JP6544286B2 - Printed matter - Google Patents

Description

  The present invention relates to a printed matter provided with a large number of grooves on the surface.

  In various printed matters such as advertisements, magazines, and posters, in recent years, display of high-definition and clear printed images is required, and in the printing technology field, a method of outputting image data to a printing medium, printing It has been considered to use any printing technology such as the method of selecting the material used for the medium and the material of the ink.

However, even if a high-definition and clear print image is printed on the print medium using the various printing techniques described above, a part of the light is reflected on the surface of the print, so that the observer Compared with the color of the printed image, it looks whitish, and there is a problem that the reading of a character or a pattern is hindered.
In addition, depending on the intensity of the light irradiated on the surface of the printed matter, the direction of irradiation, and the direction in which the observer observes the printed matter, the reflected light from the surface of the printed matter reduces the visibility of the printed image or makes visual observation difficult There is a problem that there is a possibility of becoming

  With respect to such problems, for the purpose of reducing the reflection of light on the surface to improve the visibility of the printed image, there has been proposed a printed material in which the surface of the printed material is processed. For example, Patent Documents 1 and 2 disclose a printed material having a large number of fine irregularities called moth eye on its surface. Such printed matter has fine irregularities on the surface with regularity in shape and arrangement, so that the refractive index for incident light does not change rapidly due to the principle of the moth-eye structure, and defects at the material interface can not be obtained. It is possible to suppress the reflection of light due to the continuous change in refractive index. Thereby, the reflection of light on the surface of the printed matter is reduced, and the visibility of the printed image can be improved.

JP 2012-152987 A JP 2014-71220 A

  However, although it is possible to obtain a reflectance reduction effect by having fine asperities on the surface of the printed matter, the shapes and arrangements of the individual protrusions (protrusions) and recesses (grooves) are regular, The wavelength selectivity is shown to reduce the reflectance, and depending on the wavelength region, a sufficient reflectance reduction effect can not be obtained due to the fine unevenness, and the sharpness and the visibility of the printed image of the printed matter may not be sufficient.

  The present invention has been made in view of the above problems, and it is a main object of the present invention to provide a printed material which can clearly display the color of a print image and can improve the visibility of the print image. Do.

In order to solve the above-mentioned subject, the present invention is printed matter which has a base material and a printing layer formed on the above-mentioned base material, and the outermost surface by the side of the above-mentioned printing layer of the above-mentioned printed matter The groove has an average area of 94000 nm ² or more and 131000 nm ² or less when the planar view shape of the groove portion which is a region surrounded by the side surface of the groove is approximated to an octagon. The dispersion of the maximum internal angle when the planar view shape of the groove portion of the groove portion is approximated to an octagon is within a range of 600 to 1020, and the flat surface of one groove portion and the groove portion of the one groove portion. The average distance between the centers of gravity of the other groove portions having the above-mentioned center of gravity of the above-mentioned groove mouth portion at a position closest to the center of gravity when the visual shape is approximated to octagon is 500 nm or less 8000 or more Providing a printed matter characterized by.

According to the present invention, since a large number of grooves having a predetermined variation in shape and arrangement position are formed on the outermost surface of the print layer side of the printed matter, light can be reflected in the grooves a number of times, Interference can be suppressed from increasing the intensity of light of a specific wavelength. Furthermore, in the groove portion, in addition to absorption of light by multiple reflection of light, absorption of light into the printed matter by Mie scattering also occurs, so that the reflectance can be reduced. Furthermore, the layer in which a large number of grooves are formed exhibits a high haze value due to the occurrence of Mie scattering, so total reflection on the surface on which the grooves are formed and the laminated interface in the printed matter can be prevented. The absorptivity of light other than the light related to the color tone of the above can be further enhanced.
Thereby, the printed matter of the present invention can exhibit an excellent reflectance reduction effect for light in a wide wavelength range by a large number of groove portions having a predetermined variation, and can improve the visibility of a printed image It becomes. In addition, the reflectance of light incident on the printed matter, particularly light other than light related to the color tone of the printed matter is reduced, and the absorptivity of light into the printed matter is increased, so that the color development of the printed image in the printing layer is improved. , It becomes possible to display color clearly.

  In the above invention, it is preferable that a large number of the grooves be formed on the surface of the transparent low reflection layer formed on the printing layer. This is because the printing layer is protected by the transparent low reflection layer, and a printed matter with high durability can be obtained.

  In the case of the above invention, the transparent low reflection layer has a transparent substrate, and a low reflection resin layer formed on one side of the transparent substrate and containing a transparent resin, and the above-mentioned low reflection resin layer It is preferable that many said groove parts are formed on the surface facing the surface which touches a transparent base material. Since the transparent low reflection layer having the low reflection resin layer on one side of the transparent substrate can be disposed in alignment with the position of the printing layer, the visibility of the printed image can be improved, and at the time of manufacture This is because the handling of the In addition, even if it is difficult to form the transparent low reflection layer directly on the print layer because the print layer is a curved surface, the adhesion to the print is poor, etc., the desired print can be obtained. It is because

  Moreover, in the case of the said invention, it is preferable that the said transparent low reflection layer is formed by transparent resin, and is directly formed on the said printing layer. Since the transparent low reflection layer is a single layer formed of a transparent resin and no laminated interface is formed in the transparent low reflection layer, it is possible to prevent light reflection at the laminated interface in the transparent low reflection layer. is there.

