JP6551157B2 - Printed matter, container using the printed matter, method for producing printed matter, and method for selecting printed matter - Google Patents

Description

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

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

  As one means for imparting metallic luster, a film having metallic luster is used. For example, a film having metallic gloss is laminated on a paper substrate to produce a substrate having metallic gloss, and a picture layer or the like is further printed on the substrate to produce a print having metallic gloss.

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.

Unexamined-Japanese-Patent No. 2003-2323

  Patent Document 1 discloses a paper container in which a printed layer having a metallic gloss layer region including a binder resin and a metal thin film strip is formed on a paper base material.

  The paper container of Patent Document 1 has no problem with respect to cost and curl, and has a certain level of metallic luster. However, the paper container of Patent Document 1 has a certain level of metallic luster, but has insufficient glossiness (glossiness).

  An object of this invention is to provide the printed matter and container which give a metallic luster without using the means of metal vapor deposition, and have the outstanding glossiness. In addition, the present invention provides a method for producing or selecting a printed matter that imparts a metallic luster without using metal vapor deposition means and has an excellent gloss feeling.

MEANS TO SOLVE THE PROBLEM In order to solve the said subject, this invention provides the printed material of the following [1]-[15], the container using this printed matter, the manufacturing method of printed matter, and the selection method of printed matter.
[1] A printed matter having a gloss printing layer at an arbitrary position on a substrate and further having a surface protective layer on the outermost surface on the side having the gloss printing layer, the gloss printing layer being a metal The surface protective layer is a cured product layer of an ultraviolet curable resin composition, and visible light was irradiated at an angle of 45 degrees from the normal toward the surface of the printed material on the surface protective layer side. The reflection intensity measured every 0.1 degrees in the range of -45 degrees to +45 degrees with respect to the regular reflection direction at the time of at least a part of the surface protection layer immediately above where the gloss print layer is located, Printed material satisfying the condition (1).
6.0 ≦ R _{in ± 2.5} / R _{out ± 2.5} (1)
R _{in ± 2.5} ; Sum of reflection intensities in the range of −2.5 degrees to +2.5 degrees R _{out ± 2.5} ; Reflection intensities in the range of −45 degrees to −2.6 degrees, and +2.6 Of the reflection intensity in the range of 0 degrees to +45 degrees [2]-45 degrees with respect to the regular reflection direction when the visible light is irradiated at an angle of 45 degrees from the normal toward the surface on the surface protective layer side of the printed matter The printed matter according to the above [1], wherein the reflection intensity measured every 0.1 degree in the range of to +45 degrees further satisfies the following condition (2) in at least a part of the surface protective layer.
R ₀ / R _{in ± 45} ≦ 0.040 (2)
R ₀ ; Reflection intensity at 0 degree R _{in ± 45} ; Sum of reflection intensities in the range of −45 degrees to +45 degrees

[3] The printed matter according to [1] or [2], wherein the average length and the average thickness of the metal scale satisfy the following condition (3).
Average thickness of metal scale / average length of metal scale ≦ 0.010 (3)
[4] The printed matter according to any one of the above [1] to [3], wherein the average thickness and length of the metal flakes and the thickness of the gloss print layer satisfy the following condition (4).
10 ≦ [average length of metal scale / thickness of glossy printed layer] (4)
[5] The printed matter according to any one of the above [1] to [4], wherein the average length of the metal flakes is 5.0 to 30.0 μm.
[6] The printed matter according to any one of the above [1] to [5], wherein the average thickness of the metal flakes is 0.10 μm or less.
[7] The printed matter according to any one of the above [1] to [6], wherein the thickness of the gloss print layer is 0.15 to 1.50 μm.
[8] The printed material according to any one of [1] to [7], wherein a pattern is formed by the glossy printed layer.
[9] The printed matter according to any one of the above [1] to [8], which has a hard coat layer between the substrate and the gloss print layer.
[10] The printed material according to [9], wherein the hard coat layer is a cured product layer of an ionizing radiation curable resin composition.
[11] The printed matter according to any one of the above [1] to [10], wherein the substrate is a paper substrate.
[12] The printed matter according to any one of the above [1] to [11], which has a picture layer at an arbitrary position between the substrate and the surface protective layer.
[13] A container using the printed matter according to any one of [1] to [12].

[14] A method for producing a printed matter, wherein a gloss print layer is formed at any position on a substrate, and a surface protective layer is further formed on the outermost surface on the side having the gloss print layer,
By performing the step of forming the glossy printed layer from the ink for the glossy printed layer containing metal scales, and the step of forming the surface protective layer from the ink for the surface protective layer containing the ultraviolet curable resin composition,
Reflection intensity measured at every 0.1 degree in the range of -45 degrees to +45 degrees with respect to the regular reflection direction at the time of irradiating visible light at an angle of 45 degrees from the normal toward the surface on the surface protective layer side However, the method for producing a printed matter is to satisfy the following condition (1) in at least a partial region of the surface protective layer immediately above where the glossy printed layer is located.
6.0 ≦ R _{in ± 2.5} / R _{out ± 2.5} (1)
R _{in ± 2.5} ; Sum of reflection intensities in the range of −2.5 degrees to +2.5 degrees R _{out ± 2.5} ; Reflection intensities in the range of −45 degrees to −2.6 degrees, and +2.6 [15] Sum of reflection intensity in the range of +45 to +45 degrees [15] It has a glossy printed layer containing metal scales at an arbitrary position on the substrate, and further UV curable on the outermost surface on the side having the glossy printed layer When selecting a printed matter having a surface protective layer comprising a cured product layer of a resin composition,
Reflection intensity measured at every 0.1 degree in the range of -45 degrees to +45 degrees with respect to the regular reflection direction at the time of irradiating visible light at an angle of 45 degrees from the normal toward the surface on the surface protective layer side However, the selection method of printed matter which makes the determination conditions satisfy | fill the following conditions (1) in at least one part area | region of the surface protective layer of the just upper part in which a glossy printing layer is located.
6.0 ≦ R _{in ± 2.5} / R _{out ± 2.5} (1)
R _{in ± 2.5} ; sum of reflection intensities in the range of −2.5 degrees to +2.5 degrees R _{out ± 2.5} ; reflection intensities in the range of −45 degrees to −2.6 degrees, and +2.6 Total reflection intensity in the range of +45 degrees to +45 degrees

  The printed matter and container of the present invention have an excellent gloss without using metal vapor deposition means, and are extremely excellent in cost performance. Moreover, according to the printed matter manufacturing method of the present invention, it is possible to easily manufacture a printed matter having excellent gloss and excellent cost performance. Moreover, according to the method of selecting printed matter of the present invention, printed matter having excellent glossiness can be accurately selected.

It is a sectional view showing one embodiment of a printed matter of the present invention. It is sectional drawing which shows other embodiment of the printed matter of this invention. It is a figure which shows intensity distribution of the reflected light of the printed matter of Example 1. FIG. It is a figure which shows intensity distribution of the reflected light of the printed matter of the comparative example 1. FIG. It is a figure which shows intensity distribution of the reflected light of the printed matter of the comparative example 2. It is a figure which shows intensity distribution of the reflected light of the printed matter of the comparative example 3. It is a figure which shows intensity distribution of the reflected light of the printed matter of the comparative example 4. It is a figure which shows intensity distribution of the reflected light of the printed matter of the comparative example 5.

[Printed matter]
The printed matter of the present invention is a printed matter having a glossy printed layer at an arbitrary location on a substrate, and further having a surface protective layer on the outermost surface on the side having the glossy printed layer. The layer includes metal scales, and the surface protective layer is a cured product layer of an ultraviolet curable resin composition, and visible light at an angle of 45 degrees from the normal line toward the surface of the printed material on the surface protective layer side. The reflection intensity measured every 0.1 degree in the range of -45 degrees to +45 degrees with respect to the regular reflection direction at the time of irradiating the at least a partial region of the surface protection layer directly above where the gloss print layer is located The following condition (1) is satisfied.
6.0 ≦ R _{in ± 2.5} / R _{out ± 2.5} (1)
R _{in ± 2.5} ; sum of reflection intensities in the range of −2.5 degrees to +2.5 degrees R _{out ± 2.5} ; reflection intensities in the range of −45 degrees to −2.6 degrees, and +2.6 Sum of reflection intensities in the range of degrees to +45 degrees Hereinafter, embodiments of the printed matter of the present invention will be described.

