, and the thickness of the region where the metal flakes are biased is 0.28 μm. [Example 4]

Except that the thickness of the glossy printed layer was changed to 1.00 μm, in the same manner as in Example 1, a printed matter of Example 4 was obtained. Furthermore, in Example 4, the thickness of the region where the metal flakes of the glossy printing layer are substantially absent is 0.60 μm, and the thickness of the region where the metal flakes are biased is 0.40 μm. [Example 5]

Except that the thickness of the hard coat layer was changed to 5 μm and the thickness of the glossy printed layer was changed to 1.0 μm, the same procedure as in Example 1 was carried out to obtain a printed matter of Example 5. Furthermore, in Example 5, the thickness of the area where the metal flakes of the glossy printing layer are substantially absent is 0.60 μm, and the thickness of the area where the metal flakes are biased is 0.40 μm. [Example 6]

The printed matter of Example 6 was obtained in the same manner as Example 5 except that the base material was coated paperboard (basis weight 350 g/m ^{2 ).} [Comparative Example 1]

Except that the gloss printing layer ink 1 of Example 1 was changed to the gloss printing layer ink 2 of the following formulation, and it was coated so that the thickness after drying became 1.5 μm, and the hard coat ink 1 was not applied to the substrate In the same manner as in Example 1, a printed matter of Comparative Example 1 was obtained. ＜Ink for glossy printing layer 2＞ ・Binder resin (nitrocellulose) 6 copies (Manufactured by DIC Graphics) (Trade name: XS-763 Mejiyume NT-No.1) ・Aluminum sheet 6 copies (Manufactured by Toyo Aluminium Co., Ltd., trade name: TD-180T) (The average length is 15μm, and the average thickness exceeds 0.2μm) ・Solvents (ethyl acetate, IPA, ethanol, NPAC) 88 copies [Comparative Example 2]

Prepare a vapor-deposited film having an aluminum vapor-deposited film with a thickness of 50 nm on a biaxially stretched PET film with a thickness of 12 μm. The base material (single-sided ivory paper with a basis weight of 235g/m ² ) is extruded with a low density on the side of the coating side and the side of the PET film of the vapor-deposited film using a sandwich layer method to a thickness of 15μm. Polyethylene (LDPE) was laminated together to obtain a printed matter of Comparative Example 2 (not to be a printed matter to be precise, but it is called a printed matter for convenience). [Comparative Example 3]

Except that the ink 1 for hard coat layer of Example 1 was changed to the thermoplastic resin 1 of the following formulation, and the ink 1 for hard coat layer was not coated on the substrate by extrusion coating to a thickness of 15 μm. In the same manner as in Example 1, a printed matter of Comparative Example 3 was obtained. ＜Thermoplastic resin 1＞ ・Low density polyethylene resin (density: 0.923g/cm³ , Melt Index (MI): 3.8, melting point 109°C) [Comparative Example 4]

On the coated side of the substrate (single-sided ivory paper with a basis weight of 235g/m ^{2 ), the glossy printing layer ink 1 was applied at a coating amount of 1 g/m 2} and dried to form a glossy printing layer. Comparative Example 4 was obtained Printed matter. In the printed matter of Comparative Example 4, the ink penetrated into the substrate, and it was difficult to determine the thickness after drying.

Table 1

Table 2

table 3

It can be seen from the results in Table 1 that the printed matter of Examples 1 to 7 does not use a metal vapor deposition method, and has an excellent metallic gloss with a specular gloss of 150% or more. On the other hand, since the printed matter of Comparative Example 1 does not use metal flakes, the specular gloss (metallic gloss) is poor. Since the printed matter of Comparative Example 2 used vapor-deposited PET, although it was excellent in specular gloss (metallic gloss), curling occurred. In addition, the printed matter of Comparative Example 2 had excessive specular gloss (metallic luster), which gave the viewer an uncomfortable feeling. The printed matter of Comparative Example 3 had a glossy printed layer containing metal flakes, but the thermoplastic resin layer arranged under the glossy printed layer did not exert the effect of a hard coat layer, and thus the specular gloss (metallic gloss) could not be improved. The printed matter of Comparative Example 4 has a glossy printing layer containing metal flakes, but since there is no hard coat layer under the glossy printing layer, when the glossy printing layer is formed, the solvent and resin will penetrate into the substrate, and the mirror gloss cannot be improved. Degree (metallic luster).