  In the above invention, it is preferable that a large number of the grooves be formed on the surface of the printing layer. This is because the number of layers constituting the printed matter of the present invention can be reduced, and reflection of light at the laminated interface can be prevented. In addition, since the printed matter can be made thin, it is possible to obtain a printed matter with high processability.

  In the printed material of the present invention, since the many grooves formed on the outermost surface have a predetermined variation in shape and arrangement position, a reflectance reduction effect is exhibited with respect to light in a wide wavelength range, so a printed image The present invention has the effect that it is possible to improve the visibility of the image and to clearly display the color of the print image.

It is an explanatory view explaining a slot in the present invention. It is an explanatory view explaining a slot in the present invention. It is a plane SEM image of the surface which has a groove part in the printed matter of this invention. It is a schematic sectional drawing which shows an example of the printed matter of this invention. It is a schematic sectional drawing which shows the other example of the printed matter of this invention. It is a schematic sectional drawing which shows the other example of the printed matter of this invention. It is explanatory drawing explaining the printing layer in the 2nd aspect of the printed matter of this invention.

Hereinafter, the printed matter of the present invention will be described in detail.
The printed matter of the present invention is a printed matter having a substrate and a printing layer formed on the substrate, and a large number of grooves are formed on the outermost surface of the printing layer on the printed layer side, The groove has an average area of 94000 nm ² or more and 131000 nm ² or less when the planar view shape of the groove opening which is a region surrounded by the side surface of the groove is approximated to an octagon, and the groove opening of the groove The dispersion of the maximum internal angle when the planar view shape of the portion is approximated to an octagon is within the range of 600 to 1020, and the planar view shape of the groove portion of one groove portion and the groove portion of the groove portion is octagonal The average distance between the centers of gravity of the other groove portions having the above-mentioned center of gravity of the above-mentioned groove mouth portion at a position closest to the center of gravity when approximated is 500 nm or less Yes, the above center of gravity distance Dispersion is characterized in that at least 8000.

According to the present invention, the large number of grooves formed on the outermost surface of the printed layer side of the printed matter have predetermined variations in shape and arrangement position, so that the grooves have excellent reflection against light in a wide wavelength range. The rate reduction effect can be exhibited.
That is, by having a predetermined variation in shape and arrangement position of a large number of grooves, light incident on the grooves can be reflected many times and absorbed in the layer in which the grooves are formed. It is possible to suppress the increase in the intensity of the wavelength light.
Furthermore, when the groove portion has a predetermined variation, the groove portion is formed by reflection many times in the groove portion, which is located in the outermost surface of the printed matter and is a region surrounded by the groove side surface, among others. In addition to light being absorbed into the layer, Mie scattering of light due to the shape of the groove can further increase the amount of light absorbed into the layer in which the groove is formed, resulting in a higher reflectance. It becomes possible to reduce. This is because Mie scattering has features such as "strong forward scattering" and "small wavelength dependence". That is, since Mie scattering has strong forward scattering, light incident on the groove is scattered in the layer in which the groove is formed, and the scattered light can be absorbed into the layer in which the groove is formed. . Moreover, since Mie scattering has a small wavelength dependency, it is possible to scatter light in the entire visible light region of 380 nm to 780 nm and to absorb scattered light into the layer in which the groove is formed. .

  As described above, when a large number of grooves have a predetermined variation, it is possible to exhibit an excellent reflectance reduction effect with respect to light in a wide wavelength range, and a printed matter in which the above-mentioned many grooves are formed on the outermost surface Can improve the visibility of the printed image by reducing the reflected light.

In addition, the printed matter usually displays the printed image by subtractive color mixing, and among the light incident on the printed matter, a part of the light is absorbed in the printed matter and the color tone of the light reflected without being absorbed in the printed matter is It becomes the color tone of the printed image. The fact that the reflectance of light on the surface of the print is low means that the absorptivity of light to the print is high, and in particular, the absorptivity of light other than the light relating to the color tone of the print is high.
According to the present invention, light of a wide wavelength range is absorbed into the printed matter by the reflectance reduction effect exerted by the variation of the large number of grooves. In addition, in the layer in which a large number of grooves are formed, Mie scattering occurs to increase the haze value, thereby preventing total reflection on the surface on which the grooves are formed and the lamination interface in the printed matter. The absorptivity of light other than light relating to color tone can be further increased.
As described above, the reflection of light incident on the printed matter, in particular, light other than the light related to the color tone of the printed matter is reduced, and the absorptivity into the printed matter is increased. The color developability is improved, and the color can be clearly displayed.