  FIG.1 and FIG.2 is sectional drawing which shows one Embodiment of the printed matter 10 of this invention. The printed material 10 of FIG. 1 and FIG. 2 has a hard coat layer 2, a gloss printing layer 3 and a surface protective layer 5 in this order on the substrate 1, and the surface protective layer 5 is the outermost surface of the printed material 10. . The printed matter of FIG. 2 further has a picture layer 4 between the gloss print layer 3 and the surface protective layer 5. Moreover, the glossy printed layer 3 of the printed matter 10 in FIGS. 1 and 2 has an upper metal scale unevenly distributed region 31.

Condition (1)
The printed matter of the present invention has a range of -45 to +45 degrees with respect to the regular reflection direction when the visible light is irradiated at an angle of 45 degrees from the normal toward the surface of the printed material on the surface protective layer side. The reflection intensity measured every one degree satisfies the following condition (1) in at least a partial region of the surface protection layer immediately above where the gloss print layer is located.
6.0 ≦ R _{in ± 2.5} / R _{out ± 2.5} (1)
R _{in ± 2.5} ; Sum of reflection intensities in the range of −2.5 degrees to +2.5 degrees R _{out ± 2.5} ; Reflection intensities in the range of −45 degrees to −2.6 degrees, and +2.6 Total reflection intensity in the range of +45 degrees to +45 degrees

R _{in ± 2.5} means the total reflection intensity in the range of −2.5 degrees to +2.5 degrees. Reflected light in the range of −2.5 degrees to +2.5 degrees is reflected light in a range that is difficult for humans to recognize as diffused light and easily recognized as regular reflected light (in the haze of JIS K7136: 2000, −2 degrees). .5 ° to + 2.5 ° rays are defined as parallel rays). That is, a large R _{in ± 2.5} means that the sum of reflection intensities that humans recognize as regular reflection light is large. Hereinafter, the range of −2.5 degrees to +2.5 degrees may be referred to as “regular reflection vicinity”.

At first glance, it is considered that if R _{in ± 2.5} is large, an excellent glossiness can be obtained. Even in the specular glossiness of JIS Z 8741: 1997, which is a representative example of gloss index, the gloss is managed by the intensity of regular reflection light.
However, even if the reflection intensity in the vicinity of the regular reflection direction is high, if the difference between the reflection intensity in the region near the regular reflection direction and the reflection intensity in the peripheral region deviated from the vicinity of the regular reflection direction is small, There is little contrast, and it is difficult for the human eye to recognize that the gloss is excellent. The condition (1) of the present invention is: R _{in ± 2.5} , which is the sum of the reflection intensities from −2.5 degrees to +2.5 degrees (the sum of reflection intensities near the regular reflection direction), −45 degrees to −− R _{out ± 2.5} which is the sum of the reflection intensities in the range of 2.6 degrees and the reflection intensities in the range of +2.6 degrees to +45 degrees (the sum of the reflection intensities in the peripheral region deviated from the vicinity of the regular reflection direction) This increases the correlation with the glossiness of the human eye.

When R _{in ± 2.5} / R _{out ± 2.5} is less than 6.0, the glossiness is insufficient because R _{in ± 2.5} is not sufficiently high compared to R _{out ± 2.5} . In addition, when R _{in ± 2.5} / R _{out ± 2.5} is less than 6.0, it becomes difficult to maintain the metallic gloss imparted by the gloss print layer.
Condition (1) preferably satisfies 6.2 ≦ R _{in ± 2.5} / R _{out ± 2.5, and} can satisfy 6.4 ≦ R _{in ± 2.5} / R _{out ± 2.5} More preferred. The upper limit of R _{in ± 2.5} / R _{out ± 2.5} is preferably 100.0, more preferably 50.0, even more preferably 20.0, and even more preferably 10.0.

Condition (1) only needs to be satisfied in at least a part of the surface protective layer immediately above where the glossy printed layer is located. The portion directly above where the glossy print layer is located is a range indicated by “x” in FIG. That is, in the case of FIG. 1, it is sufficient that at least a part of the range indicated by “x” satisfies the condition (1). Moreover, in order to make the effect of the present invention better, it is preferable to satisfy the condition (1) in all regions of the surface protective layer immediately above where the glossy print layer is located.
When the printed material has a pattern layer between the glossy printed layer and the surface protective layer, the value of condition (1) differs slightly depending on the color of the pattern (more specifically, the type of pigment constituting the pattern), but black It is preferable to satisfy the condition (1) in all color regions except for the above.

Condition (2)
The printed matter of the present invention has a range of -45 to +45 degrees with respect to the regular reflection direction when the visible light is irradiated at an angle of 45 degrees from the normal toward the surface of the printed material on the surface protective layer side. It is preferable that the reflection intensity measured every degree further satisfies the following condition (2) in at least a part of the surface protective layer immediately above where the glossy printed layer is located.
R ₀ / R _{in ± 45} ≦ 0.040 (2)
R ₀ : 0 degree reflection intensity R _{in ± 45} ; sum of reflection intensities in the range of −45 degrees to +45 degrees

The condition (2) means that the reflection intensity at 0 degree (the regular reflection direction) protrudes and is not strong in the range of ± 45 degrees. By satisfying the condition (2), it is possible to suppress the reflection intensity at 0 degrees (the regular reflection direction) from being protruded, and to easily prevent the viewer from feeling discomfort due to the glare. The condition (2) is preferably satisfied in the same region as the region that satisfies the condition (1).
The condition (2) more preferably satisfies R ₀ / R _{in ± 45} ≦ 0.035, and still more preferably satisfies R ₀ / R _{in ± 45} ≦ 0.030. From the viewpoint of easily satisfying the condition (1), the condition (2) is preferably 0.015 or more.

Method for Measuring Reflection Intensity First, visible light (parallel light) is irradiated at an angle of 45 degrees from the normal line toward the surface of the printed matter on the surface protective layer side. Then, regarding the reflected light, the light receiver is scanned at an angle of 0.1 degrees in the range of -45 degrees to +45 degrees with respect to the regular reflection direction, where the regular reflection direction of the irradiation light is 0 degree. Measure intensity (luminosity). At the time of intensity measurement, the brightness of the light source is made constant. When measuring the intensity (luminous intensity), the aperture angle of the light receiver detected by the diaphragm of the light receiver is set to 0.1 degree. Therefore, for example, in the measurement of 0 degree (regular reflection), the range of ± 0.05 degree is measured, and in the measurement of 1 degree, the range of 0.95 degree to 1.05 degree is measured, and the measurement of -1 degree In this case, a range of -0.95 degrees to -1.05 degrees is to be measured. In addition, about -45 degrees, it becomes a measurement of the range of -44.95 degrees--45.00 degrees, and although a measurement range becomes narrower by 0.05 degree than other angles, it is a large diffusion to reach -45 degrees There is no influence on the condition (1), since
There is no restriction | limiting in particular about the apparatus which measures intensity | strength, A general purpose goniophotometer (goniophotometer) can be used. In the present invention, as a variable angle photometer, trade name GP-200 (Luminous flux diameter: about 10.5 mm, inclination angle within luminous flux: within 0.29 degree) manufactured by Murakami Color Research Laboratory Ltd. was used.
3-8 is a figure which shows distribution of the reflection intensity of the printed matter of Example 1 and Comparative Examples 1-5.

The material of the base material is not particularly limited as long as it is a material conventionally used for printed matter, etc., and specifically, fine paper, medium paper, coated paper, synthetic paper, impregnated paper, laminated paper Papers such as coated papers for printing and coated papers for recording, plastic films such as polyethylene terephthalate film, polyethylene film, polypropylene film and polycarbonate film, or composites thereof are used.

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

It is preferable to have a hard coat layer between the hard coat layer substrate and the gloss print layer. By interposing the hard coat layer between the substrate and the gloss print layer, the metallic gloss of the gloss print layer can be easily improved. The reason is considered as follows. In addition, making metal glossiness of a gloss printing layer leads to making metal glossiness of the printed matter of this invention good.
First, the hard coat layer is difficult to permeate the solvent for the gloss printing layer ink. For this reason, when apply | coating and drying the ink for gloss printing layers on a hard-coat layer, a solvent does not easily flow below the gloss printing layer. On the other hand, the solvent tends to flow above the gloss print layer when the solvent evaporates in the drying process. And it is thought that a metal scale floats above a glossy printing layer with the flow of a solvent, metal scales are unevenly distributed on the glossy printing layer, and the glossiness of the glossy printing layer can be improved.
Moreover, although the base material mentioned above has the difference in a grade according to a kind, the surface is rough. For example, paper has a rough surface due to fibers. When a gloss print layer is formed on a substrate having a rough surface as described above, the surface of the gloss print layer is also rough and the metallic gloss can not be improved, but the hard coat layer reduces the roughness of the substrate surface. It is thought that the metallic gloss can be improved by suppressing the surface roughness of the gloss print layer.
In addition, when the surface of the substrate is scratched, the unevenness of the scratch is reflected on the surface of the gloss print layer, thereby reducing the metallic gloss of the gloss print layer. However, since the base composed of the substrate and the hard coat layer is not easily scratched, it is considered that the reflection of the unevenness due to the scratch is suppressed on the surface of the gloss printing layer, and the metallic gloss of the gloss printing layer can be made good.