From the results of Table 2 and Table 3, it can be seen that the gloss printed layer of the printed matter of Examples 1 to 4 and the vapor-deposited film of the printed matter of Comparative Example 2 can confirm that Ra is equivalent. From this, it can be seen that the glossy printed layers of Examples 1 to 4 have the same smoothness as the metal vapor-deposited film. [Industrial Utilization Possibility]

The printed matter and container of the present invention do not use metal vapor deposition methods, and are useful for imparting high metallic luster.

1: Substrate 2: Hard coating 3: Glossy printing layer 31: Metal scales are biased towards the existing area 4: Pattern layer 5: Surface protection layer 10: Printed matter

Figure 1 is a cross-sectional view showing an embodiment of the printed matter of the present invention. Figure 2 is a cross-sectional view showing another embodiment of the printed matter of the present invention.

Claims (14)

A printed matter, which is formed by sequentially having a hard coating layer and a glossy printing layer on any part of a substrate, the glossy printing layer is formed in a pattern, and the entire surface of the substrate side of the glossy printing layer is connected to Is formed on the hard coat layer, the hard coat layer is disposed on the substrate at a position corresponding to at least the area where the glossy printing layer is formed, the glossy printing layer includes metal flakes, and the metal flakes are biased to exist. On the upper part of the glossy printing layer, and the metal flakes meet the following conditions (1) and/or (2); the average thickness of the metal flakes is 0.01~0.08μm (1) 10≦the average length of the metal flakes/the glossy printing layer The thickness (2). Such as the printed matter of claim 1, wherein the average length and average thickness of the metal flakes satisfy the following condition (3); the average thickness of the metal flakes/the average length of the metal flakes≦0.010 (3). Such as the printed matter of claim 1 or 2, wherein the average length of the metal flakes is 5.0~30.0μm. Such as the printed matter of claim 1 or 2, wherein the thickness of the glossy printed layer is 0.15-1.50 μm. Such as the printed matter of claim 1 or 2, which is formed by patterning the glossy printing layer. The printed matter of claim 1 or 2, wherein the hard coat layer is a cured layer of an ionizing radiation curable resin composition. The printed matter of claim 1 or 2, wherein the substrate is a paper substrate. For example, the printed matter of claim 1 or 2 is formed by having a pattern layer on the glossy printing layer. For example, the printed matter of claim 1 or 2 is formed by having a pattern layer on the gloss printing layer and/or any part of the hard coat layer where the gloss printing layer is not formed. Such as the printed matter of claim 1 or 2, which has a surface protection layer on the outermost surface of the side with the glossy printed layer. A printed matter, which is formed by sequentially having a hard coating layer and a glossy printing layer on any part of a substrate, the glossy printing layer is formed in a pattern, and the entire surface of the substrate side of the glossy printing layer is connected to Is formed on the hard coat layer, the hard coat layer is disposed on the substrate at a position corresponding to at least the area where the glossy printing layer is formed, the glossy printing layer includes metal flakes, and the metal flakes satisfy the following Conditions (1) and/or (2), the surface of the hard coating has a JIS Z8741: 1997 60 degree mirror gloss of 85% or more; the average thickness of the metal flakes is 0.01~0.08μm (1) 10≦ Average length of metal flakes/thickness of glossy printed layer (2). A printed matter, which is formed by sequentially having a hard coating layer and a glossy printing layer on any part of a substrate, the glossy printing layer is formed in a pattern, and the entire surface of the substrate side of the glossy printing layer is connected to Is formed on the hard coat layer, the hard coat layer is disposed on the substrate at a position corresponding to at least the area where the glossy printing layer is formed, the glossy printing layer includes metal flakes, and the metal flakes satisfy the following Conditions (1) and/or (2), the surface roughness PPS of the hard coat layer of JIS P8151: 2004 is less than 1μm; the average thickness of the metal flakes is 0.01~0.08μm (1) 10≦the average of the metal flakes Length/thickness of glossy printed layer (2). A printed matter, which is formed by sequentially having a hard coating layer and a glossy printing layer on any part of a substrate, the glossy printing layer is formed in a pattern, and the entire surface of the substrate side of the glossy printing layer is connected to Is formed on the hard coat layer, the hard coat layer is disposed on the substrate at a position corresponding to at least the area where the glossy printing layer is formed, the glossy printing layer includes metal flakes, and the metal flakes satisfy the following Conditions (1) and/or (2), the substrate is a paper substrate, the surface of the glossy printing layer has a JIS Z8741: 1997 specular gloss at 60 degrees of 150% or more; the average thickness of the metal flakes is 0.01 ~0.08μm (1) 10≦average length of metal flakes/thickness of glossy printing layer (2). A container which is formed by using the printed matter of any one of claims 1 to 13.

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