  Furthermore, the printed matter of the present invention also has a feature of high structural durability by having grooves on the surface. In the case where a projection such as a moth-eye is provided on the surface, if the projection is damaged or deformed by an external impact, it is expected that the reflectance reduction effect is reduced. On the other hand, according to the present invention, since the concave groove portion is formed on the outermost surface of the printed matter, breakage, deformation and the like of the groove portion are unlikely to occur, and a high reflectance reduction effect can be exhibited over a long period of time. . For this reason, the printed matter of the present invention has high visibility over a long period of time, and it is possible to display colors clearly.

  Hereinafter, the printed matter of the present invention will be described by being divided into the groove portion of the printed matter of the present invention and the embodiment of the printed matter of the present invention.

I. Grooves A large number of grooves in the present invention are formed on the outermost surface of the printed layer side of the printed matter, and the shapes and arrangement positions of the grooves have a predetermined variation.

The groove in the present invention will be described with reference to the drawings. FIG. 1 is an explanatory view for explaining the grooves in the printed matter of the present invention. Fig.2 (a) is a schematic perspective view for demonstrating the groove part in this invention, FIG.2 (b) is a schematic plan view of Fig.2 (a).
As illustrated in FIG. 1, the large number of grooves 1 provided on the outermost surface of the printed matter 10 of the present invention have a predetermined variation in shape and arrangement position.
Here, the predetermined variation of the large number of grooves is defined by quantifying three parameters.
The first parameter depends on the size of the groove (which may be simply referred to as a groove), which is an area surrounded by the side surface of the groove. As shown in FIG. 2A, the grooves 1 and 1 ′ have grooved portions d and d ′ in the outermost surface of the printed matter 10, which are regions surrounded by the side surfaces. In the present invention, the fact that a large number of grooves have a predetermined variation means that, as shown in FIG. 2B, the grooves d and d 'of the grooves 1 and 1' have an octagonal shape in plan view. It means that the average of the areas S and S ′ is in the range of 94000 nm ² or more and 131000 nm ² or less.
The second parameter depends on the shape of the groove portion. In the present invention, that a large number of grooves have a predetermined variation means that the dispersion of the maximum internal angle is 600 or more and 1020 or less when the plan view shape of the groove mouth portion is approximated to an octagon as shown in FIG. It means that it is inside.
The third parameter depends on the positional relationship between adjacent grooves. In the present invention, the fact that a large number of grooves have a predetermined variation means that, as shown in FIG. 2B, the plan view shapes of the groove portion 1 of one groove portion and the groove opening portion of one groove portion 1 approximate an octagon. The average distance L between the centers of gravity (the distance between the closest centers of gravity) of the other grooves 1 ′ having the center O ′ when the planar view shape of the groove opening is approximated to an octagon at a position closest to the center O It means that it is 500 nm or less, and the dispersion | distribution of the said distance L between gravity centers is 8000 or more.
That is, "having a predetermined variation" in a large number of grooves means that the first to third three parameters indicate within the above-described predetermined range (hereinafter, may be referred to as a predetermined value). .

In the present invention, the reflectance reduction effect of the grooves is determined according to the degree of variation of the large number of grooves, and the effects of the present invention due to the above-mentioned reflectance reduction effect can be achieved by the large number of grooves having predetermined dispersion. Can.
Variations in groove shape and arrangement position are defined by quantifying three parameters of “size of groove opening”, “shape of groove opening”, and “positional relationship between adjacent grooves”, and each parameter is defined by By showing the above-mentioned predetermined value, many said groove parts can have predetermined variation.
Hereinafter, the quantification method of each parameter and the value of each parameter specified by the quantification method will be described.

A. Parameter Quantification Method Variations in the shape and arrangement position of the groove portions in the present invention are calculated by extracting and quantifying a desired score among a large number of groove portions provided on the outermost surface of the print layer side of the printed matter.
The grooves are extracted using a scanning electron microscope (SEM), an atomic force microscope (AFM) or the like, and the printed image grooves are made at a magnification of 10000 times and a field of view of 4 μm in length × 4 μm in width A plan view observation is performed from the surface side, an in-plane arrangement of grooves in the above view range is detected by an image, and a desired score is extracted from the image.

Each parameter in the present invention is calculated with 30 points being the minimum extraction points of the groove per field of view range. It is preferable that the number of extraction points of the groove be as large as possible, and the number of extraction points is preferably 30 or more, and more preferably 50 or more. Further, the number of detections of the visual field range for extracting the groove portion is preferably 3 or more, more preferably 5 or more, particularly 10 or more per unit area (2500 mm ² ) of the surface provided with the groove portion of the printed matter.
By defining the number of extraction points and the number of detections of the visual field range in the above range, three parameters can be quantified with higher accuracy, and variations in the shape and arrangement position of the groove can be accurately defined. is there.