  The hard coat layer is preferably formed at a location corresponding to a location where a glossy print layer described later is formed. In addition, from the viewpoint of eliminating the complexity of the alignment between the hard coat layer and the gloss print layer, the hard coat layer is preferably provided on the entire surface of the area of the substrate on which the gloss print layer is to be formed. Moreover, it is preferable to form a hard-coat layer on the whole surface of a base material from a viewpoint which makes the physical property of the base | substrate which consists of a base material and a hard-coat layer uniform, and suppresses a deformation | transformation etc. of a base | substrate.

  It is preferable that the surface of the hard coat layer (the surface of the hard coat layer opposite to the substrate) is smoothed. When the surface of the hard coat layer is rough, the surface area of the hard coat layer increases, and the solvent easily penetrates when forming the glossy print layer. On the other hand, when the surface of the hard coat layer is smoothed, the solvent does not easily penetrate into the hard coat layer. it can. Further, when the surface of the hard coat layer is rough, the unevenness of the hard coat layer is reflected in the glossy print layer, and the surface of the gloss print layer is also roughened. On the other hand, when the surface of the hard coat layer is smoothed, the surface of the glossy printed layer is also smoothed, and the metallic gloss of the glossy printed layer can be improved.

As a parameter | index of smoothing of the surface of a hard-coat layer, the specular glossiness of JISZ8741: 1997 and arithmetic mean roughness Ra of JISB0601: 2001 are mentioned.
The specular gloss at 60 degrees of JIS Z8741: 1997 on the hard coat layer surface is preferably 85% or more, and more preferably 90% or more.

Further, the arithmetic average roughness Ra (Ra _0.08HA ) of JIS B0601: 2001 on the hard coat layer surface when the cut-off value is 0.08 mm is preferably 0.080 μm or less, and 0.060 μm or less. And more preferably 0.040 μm or less.
The cut-off value indicates the fineness of the filter that removes the waviness component (low frequency component) from the cross-sectional curve. More specifically, the cross-sectional curve can be divided into a swell component (low frequency component) and a roughness component (high frequency component). The smaller the cutoff value (the finer the filter), the lower the frequency component is removed. As a result, the ratio of high frequency components increases. For this reason, Ra _{0.08 HA} indicates the unevenness of the high frequency component of the hard coat layer, and Ra _{0.8 HA} described later indicates the unevenness of the low frequency component of the hard coat layer.
When the hard coat layer contains many irregularities of high frequency components, the surface area of the hard coat layer is expanded and the solvent is easily penetrated, so that the metal flakes of the gloss print layer are difficult to be unevenly distributed on the top, and the metal gloss is impaired. _Therefore , it is preferable to make Ra _{0.08 HA} into the above range.

Further, the arithmetic average roughness Ra (Ra _0.8HA ) of JIS B0601: 2001 on the surface of the hard coat layer when the cut-off value is 0.8 mm is preferably 0.400 μm or less, and 0.370 μm or less. More preferably, it is 0.350 μm or less.
Although the unevenness of the low frequency component is not as large as the unevenness of the high frequency component, the surface area of the hard coat layer is expanded. Therefore, it is preferable to set Ra _{0.8 HA} to the above range. In addition, when the unevenness of the low frequency component of the hard coat layer disappears, the unevenness due to the unevenness of the low frequency component of the hard coat layer can not be formed on the surface of the gloss print layer, and the gloss print layer is excessively smoothed. There is a tendency. In this case, the surface protective layer on the outermost surface is also excessively smoothed, and the reflected light in the regular reflection direction of the surface protective layer may be too strong, which may cause a sense of discomfort to the viewer. For this reason, Ra _0.8HA is preferably 0.100 μm or more, and more preferably 0.200 μm or more.

Furthermore, the arithmetic mean roughness Ra (Ra _{0.08 BA} ) of the substrate surface when the cutoff value is 0.08 mm, and the JIS when the cutoff value is 0.8 mm. The arithmetic mean roughness Ra (Ra _{0.8 BA} ) of B0601: 2001, the above Ra _{0.08 HA} , and the Ra _{0.8 HA} preferably satisfy the following condition (a).
[Ra _0.8HA / Ra _0.8BA ]> [Ra _0.08HA / Ra _0.08BA ] (a)
The ratio of Ra of the hard coat layer and Ra of the base material indicates the degree to which the hard coat layer relaxes the unevenness of the base material. The above condition (a) indicates that the degree of relaxation of the high frequency component is larger than the degree of relaxation of the low frequency component of the unevenness of the substrate by the hard coat layer.
As described above, increasing the surface area of the hard coat layer is greatly affected by the unevenness of the high-frequency component. For this reason, it is preferable that the hard coat layer relieves the unevenness of the high frequency component of the substrate. On the other hand, if the unevenness of the low frequency component of the base material is excessively relaxed, the texture of the base material is impaired, and the reflected light in the regular reflection direction of the glossy printed layer may become too strong. Therefore, it is very significant to satisfy the above-mentioned condition (a) which indicates that the degree of relaxation of the high frequency component is larger than the degree of relaxation of the low frequency component of the unevenness of the substrate.

In order to more easily exhibit the above effects, it is preferable that the above Ra _{0.08 HA} , Ra _{0.8 HA} , Ra _{0.08 BA} , and Ra _{0.8 BA} satisfy the following condition (b).
1.8 ≦ [Ra _{0.8 HA} / Ra _{0.8 BA} ] / [Ra _{0.08 HA} / Ra _{0.08 BA} ] (b)
The condition (b) more preferably satisfies 2.2 ≦ [Ra _0.8HA / Ra _0.8BA ] / [Ra _0.08HA / Ra _0.08BA ] ≦ 4.0, and 2.5 ≦ [Ra it is further preferred to satisfy the _{0.8HA / Ra 0.8BA] / [Ra} 0.08HA / Ra 0.08BA] ≦ 3.5.

Specific examples of the hard coat layer include a cured product layer of an ionizing radiation curable resin composition (hereinafter sometimes referred to as “cured product layer”), a clay coat layer, and the like. It is preferable that it is a hardened | cured material layer of an ionizing radiation curable resin composition from a viewpoint of making permeation prevention property better.
Furthermore, when the hard coat layer is formed of an ionizing radiation curable resin composition, the hard coat layer can be instantaneously cured by irradiation with ionizing radiation, so the surface shape of the hard coat layer is formed in the process of forming the hard coat layer. Can be prevented from being followed by the unevenness of the high frequency component of the base material. In other words, when the hard coat layer is formed from the ionizing radiation curable resin composition, the unevenness of the high-frequency component of the substrate can be alleviated by the hard coat layer. On the other hand, until the hard coat layer is cured (during the drying process), the surface shape of the hard coat layer appropriately follows the irregularities of the low frequency component of the substrate. That is, when the hard coat layer is formed of the ionizing radiation curable resin composition, the surface of the hard coat layer can be formed into a shape having appropriate low frequency component unevenness while suppressing the unevenness of the high frequency component, The effects described above (suppression of the penetration of the solvent into the hard coat layer, maintenance of the feel of the substrate, etc.) can be easily exhibited.

The ionizing radiation curable resin composition for forming a cured product layer cured product 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 bond groups such as (meth) acryloyl group, vinyl group and allyl group, and epoxy group and oxetanyl group. As the ionizing radiation curable compound (in the case of ultraviolet curing, sometimes referred to as “ultraviolet curable compound”), a compound having an ethylenically unsaturated bond group is preferable, and has two or more ethylenically unsaturated bond groups. The compounds are more preferable, and among them, polyfunctional (meth) acrylate compounds having two or more ethylenically unsaturated bonding groups are more preferable. As the polyfunctional (meth) acrylate-based compound, any of a monomer and an oligomer can be used. However, a monomer is preferable from the viewpoint of improving scratch resistance and penetration resistance due to high crosslinking density.
Note that ionizing radiation means any of electromagnetic waves or charged particle beams that have an energy quantum capable of polymerizing or crosslinking molecules, and usually, ultraviolet light (UV) or electron beam (EB) is used, and others, Electromagnetic waves such as X-rays and γ-rays, and charged particle beams such as α-rays and ion beams can also be used.