Each parameter is quantified by the following procedure.
(1) The in-plane arrangement of the grooves is detected using a scanning electron microscope (SEM) or an atomic force microscope (AFM). A desired number of grooves are extracted from the detected in-plane array, and a plan view shape of the groove opening which is an area surrounded by the groove side surfaces is detected for each groove. The planar view shape of the groove portion can be detected from the black-and-white contrast in the SEM image and from the contrast in color in the AFM image.
The specific detection method of the planar view shape of the groove portion is not particularly limited. For example, the intensity of the edge is calculated by calculating the gradient with the first derivative of the contrast in the image, and the direction of the gradient The local change of the edge can be predicted from the above, and it can be detected by searching for a point where the gradient in that direction is locally maximum.

(2) Subsequently, the plan view shape of the groove opening obtained for each groove is approximated to an octagon from the SEM image and the AFM image. At this time, partially broken lines are complemented. As a complementation method, for example, a method of providing a certain threshold to create a closed space can be used.
As a method of approximating the shape in plan view of the groove portion, a conventionally known method used in approximating a shape from an image can be applied, and the above method is not particularly limited. For example, template matching, generalized Hough transform Methods such as the Douglas-Peucker method can be used.
Template matching prepares a template representing a shape in advance, and moves the template with respect to image data to be subjected to image recognition while examining a similarity index such as a correlation coefficient while moving the template It is a technology to recognize. For an image approximation method using template matching, for example, "Nakada Takayuki, Tsukuei, Naofuji Fujiwara:" Figure recognition using Log-Polar transform in a three-dimensional environment ", Journal of the Institute of Electronics, Information and Communication Engineers (D-II), Vol. .88, No. 6, pp. 985-993 (2005.6), "Fumihiko Saito:" Semiconductor chip image template matching by partial random search and adaptive search ", Journal of Japan Society for Precision Engineering, Vol. 61, No. 11, pp. No. 1604-1608 (1995. 11).
Also, the generalized Hough transform is a generalization of the Hough transform that determines the straight line that most passes the feature points in the image data among the straight lines existing infinitely, and is applied to the curve. Also, shape recognition of image data can be performed using a reference table prepared in advance. For the image approximation method by the generalized Hough transform, for example, “BALLAD, DH:“ GENERALIZING THE HOUGH TRANSFORM TO DETECT ARBITRARY SHAPES ”, Pattern Recognition, Vol. 13, No. 2, pp. 111-122 (1981) or , "Akira Kimura, Takashi Watanabe:" Generalized Hough Transform Extended as Affine-Invariant Arbitrary Shape Detection Method, "Journal of the Institute of Electronics, Information and Communication Engineers (D-II), Vol. J84-D-II, No. 5 , pp. 789-798 (2001.5).
The Douglas-Peucker method is a method of performing shape recognition by polygonal line approximation. For an image approximation method by the Douglas-Peucker method, for example, “Wu, ST, MRG:“ A non-self-intersection Douglas-Peucker Algorithm ”, Proceeding of Sixteenth Brazilian Symposium on Computer Graphics and Image Processing, IEEE, pp. 60 -66 (2003) ".

(3) Next, for each groove portion, the area in a plan view shape of the groove mouth portion approximated to an octagon (hereinafter sometimes referred to as the area of the groove mouth portion) is calculated. The area of the gutter can be calculated from the contrast between the pixel size of the image scale and the number of pixels included in the octagon. The calculated area is statistically processed to obtain an average value and a variance. Existing spreadsheet software can be used for statistical processing. In addition, when calculating | requiring the average value and dispersion | distribution of the said area, it is desirable to exclude an outlier. The outlier means that the absolute value of the standardized score calculated by the following formula is 3 or more.
Standardized score = (area of individual groove mouth-average value of area of groove mouth) / standard deviation

(4) Next, for each groove, the maximum internal angle (hereinafter sometimes referred to as the maximum internal angle of the groove opening) when the planar view shape of the groove opening is approximated to an octagon is extracted, and the average processing is performed by statistical processing And seek variance. Use existing spreadsheet software for statistical processing. In addition, it is desirable to exclude outliers when obtaining the variance of the maximum interior angle. The outlier means that the absolute value of the standardized score calculated by the following formula is 3 or more.
Standardized score = (maximum internal angle of each groove-average value of maximum internal angle of groove) / standard deviation

(5) Next, for each groove portion, the center of gravity in a plan view shape of the groove portion approximated to an octagon (hereinafter, may be referred to as the center of gravity of the groove portion) may be calculated to define the position of the groove. The center of gravity of the gutter is defined by the following method. First, as described above, the planar view shape of the gutter is approximated to an octagon, the diagonals are connected from one vertex of the octagon and divided into six triangles, and the center of gravity of each triangle is determined. Next, the centroids of the six triangles are connected to form a hexagon, and in a similar manner, one vertex of the hexagon is connected to a diagonal and divided into four triangles, and the centroid of each triangle is determined. Next, connect the centroids of the four triangles to form a square. Then, divide the rectangle into two triangles with one diagonal, find the centroids of the two triangles, connect the two centroids with a straight line, and similarly divide the rectangle into two triangles with another diagonal Find the centroids of the three triangles and connect the two centroids with a straight line. The intersection of the two straight lines is the octagonal center of gravity, that is, the center of gravity of the groove.

(6) Subsequently, the position of the center of gravity of the groove portion of each groove portion is coordinateized. The origin of the coordinates and the axis can be in any direction. For example, with the lower left in the SEM image or the AFM image as the origin, the right direction parallel to the sheet surface from the above origin is the x axis, and the upper direction (sheet surface width direction) orthogonal to the x axis is the y axis Do. By setting the image as a coordinate plane in this manner, the position of the center of gravity of the groove portion of the groove portion can be coordinated.
From the coordinates of the position of the center of gravity of the groove mouth of each groove, the distance between the grooves, that is, the distance between the specific groove and the adjacent grooves is calculated. The distance between the centers of gravity can be calculated by the following formula. Among the calculated distances between the centers of gravity, the minimum distance is defined as "the closest distance between the centers of gravity".
Center-of-gravity distance = {(x ₁ −x ₂ ) ² + (y ₁ −y ₂ ) ² } ^1/2 }
Note that x ₁ and y ₁ in the equation are an x coordinate and ay coordinate indicating the position of the center of gravity of the specific one groove. Further, x ₂ and y ₂ are an x-coordinate and a y-coordinate indicating the position of the center of gravity of the groove adjacent to the specific one groove.
The distance between the centers of gravity can be calculated from the contrast between the pixel size and the number of pixels of the scale of the SEM image or the AFM image.

(7) The closest distance between the center of gravity of each groove is extracted by the above method, and the average value and the variance of the closest distance between the centers of gravity are calculated by performing statistical processing with existing spreadsheet software. Note that it is desirable to exclude outliers when obtaining the average value and the variance of the closest distance between the centers of gravity. The outlier means that the absolute value of the standardized score calculated by the following formula is 3 or more.
Standardized score = (distance between closest centers of gravity of individual grooves − average value of distances between closest centers of gravity) / standard deviation

  The value of the variance calculated in the quantification of each parameter is generally calculated by dividing the sum of the root mean square of the difference between the measured value and the average value of the measured values by the number of extraction points. It is a value.

B. Parameters Next, respective parameters for defining the variation of the shape and arrangement position of the groove portion in the present invention will be described.

1. The size of the groove mouth portion The size of the groove mouth portion is defined by the area (area of the groove mouth portion) when the plan view shape of the groove mouth portion is approximated to an octagon. The area of the groove portion is a portion shown by S and S ′ in FIG. 2 (b) and FIG. 3 (a). In addition, FIG. 3 is a plane SEM image of the surface having the groove portion in the printed matter of the present invention, and the symbols not described with reference to FIG. 3 are the same as those in FIG. 1 and FIG.

In the present invention, the average area of Mizoguchi portion, may be within the range of 94000Nm ² more 131000Nm ² or less, is preferably Among them 99000Nm ² more 121000Nm ² within the following ranges.
In spherical particles, the diameter at which geometrical optical scattering is controlled is several μm or more, but the scattering at the groove edge shows different behavior, and in the present invention, the groove edge has an area within the above range, so Mie scattering It is presumed to be dominant. If the average area of the groove mouth portion is larger than the above range, geometrical optical scattering becomes dominant rather than Mie scattering, so that forward scattering hardly occurs and absorption of light into the layer in which the grooves are formed is reduced. The desired reflectance reduction effect may not be obtained. On the other hand, if the average of the area of the groove mouth portion is smaller than the above range, Rayleigh scattering becomes dominant, so that forward scattering hardly occurs and light absorption into the layer in which the groove portion is formed may be reduced. .

When the average of the area of the groove portion is in the above range, the dispersion of the area of the groove portion is preferably in the range of 4.08E + 9 to 1.06E + 10. It is because it can suppress that the intensity | strength of the light of a specific wavelength is strengthened by interference. The unit of dispersion of the area of the gutter is (nm ² ) ² .

2. The shape of the groove mouth portion The shape of the groove mouth portion is defined by the size of the maximum internal angle when the plan view shape of the groove mouth portion is approximated to an octagon. The maximum internal angle of the groove portion means, for example, a portion indicated by θ _max in FIG. 3 (b).

As the maximum internal angle increases, the variation in the shape increases as the maximum internal angle increases, and the variation in shape decreases as the maximum internal angle decreases. Therefore, as the dispersion of the maximum internal angle calculated for each of the extracted grooves is larger, the shape of the shape of the groove opening in each groove in plan view also has a larger dispersion.
In the present invention, the dispersion of the maximum internal angle of the groove portion may be in the range of 600 to 1020, and preferably in the range of 640 to 980, and particularly preferably in the range of 640 to 810. If the dispersion of the maximum internal angle of the groove portion is larger than the above range, design of the groove may be difficult in manufacture, and if it is smaller than the above range, the intensity of light of a specific wavelength may be increased due to interference. It is because there is. The unit of dispersion of the maximum internal angle of the groove portion is degrees (°).