Among the polyfunctional (meth) acrylate monomers, as a bifunctional (meth) acrylate monomer, ethylene glycol di (meth) acrylate, bisphenol A tetraethoxy diacrylate, bisphenol A tetrapropoxy diacrylate, 1,6-hexanediol Diacrylate etc. are mentioned.
Examples of the tri- or higher functional (meth) acrylate monomer include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, di Examples include pentaerythritol tetra (meth) acrylate and isocyanuric acid-modified tri (meth) acrylate.
Further, the (meth) acrylate monomer may be one in which a part of the molecular skeleton is modified, and is modified by ethylene oxide, propylene oxide, caprolactone, isocyanuric acid, alkyl, cyclic alkyl, aromatic, bisphenol or the like. Can also be used.
2-6 are preferable and, as for the number of functional groups of a polyfunctional (meth) acrylate monomer, 2-3 are more preferable.

Moreover, examples of the polyfunctional (meth) acrylate oligomer include acrylate polymers such as urethane (meth) acrylate, epoxy (meth) acrylate, polyester (meth) acrylate, and polyether (meth) acrylate.
Urethane (meth) acrylates are obtained, for example, by the reaction of polyhydric alcohols and organic diisocyanates with hydroxy (meth) acrylates.
Preferred epoxy (meth) acrylates are (meth) acrylates obtained by reacting trifunctional or higher functional aromatic epoxy resins, alicyclic epoxy resins, aliphatic epoxy resins, etc. with (meth) acrylic acid, and bifunctional (Meth) acrylates obtained by reacting the above aromatic epoxy resins, alicyclic epoxy resins, aliphatic epoxy resins and the like with polybasic acids and (meth) acrylic acid, and bifunctional or higher functional aromatic epoxy resins, (Meth) acrylates obtained by reacting an alicyclic epoxy resin, an aliphatic epoxy resin or the like, a phenol and (meth) acrylic acid.
The ionizing radiation curable compounds can be used alone or in combination of two or more. The ionizing radiation curable compound preferably contains 50% by mass or more, more preferably 80% by mass or more of a polyfunctional (meth) acrylate monomer.

When the ionizing radiation curable compound is an ultraviolet curable compound, the ionizing radiation curable composition (ultraviolet curable resin composition) preferably contains additives such as a photopolymerization initiator and a photopolymerization accelerator. .
Examples of the photopolymerization initiator include one or more selected from acetophenone, benzophenone, α-hydroxyalkylphenone, Michler's ketone, benzoin, benzylmethyl ketal, benzoylbenzoate, α-acyloxime ester, thioxanthones, and the like.
The photopolymerization accelerator can reduce polymerization inhibition by air during curing and increase the curing speed. For example, p-dimethylaminobenzoic acid isoamyl ester, p-dimethylaminobenzoic acid ethyl ester, etc. One or more selected may be mentioned.
The ionizing radiation curable resin composition may contain additives such as a light stabilizer, an antioxidant, and a leveling agent.
The ionizing radiation curable resin composition may contain a resin component other than the ionizing radiation curable compound (thermoplastic resin or thermosetting resin). However, in order to easily achieve the effect described above, the proportion of the ionizing radiation curable compound in the total resin components of the ionizing radiation curable resin composition is preferably 90% by mass or more, and 95% by mass or more. Is more preferable, and 100% by mass is more preferable.

  The cured product layer preferably has a thickness of 2 μm or more from the viewpoint of smoothing and scratching of the substrate. The thickness of the cured product layer is more preferably 3 to 20 μm, further preferably 4 to 10 μm, and 5 to 7 μm, because the processability is reduced when the thickness of the cured product layer is too large. Is even more preferred.

  The cured product layer can be formed by applying, on a substrate, an ink for a cured product layer containing an ionizing radiation curable resin composition and a solvent to be added as needed, drying, and ionizing radiation irradiation. In addition, drying is unnecessary when the solvent is not contained in the ink for cured | curing material layers.

Clay Coat Layer The clay layer contains clay, a binder resin and the like.
Any clay can be used without particular limitation as long as it is generally called clay or clay. Furthermore, kaolin, talc, bentonite, smectite, vermiculite, mica, chlorite, kibushi clay, gyrome clay , Halloysite and the like can be used.

  The clay coat layer preferably contains pigments such as calcium carbonate, titanium dioxide, amorphous silica, expandable barium sulfate, and satin white in addition to clay. By using calcium carbonate or titanium dioxide as the pigment, the surface smoothness of the clay coat layer can be easily improved. Furthermore, calcium carbonate is preferably used because it is inexpensive.

  The binder resin may, for example, be a latex binder resin (for example, styrene butadiene latex, acrylic latex vinyl acetate latex), or a water soluble binder resin (for example, starch (modified starch, oxidized starch, hydroxyethyl etherified starch, phosphoric acid) Esterified starch), polyvinyl alcohol, casein and the like.

The mass ratio of clay: pigment: binder resin in the clay coat layer is preferably 1 to 20: 50 to 90: 10 to 30.
The clay coat layer may contain additives such as pigment dispersants, antifoaming agents, antifoaming agents, viscosity modifiers, lubricants, water resistance agents, water retention agents, colorants, and printability improvers. Good.

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

  The clay coat layer can be formed by applying and drying a clay coat layer ink obtained by diluting a material constituting the clay coat layer in a solvent on a substrate.

Glossy Print Layer The glossy print layer is a layer located on the substrate or the hard coat layer, and is formed by printing a glossy print layer ink. By forming the layer providing gloss as described above by printing instead of vapor deposition, it is possible to reduce the cost and to suppress the occurrence of curling. The gloss print layer is preferably formed on the hard coat layer, and more preferably in contact with the hard coat layer, from the viewpoint of uneven distribution of the metal flakes.
Further, as shown in FIG. 1, the glossy printed layer is formed in a desired pattern in a partial area on the base material or the hard coat layer, and letters, numbers, figures, symbols, landscapes, people, animals, characters, etc. The pattern may be formed on the entire surface of the substrate or the hard coat layer as shown in FIG.

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

  Moreover, it is preferable that the metal scale is unevenly distributed on the upper part of the glossy printed layer (on the side opposite to the hard coat layer of the glossy printed layer). By unevenly distributing the metal flakes to the upper part of the gloss print layer, it is possible to improve the metallic gloss and to improve the adhesion between the gloss print layer and the substrate or the hard coat layer.

  The metal scales can be unevenly distributed on the glossy printed layer in the process of forming the glossy printed layer. More specifically, when the solvent for the glossy printing layer ink volatilizes during the heat drying process of the glossy printing layer, the solvent flows upward. And it is thought that a metal scale floats with the flow of a solvent, and a metal scale is unevenly distributed in the upper part of a glossy printed layer. In particular, by positioning a hard coat layer in which the solvent does not easily penetrate into the lower layer of the glossy printed layer, the solvent can be prevented from flowing downward and the solvent flows almost upward. Can be easily distributed. Further, when the hard coat layer is a cured product layer of the ionizing radiation curable resin composition, it is considered that the uneven distribution of the metal scales can be made more remarkable.

The degree of uneven distribution of the metal scales can be confirmed by imaging the cross section of the printed matter with an electron microscope and checking the density difference in the glossy printed layer of the photographed image. More specifically, the uneven distribution of metal flakes is observed white because the reflection of electrons is remarkable, and the region substantially free of metal flakes is observed in gray.
The ratio of the thickness of the unevenly distributed area of the metal scale in the glossy printed layer [(the thickness of the unevenly distributed area of the metal scale / total thickness of the glossy printed layer)] is 10 to 60% from the viewpoint of the balance between the metallic gloss and the adhesiveness. It is preferably 20 to 50%, more preferably 25 to 45%.

It is preferable that the metal flakes satisfy the following condition (3).
Average thickness of metal scale / average length of metal scale ≦ 0.010 (3)
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 effect due to the metal flakes tilting increases with the increase of the content of the metal flakes, but if the above condition (3) is satisfied, the metal flakes are difficult to tilt, so the content of the metal flakes is increased It is easy to improve the metallic luster.
In addition, when the average thickness of a metal scale piece becomes thin with respect to the average length of a metal scale piece, handling property may become difficult or sufficient metallic gloss may not be expressed.
For this reason, it is preferable that the condition (3) 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 | fill thickness <= 0.008, and it is still more preferable to satisfy | fill 0.002 <= average thickness of a metal scale / average length of a metal scale <= 0.005.