  At this time, it is preferable that the average of the maximum internal angle of the groove portion is in the range of 200 ° or more and 230 ° or less. If the average of the maximum internal angle of the groove portion is larger than the above range, design of the groove may be difficult in manufacturing, while if it is smaller than the above range, the light intensity of a specific wavelength may increase due to interference. It is because there is.

3. Positional relationship between adjacent groove portions The position of the groove portion refers to the position of the center of gravity (the center of gravity of the groove opening portion) when the planar view shape of the groove opening portion is approximated to an octagon, shown by O or O 'in FIG. It is a part.
The positional relationship between adjacent grooves is the distance between the centers of gravity of one groove and the other groove having the center of gravity of the groove at the position closest to the center of gravity of the groove of the groove, ie the closest center of gravity It is defined by the average of the distances.

  Here, although the closest distance between the centers of gravity is calculated and quantified by the method described above, it will be further described with reference to the drawings. Among the grooves adjacent to the groove 1A, the closest distance between the centers of gravity, as shown in FIG. 3C, is closest to the gravity center O when the planar view shape of the groove opening of the groove 1A is approximated to octagonal. The groove portion 1B having the center of gravity O when the planar view shape of the groove mouth portion is approximated to an octagon is extracted, and the distance L1 between the centers of gravity is calculated as the closest distance between the centers of gravity. Next, among the groove portions adjacent to the groove portion B, a groove portion 1C having a gravity center O when the plan view shape of the groove port portion approximates an octagon is extracted at a position closest to the center O of gravity of the groove port portion of the groove portion 1B, The distance L2 between the centers of gravity is calculated as the closest distance between the centers of gravity. The average of the closest distance between the centers of gravity is calculated by repeatedly performing the above operation to calculate the sum of the closest distance between the centers of gravity for the number of extraction points of the groove and dividing by the number of extraction points.

In the present invention, the average distance between the closest centers of gravity may be 500 nm or less, preferably 420 nm or less, particularly preferably 410 nm or less. If the average distance between closest centers of gravity is larger than the above range, adjacent grooves are not in close contact, and many flat regions (hereinafter sometimes referred to as non-groove regions) where grooves are not formed exist. Thus, the reflectance reduction effect may be reduced due to the reflection of light generated in the non-groove region.
The lower limit of the average of the closest distance between the centers of gravity is not particularly limited, and can be set in a range that can be designed in manufacturing, and is preferably, for example, 330 nm or more.

The dispersion of the closest point-to-center-to-centre distance when the average of the closest point-to-centre-center distance is within the above range may be 8000 or more, preferably 11,000 or more, particularly 12000 or more. If the dispersion of the distance between the closest centers of gravity is smaller than the above range, a large number of grooves will be arranged with an equal pitch width, the intensity of light of a specific wavelength will be increased by interference, and the desired reflectance reduction effect is exhibited In some cases it is difficult to
The upper limit of the dispersion is not particularly limited, and can be set in a range that can be designed for manufacturing, and is preferably, for example, 20000 or less. The unit of dispersion of the closest distance between the centers of gravity is nm ² .

C. Others The depth of the groove is not particularly limited as long as the above three parameters can be set to predetermined values, but for example, it is preferably in the range of 100 nm to 10 μm, and more preferably in the range of 300 nm to 1 μm. Is preferred. If the depth of the groove is smaller than the above range, the curvature of the groove becomes large, so geometric optical scattering becomes dominant rather than Mie scattering, so that forward scattering is less likely to occur, and therefore, into the layer in which the groove is formed. Light absorption may be reduced. On the other hand, when the depth of the groove is larger than the above range, it may be difficult to manufacture it into a desired groove shape.
The depth of the groove, refers to the average length of from the surface of the groove is formed a layer to the tip of the groove bottom, a portion indicated by h ₁ in FIG. 1.

  As for the depth of the groove, for example, an atomic force microscope (AFM) or the like is used to detect the maximum point and the minimum point of the depth of each groove, and from the detected maximum point The difference of relative depth of each local maximum point position from the outermost surface position of the printing layer included inside is set as "depth = 0.) is acquired and made into a histogram, it is calculated from the frequency distribution by the histogram, and the average Is the value to be converted. For detection of local maximum and local minimum points, for example, various methods such as a method of obtaining a planar view shape and a magnified picture of a corresponding cross-sectional shape are sequentially compared, a method of obtaining it by image processing of a planar view magnified picture, etc. Can.