In addition, at the time of applying the ink for the glossy printed layer, from the viewpoint of suppressing the metal scale from tilting with respect to the horizontal direction of the glossy printed layer, and suppressing the metal scale from protruding from the surface of the glossy printed layer. The average length of the metal scales and the thickness of the glossy printed layer preferably satisfy the following condition (4).
10 ≦ average length of metal flakes / thickness of glossy print layer (4)
Note that 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. Therefore, condition (4) is 12 ≦ average of metal scale. More preferably, the length / gloss print layer thickness ≦ 60 is satisfied, and 14 ≦ the average length of the metal flakes / gloss print layer thickness ≦ 50.

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

The average length of the metal flakes is preferably 5.0 to 30.0 μm, and more preferably 8.0 to 20.0 μm from the viewpoint of dispersion suitability, uneven distribution, and arrangement of the metal flakes.
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 piece can be measured by using a laser interference type three-dimensional shape analysis apparatus in a state where the metal scale pieces are 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 largest diameter at the time of observing each metal scale piece from an arbitrary direction in a plane is the main point which unifies the direction which measures the largest diameter of each metal scale piece. For example, when the X-axis direction on the screen on which the measurement result of the three-dimensional shape analysis apparatus is image-processed is taken as an arbitrary direction (measurement direction), the maximum diameter is measured in the 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 gloss print layer preferably further contains a binder resin.
Examples of the binder resin include thermoplastic resins such as polyester resin, urethane resin, epoxy resin, melamine resin, alkyd resin, phenol resin, acrylic resin and cellulose resin, and thermosetting resin. Moreover, you may use the hardened | cured material of the ultraviolet curable resin composition mentioned above as binder resin.

  The compounding ratio of the binder resin to the metal flakes is preferably 55:45 to 30:70 in solid content mass ratio, and more preferably 50:50 to 35:65. By setting the metal flakes to 45 or more with respect to the binder resin 55, sufficient metallic gloss can be easily obtained, and by setting the metal flakes to 70 or less with respect to the binder resin 30, the printability of the gloss print layer, the printed matter The processability can be easily improved. In addition, in this invention, since it has a hard-coat layer under a glossy printing layer, even if it uses a lot of metal scales as mentioned above, a metal scale can be unevenly distributed on the upper part of a glossy print layer.

The thickness of the gloss print layer is preferably 0.15 to 1.50 μm, and more preferably 0.20 to 1.00 μm from the viewpoint of uneven distribution and arrangement of metal flakes and the viewpoint of concealability. And 0.25 to 0.75 μm.
In addition, the thickness of the glossy printed layer is measured at, for example, 20 thicknesses from a cross-sectional image taken using a scanning electron microscope (SEM), a transmission electron microscope (TEM), or a scanning transmission electron microscope (STEM). And it can calculate from the average value of the value of 20 places. When the film thickness to be measured is on the order of μm, it is preferable to use SEM, and in the case of nm order, it is preferable to use TEM or STEM. In the case of SEM, the acceleration voltage is preferably 1 kv to 10 kV and the magnification 1000 to 7000 times, and in the case of TEM or STEM, the acceleration voltage is preferably 10 kv to 30 kV and the magnification 50,000 to 300,000 times.
The thickness of layers other than the gloss print layer can also be measured by the same method as described above.

  The gloss print layer may contain a coloring agent such as titanium oxide, zinc flower, carbon black, iron oxide, iron yellow, ultramarine blue, metallic pigment, pearl pigment, etc. in order to make the gloss print layer have a desired color. .

The gloss print layer is 0.1 degree in the range of -45 degrees to +45 degrees with respect to the regular reflection direction when irradiated with visible light at an angle of 45 degrees from the normal line of the gloss print layer toward the gloss print layer. It is preferable that the reflection intensity measured for each satisfies the following condition (5).
3.0 ≦ GR _{in ± 2.5} / GR _{out ± 2.5} (5)
GR _{in ± 2.5} ; sum of reflection intensity of gloss printing layer in the range of −2.5 ° to + 2.5 ° GR _{out ± 2.5} ; gloss printing layer in the range of −45 ° to −2.6 ° Sum of reflection intensity of light and glossy printing layer in the range of +2.6 degrees to +45 degrees

By satisfying the condition (5), the condition (1) described above can be easily satisfied.
The condition (5) more preferably satisfies 3.0 ≦ GR _{in ± 2.5} / GR _{out ± 2.5} ≦ 6.0, and 3.2 ≦ GR _{in ± 2.5} / GR _{out ± 2.} More preferably, ₅ ≦ 5.0 is satisfied.

The gloss print layer is 0.1 degree in the range of -45 degrees to +45 degrees with respect to the regular reflection direction when irradiated with visible light at an angle of 45 degrees from the normal line of the gloss print layer toward the gloss print layer. It is preferable that the reflection intensity measured for each satisfies the following condition (6).
GR ₀ / GR _{in ± 45} ≦ 0.030 (6)
GR ₀ ; Reflection intensity of gloss print layer at 0 degree GR _{in ± 45} ; Sum of reflection intensities of gloss print layer in the range of −45 degrees to +45 degrees

By satisfying the condition (6), the above-described condition (2) can be easily satisfied.
Condition (6) more preferably satisfies 0.010 ≦ R ₀ / R _{in ± 45} ≦ 0.030, and further satisfies 0.015 ≦ R ₀ / R _{in ± 2.5} ≦ 0.027 preferable.

  The specular glossiness at 60 degrees of JIS Z8741: 1997 of the surface of the gloss print layer is preferably 150% or more, more preferably 200% or more, and still more preferably 250% or more. The upper limit of the specular gloss on the surface of the glossy printed layer is about 500%. By setting the specular glossiness of the gloss print layer in the above range, the metal gloss of the gloss print layer can be improved, and thus the metal gloss of the printed matter can be improved.

  The glossy printed layer preferably has a predetermined surface shape in order to easily satisfy the condition (5), the condition (6) and the above-described specular gloss.

The surface of the glossy printed layer preferably has an arithmetic average roughness Ra (Ra _0.08GL ) of JIS B0601: 2001 when the cut-off value is 0.08 mm is 0.100 μm or less. From the viewpoint of suppressing the reflection in the regular reflection direction to improve the visibility, it is preferable that Ra _0.08GL is not too small. _{Therefore, Ra 0.08GL} is more preferably 0.010μm ≦ _{Ra 0.08GL} ≦ 0.070μm, more preferably from 0.020μm ≦ _{Ra 0.08GL} ≦ 0.050μm.

The surface of the glossy printed layer preferably has an arithmetic average roughness Ra (Ra _0.8GL ) of JIS B0601: 2001 of _0.500 μm or less when the cut-off value is 0.8 mm, and is 0.450 μm or less. More preferably, it is more preferably 0.400 μm or less. The lower limit of Ra _{0.08GL on} the surface of the glossy printed layer is about 0.250 μm.

The gloss printing layer can be formed by applying a gloss printing layer ink obtained by diluting a component forming the gloss printing layer with a solvent, drying the ink on the hard coat layer, and irradiating with ultraviolet rays as necessary.
The gloss printing layer ink preferably contains 600 to 1,100 parts by mass of a solvent with respect to 100 parts by mass of the total solid content, from the viewpoint of coexistence of uneven distribution of metal flakes and drying efficiency.
Since the permeability of the solvent varies depending on the resin composition of the hard coat layer, suitable types of solvents cannot be generally specified. For example, ethyl acetate, isopropyl alcohol (IPA), ethanol, normal propyl acetate (NPAC), and these A mixture or the like can be used.

Picture layer It is preferable that the printed matter of the present invention has a picture layer at an arbitrary position between the base and the surface protective layer for the purpose of enhancing the design of the printed matter. For example, the pattern layer can be formed at any location on the glossy printed layer and / or on the substrate where the glossy printed layer is not formed.
The pattern layer is formed by printing or the like. The pattern layer can be formed by multicolor printing with normal yellow, red, blue, and black process colors, or can be formed by multicolor printing with special colors prepared by preparing individual color plates constituting the pattern. . The pattern of the pattern layer can be used without any particular limitation as long as it is a pattern used in normal printing (for example, letters, numbers, figures, symbols, landscapes, people, animals, characters, etc.).

As the ink used for forming the pattern layer, an ink obtained by appropriately mixing a binder resin with a colorant such as a pigment or dye, an extender pigment, a solvent, a stabilizer, a plasticizer, a catalyst, or a curing agent is used.
The binder resin is not particularly limited, and, for example, acrylic resin, styrene resin, polyester resin, urethane resin, chlorinated polyolefin resin, vinyl chloride-vinyl acetate copolymer resin, polyvinyl butyral resin, alkyd resin And petroleum resins, ketone resins, epoxy resins, melamine resins, fluorine resins, silicone resins, cellulose 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.

The pattern layer has a reflection intensity measured at every 0.1 degrees in the range of -45 degrees to +45 degrees with respect to the regular reflection direction when irradiated with visible light at an angle of 45 degrees from the normal of the pattern layer. It is preferable to satisfy the condition (7).
3.5 ≦ DR _{in ± 2.5} / DR _{out ± 2.5} (7)
DR _{in ± 2.5} ; Sum of reflection intensity of the pattern layer in the range of −2.5 degrees to +2.5 degrees DR _{out ± 2.5} ; reflection of the pattern layer in the range of −45 degrees to −2.6 degrees Sum of intensity and reflection intensity of pattern layer in the range of +2.6 degrees to +45 degrees

By satisfying the condition (7), the condition (1) described above can be easily satisfied.
Condition (7) more preferably satisfies 4.0 ≦ DR _{in ± 2.5} / DR _{out ± 2.5} ≦ 6.0.
Further, DR _{in ± 2.5} / DR _{out ± 2.5} is preferably larger than GR _{in ± 2.5} / GR _{out ± 2.5} .

Surface protective layer The printed matter of the present invention has a surface protective layer on the outermost surface on the side having the glossy printed layer. By forming the surface protective layer on the outermost surface, it is possible to improve the abrasion resistance and the weather resistance of the printed matter. For the effect, the surface protective layer is preferably formed to cover the entire area of the gloss print layer and the image layer provided as needed. Moreover, when it has a hard-coat layer, it is more preferable to form a surface protective layer so that the whole area | region of a hard-coat layer may be covered further.

Further, in the present invention, the surface protective layer is a cured product layer of the ultraviolet curable resin composition.
When the surface protective layer is formed from an ultraviolet curable resin composition, the surface protective layer can be instantaneously cured by irradiation with ultraviolet rays. Therefore, in the process of forming the surface protective layer, the surface shape of the surface protective layer is lower (for example, It is possible to suppress following the unevenness of the high frequency component of the glossy printed layer or the like. For this reason, the surface protective layer can reduce the unevenness of the high-frequency component as much as possible, it becomes easy to satisfy the condition (1) described above, the glossiness can be improved, and the metallic gloss of the glossy printed layer can be maintained. On the other hand, until the ultraviolet curable resin composition is irradiated with ultraviolet rays (until the curing of the ultraviolet curable resin composition starts), the surface shape of the surface protective layer is the lower layer (for example, glossy printing layer). Appropriately follows the irregularities of the low-frequency component. For this reason, although a small amount of low frequency component unevenness is maintained in the surface protective layer, the surface of the surface protective layer is excessively smoothed, so that the reflected light in the regular reflection direction becomes too high. It can suppress giving a viewer a discomfort. In addition, in order to make it easier to achieve the said effect, it is preferable that an ultraviolet curable resin composition does not contain a solvent.

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

  From the viewpoint of easily satisfying the above condition (1), it is preferable that the surface protective layer does not substantially contain particles. Having substantially no 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 preferably has a predetermined surface shape in order to easily satisfy the conditions (1) and (2).

The surface of the surface protective layer preferably has an arithmetic average roughness Ra (Ra _0.08SA ) of JIS B0601: 2001 at a cutoff value of 0.08 mm of 0.100 μm or less, and 0.050 μm or less. More preferably, it is 0.030 μm or less. The lower limit of Ra _{0.08SA on} the surface of the surface protective layer is about 0.010 μm.

The surface of the surface protective layer preferably has an arithmetic average roughness Ra (Ra _0.8SA ) of JIS B0601: 2001 at a cutoff value of 0.8 mm of 0.500 μm or less, and 0.450 μm or less. More preferably, it is 0.350 μm or less. The lower limit of Ra _{0.8SA on} the surface of the surface protective layer is about 0.200 μm.
Furthermore, the surface of the surface protective layer preferably satisfies 0.050 <Ra _0.08SA / Ra _0.8SA <0.150, and satisfies 0.060 <Ra _0.08SA / Ra _0.8SA <0.130. _Are more preferable, and it is more preferable to satisfy 0.070 <Ra _0.08SA / Ra _0.8SA <0.100.

The surface of the surface protective layer preferably has a maximum valley depth Rv (Rv _0.08SA ) of JIS B0601: 2001 at a cutoff value of 0.08 mm of 0.200 μm or less. More preferably, it is 150 μm, and further preferably 0.030 to 0.075 μm.

The surface of the surface protective layer preferably has a maximum valley depth Rv (Rv _0.8SA ) of JIS B0601: 2001 of _1.000 μm or less when the cut-off value is 0.8 mm, and 0.900 μm or less. More preferably, it is 0.800 μm or less. The lower limit of Rv _{0.8SA on} the surface of the surface protective layer is about 0.500 μm.
Furthermore, the surface of the surface protective layer preferably satisfies 0.030 <Rv _0.08SA / Rv _0.8SA <0.200, and satisfies 0.040 <Rv _0.08SA / Rv _0.8SA <0.150. _Are more preferable, and it is more preferable to satisfy 0.050 <Rv _0.08SA / Rv _0.8SA <0.100.

The surface shape of the surface protective layer such as Ra _0.08SA , Ra _0.8SA , Rv _0.08SA and Rv _0.8SA is within the above range in at least a part of the surface protective layer immediately above where the glossy printed layer is located. Is preferable, and it is more preferable that the above range is satisfied in all regions.

  The surface protective layer can be formed by applying, on a substrate, an ink for a surface protective layer containing an ultraviolet curable resin composition and a solvent added as needed, drying, and ionizing radiation. In addition, when a solvent is not contained in the ink for surface protective layers, drying is unnecessary.

[container]
The container of the present invention is formed using the above-described printed material of the present invention.
Examples of the container include, but are not limited to, a beverage container and a food container. The container of the present invention has an excellent gloss and is excellent in design. Further, since the curling of the printed matter is suppressed, it is possible to prevent the occurrence of a trouble caused by the curling in the process of manufacturing the container.

[Method for producing printed matter]
The method for producing a printed matter according to the present invention is a method for producing a printed matter, wherein a gloss print layer is formed at any position on a substrate, and a surface protective layer is formed on the outermost surface on the side having the gloss print layer. ,
By performing the step of forming the glossy printed layer from the ink for the glossy printed layer containing metal scales, and the step of forming the surface protective layer from the ink for the surface protective layer containing the ultraviolet curable resin composition,
Reflection intensity measured at every 0.1 degree in the range of -45 degrees to +45 degrees with respect to the regular reflection direction at the time of irradiating visible light at an angle of 45 degrees from the normal toward the surface on the surface protective layer side However, the following condition (1) is satisfied in at least a partial area of the surface protection layer immediately above where the glossy print layer is located.
6.0 ≦ R _{in ± 2.5} / R _{out ± 2.5} (1)
R _{in ± 2.5} ; Sum of reflection intensities in the range of −2.5 degrees to +2.5 degrees R _{out ± 2.5} ; Reflection intensities in the range of −45 degrees to −2.6 degrees, and +2.6 Total reflection intensity in the range of +45 degrees to +45 degrees

The specular gloss of JIS Z 8741: 1997, which is a representative example of the gloss index, evaluates the gloss by the specular reflection intensity. However, even if the regular reflection intensity is high, it is difficult for the human eye to recognize that the glossiness is excellent unless there is a small difference between the regular reflection intensity and the reflection intensity in the peripheral region outside the vicinity of the regular reflection direction. In other words, even if the manufacturing process of the printed material is managed only by the mirror glossiness, it may not be possible to manufacture a printed material that matches the glossiness of human eyes.
On the other hand, the condition (1) of the present invention is that R _{in ± 2.5} , which is the sum of reflection intensities in the vicinity of the regular reflection direction, and R _{out ± 2,} which is the sum of reflection intensities in the peripheral region out of the vicinity of the regular reflection direction. Because it is a ratio to _.5 , the correlation with the glossiness by human eyes is high. Therefore, according to the method for producing a printed matter of the present invention, a printed matter which conforms to the glossiness by human eyes and whose quality is standardized can be produced easily and stably. Moreover, the printed material manufactured so as to satisfy the condition (1) can maintain the metallic gloss imparted by the gloss print layer, and therefore is excellent in metallic gloss.