In addition, when the depth of the groove is within the above range, the aspect ratio of the depth to the maximum diameter of the shape in plan view of the groove portion may be a ratio that can exhibit a desired reflectance reduction effect. For example, the inside of the range of 0.3-30 is preferable, and the inside of the range of 0.8-3 is especially preferable. When the aspect ratio is smaller than the above range, light may not be easily reflected in the groove and the reflectance reduction effect may not be sufficiently exhibited. On the other hand, if the aspect ratio is larger than the above range, shaping may be difficult and the groove may not have a desired shape.
The maximum diameter of the shape of the groove mouth in plan view refers to the maximum width passing the center of the groove mouth, that is, the widest point when the shape of the groove mouth is approximated to an octagon.

The grooves form a concave pyramidal structure. For this reason, the printed material of the present invention can form the shape of the groove portion with high accuracy, and has a manufacturing advantage of improving productivity.
In general, in a printed material in which grooves are regularly arranged, in order to improve the reflectance reduction effect, a method is used in which the shape of the groove bottom is made a multi-groove shape with branched tips and the surface area is increased. However, such a shape may not be accurately shaped.
On the other hand, in the present invention, since the reflectance reduction effect is exerted by giving predetermined variations to the groove portions, it is not necessary to make the groove portions into a multi-groove shape, and it becomes possible to accurately mold each groove portion. .
The tip of the groove bottom of the groove may be sharp or may have a curvature. Above all, it is preferable that the tip be pointed because the light absorption into the layer in which the groove is formed by Mie scattering is increased.

The plan view shape of the groove mouth part is not particularly limited as long as it is a shape that can be approximated to an octagon, and for example, a polygon such as a pentagon, a hexagon, an octagon, a dodecagon, etc. A shape etc. can be mentioned.
In addition, the side surface shape of the groove may be linear or curved. Furthermore, the side surface shape of the groove may be multistage. Among them, it is preferable that the side surface of the groove portion be multistaged. This is because multiple reflections and Mie scattering are more likely to occur in the grooves.

II. Embodiment Next, an embodiment of the printed matter of the present invention will be described.
The printed matter of the present invention may be any printed matter on the printed layer side having a large number of grooved portions having the predetermined variation described in the section "I. Grooved portions" described above, C) listing the first aspect formed on the surface of the transparent low reflection layer formed on the print layer, and the second aspect in which a large number of the grooves are formed on the surface of the print layer it can.
Each aspect will be described below.

A. First Aspect A first aspect of the printed matter of the present invention (hereinafter, this section may be referred to as the present aspect) will be described. The printed matter according to this aspect is one in which a large number of the grooves are formed on the surface of the transparent low reflection layer formed on the printing layer. Specifically, the printed matter of the present embodiment has a substrate, a printing layer formed on the substrate, and a transparent low reflection layer formed on the printing layer, and a large number of them are on the surface of the transparent low reflection layer. The groove portion of is formed so as to have a predetermined variation.
In this aspect, the transparent low reflection layer is usually located on the outermost surface of the printed layer side of the printed matter.

The printed matter of this embodiment will be described with reference to the drawings. FIG. 4 is a schematic cross-sectional view showing an example of the printed matter of the present embodiment. As shown in FIG. 4, the printed material 10 of this embodiment is formed on the substrate 2, the printing layer 3 formed on the substrate 2 and constituting the printed image, and the transparent low reflection layer 4 formed on the printing layer 3. It is possessed. On the surface of the transparent low reflection layer 4, a large number of grooves 1 having a predetermined variation in shape and arrangement position are provided.
In the printed matter of the present embodiment illustrated in FIG. 4, the transparent low reflection layer 4 has a layer structure in which the transparent substrate 11 and the low reflection resin layer 12 containing a transparent resin are laminated, and is the outermost layer. A large number of grooves 1 are formed on the surface of the reflective resin layer 12 facing the surface in contact with the transparent substrate 11 with a predetermined variation. The transparent low reflection layer 4 is formed on the printing layer 3 via the adhesive layer 13.
The predetermined variation of a large number of grooves is defined by quantifying three parameters. The three parameters for causing a large number of groove portions to have a predetermined variation and the predetermined values thereof are the same as the contents described in the section of “I. groove portion” described above, and thus the description thereof is omitted here.

In this aspect, since the printing layer is protected by the transparent low reflection layer, a highly durable printed material can be obtained.
Hereinafter, each structure of the printed matter of this aspect is demonstrated.

1. Transparent Low Reflecting Layer The transparent low reflective layer in this aspect is formed with a large number of grooves on the surface with a predetermined variation.
The details of the grooves formed on the surface of the transparent low reflection layer are the same as the contents described in the above-mentioned “I. groove”, and thus the description thereof is omitted here.