In order to obtain a printed material satisfying the condition (1), it is preferable to form a hard coat layer before forming the gloss print layer.
In order to improve the design, it is preferable to form the pattern layer after forming the glossy print layer.

  In the method for producing a printed material of the present invention, it is further preferable to obtain the printed material so as to satisfy the condition (2) described above. Moreover, it is preferable to obtain a printed matter so as to satisfy suitable conditions (for example, the specular gloss of the gloss print layer) such as the hard coat layer, the gloss print layer, the pattern layer, the surface protective layer and the like described above.

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

[How to select printed materials]
The method for selecting a printed material according to the present invention includes a glossy printed layer containing metal scales at an arbitrary location on the substrate, and further curing the ultraviolet curable resin composition on the outermost surface on the side having the glossy printed layer. When selecting a printed matter having a surface protection layer consisting of
Reflection intensity measured at every 0.1 degree in the range of -45 degrees to +45 degrees with respect to the regular reflection direction at the time of irradiating visible light at an angle of 45 degrees from the normal toward the surface on the surface protective layer side However, the determination condition is that the following condition (1) is satisfied in at least a part of the surface protective layer immediately above where the glossy printed layer is located.
6.0 ≦ R _{in ± 2.5} / R _{out ± 2.5} (1)

  As described above, even if the specular glossiness is used as a determination condition, a printed matter that matches the glossiness of the human eye may not be selected. In addition, the quality of printed matter cannot be standardized only by evaluation by human eyes, depending on the individual's visual acuity, color vision, physical condition, and the like. According to the method of selecting printed matter of the present invention, it is possible to accurately select a printed matter that matches the glossiness by human eyes and to standardize the quality of the printed matter. Further, the printed matter selected with the condition (1) as the determination condition maintains the metallic gloss imparted by the glossy printed layer, and is excellent in metallic gloss.

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

  In the printed matter selection method of the present invention, it is preferable that the above-described condition (2) be a determination condition. Moreover, it is also preferable to add suitable conditions (for example, specular glossiness of a gloss printing layer), such as a hard-coat layer, a gloss printing layer, a pattern layer, a surface protective layer etc. mentioned above as a judgment condition.

  The embodiment of the printed substrate, hard coat layer, gloss print layer, pattern layer, surface protective layer selected by the print selection method of the present invention is the print substrate of the present invention, hard coat layer, gloss print layer This is the same as the embodiment of the pattern layer and the surface protective layer.

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

1. Measurement and Evaluation The following measurements and evaluations were performed on the printed materials prepared in Examples and Comparative Examples. The results are shown in Table 1.
1-1. Reflection intensity distribution Using a goniophotometer (trade name GP-200, manufactured by Murakami Color Research Laboratory Co., Ltd.), irradiates visible light (parallel light) at an angle of 45 degrees from the normal to the outermost surface of the printed matter. did. With respect to the reflected light, the light receiver was scanned at an angle of 0.1 degrees in a range of −45 degrees to +45 degrees with respect to the regular reflection direction of the irradiation light, and the intensity (light intensity) at each angle was measured. At the time of intensity (light intensity) measurement, the opening angle of the light receiver detected by the diaphragm of the light receiver is 0.1 degree. From the measurement results, “R _{in ± 2.5} / R _{out ± 2.5} ” and “R ₀ / R _{in ± 45} ” were calculated.

1-2. Mirror glossiness According to JIS Z8741: 1997, using the micro-TRI-gloss of BYK Gardner as a measuring instrument, the printed matter of Examples 1 to 4 and Comparative Examples 1 to 6, or the gloss printed layer of the printed matter intermediate The 60 ° specular gloss of the deposited film was measured.

1-3. Arithmetic mean roughness Ra and maximum valley depth Rv
For the printed materials of Examples 1 to 4 and Comparative Examples 1 to 6, the arithmetic average roughness Ra and Rv of JIS B0601: 2001 when the cut-off value was 0.08 mm, and the cut-off value was 0.8 mm. The arithmetic average roughness Ra and Rv of JIS B0601: 2001 was measured. In addition, Ra and Rv were measured using the trade name SE-340 manufactured by Kosaka Laboratory Ltd. under the following measurement conditions.
[The stylus of the surface roughness detection unit]
Kosaka Research Institute product name SE2555N (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: 0.5 mm / s
Spare length: (cutoff value λc) × 2
・ Vertical magnification: 2000 times ・ Lateral magnification: 10 times

1-4. Glossiness The glossiness of the printed materials of Examples 1 to 4 and Comparative Examples 1 to 6 was visually evaluated. As a result, those having high reflection contrast and excellent glossiness are "A", those having glossiness but having inferiority to the glossiness of the printed matter of Example 1 are "B", those having low glossiness "C". It was.

1-5. Metallic Gloss With reference to the printed matter of Comparative Example 1, the metallic gloss of the printed matter of Examples 1 to 4 and Comparative Examples 2 to 6 was visually evaluated. As a result, “A” indicates a metal luster equivalent to that of the reference, “B” indicates a metal luster that is inferior to the reference, but “C”.

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

2. Production of Printed Matter [Example 1]
Apply the ink 1 for hard coat layer of the following formulation to the entire surface on the coated side of the base (one-sided ivory paper with a basis weight of 235 g / m ² ) so that the thickness after drying is 6 μm, And a hard coat layer (cured product layer of ionizing radiation curable resin composition).
Next, the gloss printing layer ink 2 of the following formulation was applied to the entire surface of the hard coat layer so as to have a dry thickness of 0.50 μm, and dried to form a gloss printing layer. The thickness of the region substantially free of metal flakes in the gloss print layer was 0.30 μm, and the thickness of the metal flake unevenly distributed region was 0.20 μm.
Next, an amber pattern layer was formed by offset printing at an arbitrary position on the gloss print layer. Next, the surface protective layer ink 3 having the following formulation was applied so that the thickness after drying was 1.0 μm so as to cover the entire surface of the pattern layer and the glossy printed layer, and the surface protective layer (solvent-free) was applied. The cured product layer of the ultraviolet curable resin composition of the mold was formed, and the printed matter of Example 1 was obtained.

<Hard coat layer ink 1>
・ Ionizing radiation curable compound 70 parts (BASF Japan, trade name: Lumogen OVD Primer301)
(Mixture of bifunctional acrylate monomer and trifunctional acrylate monomer)
・ 30 parts of solvent (ethyl acetate)

<Glossy printing layer ink 2>
-Binder resin (nitrified cotton) 4.8 parts (made by DIC Graphics)
(Brand name: XS-763 Medium NT-No. 1)
-Aluminum flakes 7.2 parts (average length 14 μm, average thickness 0.04 μm)
・ 88 parts of solvent (ethyl acetate, IPA, ethanol, NPAC)

<Ink for surface protective layer 3 (solvent-free type)>
-UV curable compound 100 parts (manufactured by DIC Graphics, trade name: UV low odor coat varnish S)
・ Solvent 0 parts

In addition, in Example 1, arithmetic mean roughness Ra of JISB0601: 2001 when the cutoff value of the base-material surface is set to 0.08 mm was 0.129 micrometer. Moreover, arithmetic mean roughness Ra of JISB0601: 2001 at the time of setting the cutoff value of the substrate surface to 0.8 mm was 0.524 micrometer.
Moreover, in Example 1, arithmetic mean roughness Ra of JISB0601: 2001 when the cutoff value of the hard-coat layer surface is 0.08 mm was 0.026 micrometer. The arithmetic average roughness Ra of JIS B0601: 2001 when the cut-off value on the hard coat layer surface was 0.8 mm was 0.305 μm.
Moreover, in Example 1, arithmetic mean roughness Ra of JISB0601: 2001 at the time of setting the cutoff value of the gloss printing layer surface to 0.08 mm was 0.036 micrometer. The arithmetic average roughness Ra of JIS B0601: 2001 when the cut-off value on the glossy printed layer surface was 0.8 mm was 0.359 μm.

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

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

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

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

Comparative Example 2
A printed material of Comparative Example 2 was obtained in the same manner as Example 1, except that the surface protective layer was not formed on the design layer.

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

<Ink for surface protection layer 4>
-Ultraviolet curable resin composition (made by DIC Graphics, trade name: UV Karton ACT OP varnish)
(Mixture containing 55 to 65% by mass of UV curable monomer, 10 to 20% by mass of synthetic resin, 5 to 15% by mass of particles, and 5 to 15% by mass of auxiliary agent as main components)

Comparative Example 4
A vapor deposition film having an aluminum vapor deposition film having a thickness of 50 nm was prepared on a biaxially stretched PET film having a thickness of 12 μm. Then, the thickness of low density polyethylene (LDPE) is made using sand lamination method on the coated surface side of the substrate (one-sided ivory paper with a basis weight of 235 g / m ² ) and the PET film side of the deposited film Bonding was performed while extruding to 15 μm to obtain a laminate substrate.
Next, an amber pattern layer was formed by gravure printing on the deposited film of the laminar and the substrate. Next, the surface protective layer ink 5 having the following formulation was applied and dried so that the thickness after drying was 1.0 μm so as to cover the entire surface of the pattern layer and the deposited film, and a surface protective layer was formed. The print of Example 4 was obtained.

<Ink for surface protection layer 5>
-70 parts of thermosetting resin (made by DIC Graphics, trade name: Dick Safe G-310 OP varnish)
・ Solvent (water / IPA = 2/8) 30 parts

  In addition, in the comparative example 4, arithmetic mean roughness Ra of JISB0601: 2001 when the cutoff value of a vapor deposition film is set to 0.08 mm was 0.048 micrometer. The arithmetic average roughness Ra of JIS B0601: 2001 when the cutoff value of the deposited film was 0.8 mm was 0.301 μm.

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

<Glossy printing layer ink 6>
・ Binder resin (nitration cotton) 6 parts (made by DIC Graphics)
(Product name: XS-763 Medium NT-No. 1)
・ Aluminum piece 6 parts (made by Toyo Aluminum Co., Ltd., trade name: TD-180T)
(Average length 15μm, average thickness over 0.2μm)
・ Solvent (ethyl acetate, IPA, ethanol, NPAC) 88 parts

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

  In Comparative Example 5, the arithmetic average roughness Ra of JIS B0601: 2001 when the cutoff value of the glossy printed layer was 0.08 mm was 0.150 μm.

Comparative Example 6
Using a melt extrusion method, low density polyethylene (LDPE) is extruded to a thickness of 15 μm on the entire coated surface side of a substrate (one-sided ivory paper with a basis weight of 235 g / m ² ) to form a thermoplastic resin layer Formed.
Next, the gloss printing layer ink 2 having the above formulation was applied on the entire surface of the thermoplastic resin layer so that the thickness after drying was 0.70 μm, and dried to form a gloss printing layer.
Next, a yellow pattern layer was formed by offset printing at an arbitrary position on the glossy printed layer. Next, the surface protective layer ink 3 having the above formulation was applied so that the thickness after drying was 1.0 μm so as to cover the entire surface of the pattern layer and the glossy printed layer, and the surface protective layer (solvent-free) was applied. The hardened | cured material layer of the ultraviolet curable resin composition of type | mold was formed, and the printed matter of the comparative example 5 was obtained.

  From the results of Table 1, it can be seen that the printed materials of Examples 1 to 4 have a metallic luster and an excellent gloss feeling without using metal vapor deposition means. Moreover, although the printed matter of Examples 1 to 4 has a surface roughness of a predetermined low frequency component although the surface roughness of a high frequency component is small, the reflection intensity in the regular reflection direction does not become excessive because of the glare. There was no discomfort.

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

1: Base material 2: Hard coat layer 3: Glossy print layer 31: Metal scale unevenly distributed region 4: Picture layer 5: Surface protective layer 10: Printed matter

Claims (15)

A printed matter comprising a gloss print layer at any position on a substrate and further having a surface protective layer on the outermost surface on the side having the gloss print layer, the gloss print layer comprising a metal scale The surface protective layer is a cured product layer of an ultraviolet curable resin composition, and the surface protective layer side surface of the printed material is positive when irradiated with visible light at an angle of 45 degrees from the normal line. The reflection intensity measured every 0.1 degree in the range of −45 degrees to +45 degrees with respect to the reflection direction is the following condition (at least a partial area of the surface protection layer immediately above where the gloss print layer is located) Printed material that satisfies 1).
6.0 ≦ R _{in ± 2.5} / R _{out ± 2.5} (1)
R _{in ± 2.5} ; sum of reflection intensities in the range of −2.5 degrees to +2.5 degrees R _{out ± 2.5} ; reflection intensities in the range of −45 degrees to −2.6 degrees, and +2.6 Sum of reflection intensity in the range of degrees to +45 degrees It was measured every 0.1 degree in the range of -45 degrees to +45 degrees with respect to the regular reflection direction at the time of irradiating visible light at an angle of 45 degrees from the normal toward the surface protection layer side of the printed matter. The printed matter according to claim 1, wherein the reflection intensity further satisfies the following condition (2) in at least a part of the surface protective layer.
R ₀ / R _{in ± 45} ≦ 0.040 (2)
R ₀ ; Reflection intensity at 0 degree R _{in ± 45} ; Sum of reflection intensities in the range of −45 degrees to +45 degrees The printed matter according to claim 1 or 2, wherein an average length and an average thickness of the metal scale satisfy the following condition (3).
Average thickness of metal flakes / average length of metal flakes ≦ 0.010 (3) The printed matter according to any one of claims 1 to 3, wherein the average length of the metal flakes and the thickness of the gloss print layer satisfy the following condition (4).
10 ≦ [average length of metal flakes / thickness of gloss print layer] (4)   The printed matter according to any one of claims 1 to 4, wherein the average length of the metal flakes is 5.0 to 30.0 μm.   The average thickness of the said metal scale piece is 0.10 micrometer or less, Printed matter of any one of Claims 1-5.   The printed matter according to any one of claims 1 to 6, wherein the gloss print layer has a thickness of 0.15 to 1.50 m.   The printed matter according to any one of claims 1 to 7, wherein a pattern is formed by the glossy print layer.   The printed matter according to any one of claims 1 to 8, further comprising a hard coat layer between the substrate and the gloss print layer.   The printed matter according to claim 9, wherein the hard coat layer is a cured product layer of an ionizing radiation curable resin composition.   The printed material according to claim 1, wherein the substrate is a paper substrate.   The printed matter according to any one of claims 1 to 11, further comprising a pattern layer at an arbitrary position between the substrate and the surface protective layer.   A container using the printed matter according to any one of claims 1 to 12. A method for producing a printed matter, wherein a gloss print layer is formed at any position on a substrate, and a surface protective layer is formed on the outermost surface on the side having the gloss print layer,
By performing the step of forming the glossy printed layer from the ink for the glossy printed layer containing metal scales, and the step of forming the surface protective layer from the ink for the surface protective layer containing the ultraviolet curable resin composition,
Reflection intensity measured every 0.1 degrees in the range of -45 degrees to +45 degrees with respect to the regular reflection direction when irradiated with visible light at an angle of 45 degrees from the normal toward the surface on the surface protective layer side However, the method for producing a printed matter is to satisfy the following condition (1) in at least a partial region of the surface protective layer immediately above where the glossy printed layer is located.
6.0 ≦ R _{in ± 2.5} / R _{out ± 2.5} (1)
R _{in ± 2.5} ; sum of reflection intensities in the range of −2.5 degrees to +2.5 degrees R _{out ± 2.5} ; reflection intensities in the range of −45 degrees to −2.6 degrees, and +2.6 Total reflection intensity in the range of +45 degrees to +45 degrees A gloss print layer containing metal flakes is provided at any position on the substrate, and the outermost surface on the side having the gloss print layer has a surface protective layer consisting of a cured product of a UV curable resin composition. When selecting the printed material
Reflection intensity measured at every 0.1 degree in the range of -45 degrees to +45 degrees with respect to the regular reflection direction at the time of irradiating visible light at an angle of 45 degrees from the normal toward the surface on the surface protective layer side A method of selecting printed matter, wherein the judgment condition is that the following condition (1) is satisfied in at least a partial area of the surface protection layer immediately above where the glossy print layer is located.
6.0 ≦ R _{in ± 2.5} / R _{out ± 2.5} (1)
R _{in ± 2.5} ; sum of reflection intensities in the range of −2.5 degrees to +2.5 degrees R _{out ± 2.5} ; reflection intensities in the range of −45 degrees to −2.6 degrees, and +2.6 Sum of reflection intensity in the range of degrees to +45 degrees