The transparent low reflection layer preferably exhibits a low reflectance with respect to the entire wavelength range of visible light. Specifically, the maximum reflectance of the transparent low reflection layer in the visible light range of 380 nm to 780 nm is preferably 2.0% or less, and more preferably 1.5% or less.
By setting the maximum reflectance of the transparent low reflection layer to the above-mentioned upper limit value or less, it is possible to show a low reflectance to the entire wavelength range of visible light, and the reflectance reduction effect by the groove portion is sufficiently exhibited. And the visibility of the printed image can be improved. In addition, since the absorptivity of light to the printed matter is increased by the reflectance reduction effect by the groove portion, the coloring property of the printed image is improved, and the color can be clearly displayed.
The maximum reflectance is obtained by measuring total reflection with respect to 8 ° incident light (wavelength region of 380 nm to 780 nm) using a Scanning Spectrophotometer UV-3100PC (manufactured by Shimadzu Corporation) as a measurement device. The maximum reflectance of the transparent low reflection layer can be measured, for example, by using a printing layer described later as a black printing layer.

The transparent low reflection layer preferably has a high haze value. The higher the haze value, the greater the variation in the shape of the groove and the arrangement position, so that the entire transparent low reflection layer can exhibit an excellent reflectance reduction effect, and the color development and visibility of the printed image in printed matter are improved. It is because you can do it.
In addition, as the haze value of the transparent low reflection layer is higher, light scattering due to Mie scattering is increased, and total reflection on the surface on which the groove portion is formed or the laminated interface in the printed matter can be prevented. As a result, the light other than the light relating to the color tone of the printed matter is reduced in reflection and the absorptivity into the printed matter is increased, so that the color development of the printed image in the printed layer is further improved and the color is displayed more clearly. It is because it becomes possible.
The haze value of the transparent low reflection layer may be 70% or more, preferably 80% or more. The upper limit of the haze value is preferably 95% or less. If the haze value is smaller than the above range, the groove portion does not have a predetermined variation in shape and arrangement position, and absorption of light to the transparent low reflection layer due to multiple reflections of light and Mie scattering hardly occurs. This is because the reflectance reduction effect may not be exhibited. On the other hand, when the haze value is larger than the upper limit, it may be difficult to manufacture a desired groove shape.
A haze value is a value in the area | region in which the groove part of the transparent low reflection layer was formed, and is measured by the method based on JISK7361 using a haze meter (product name: Hayashi guard made from Toyo Seiki Seisaku-sho).

The transparent low reflection layer in this aspect is not particularly limited as long as it is a layer in which a large number of grooves are formed on the surface with the above-mentioned variation and can exhibit a desired maximum reflectance and haze value. However, it can be roughly divided into the following two specifications.
That is, in the transparent low reflection layer in this embodiment, as illustrated in FIG. 4, the transparent low reflection layer 4 is formed on one surface side of the transparent substrate 11 and the transparent substrate 11 and contains a transparent resin. Specifications having a plurality of grooves 1 formed on the surface of the low reflection resin layer 12 facing the surface in contact with the transparent substrate 11 (hereinafter referred to as the first specification of the transparent low reflection layer). And the specification that the transparent low reflection layer 4 is a single layer formed of a transparent resin (hereinafter referred to as the second specification of the transparent low reflection layer), as illustrated in FIG. can do.
Hereinafter, each specification of a transparent low reflective layer is demonstrated.

(1) First specification of the transparent low reflection layer The first specification of the transparent low reflection layer (hereinafter referred to as "this specification" in this section) includes a transparent substrate and one surface of the transparent substrate It has a low reflection resin layer formed on the side and containing the transparent resin, and a large number of the grooves are formed on the surface of the low reflection resin layer facing the surface in contact with the transparent base.

The transparent low reflection layer of this specification can be made into a printed material by forming a low reflection resin layer on a transparent substrate and then sticking it on a printing layer. For this reason, the transparent low reflection layer of this specification can be arrange | positioned according to the position of a printing layer, and it has the manufacturing advantage that handling property improves.
In addition, the transparent low reflection layer of this specification is a case where it is difficult to form the transparent low reflection layer directly on the printing layer because the printing layer is a curved surface, the adhesion to the printed matter is poor, etc. Even in the point that it is possible to form a desired printed matter, it is effective.

(A) Low Reflection Resin Layer The low reflection resin layer is formed of a transparent resin. In order for the groove to exhibit the desired reflectance reduction effect, it is necessary to have a predetermined variation defined by quantifying the three parameters described in the above-mentioned "I. groove", and it is formed of a transparent resin By forming the grooves on the low reflection resin layer, it is possible to increase the accuracy of the shape of each groove and to show a predetermined variation.

  The transparent resin constituting the low reflection resin layer is not particularly limited as long as it can form a large number of grooves having the above-mentioned predetermined variation, and for example, ionization of acrylate, epoxy, polyester, etc. Radiation curable resin, thermosetting resin such as acrylate resin, urethane resin, epoxy resin, polysiloxane resin, various materials such as thermoplastic resin such as acrylate resin, polyester resin, polycarbonate resin, polycarbonate resin, polyethylene resin, and polypropylene resin, and various materials Curing forms of the molding resin can be used. In addition, ionizing radiation means electromagnetic waves or charged particles having energy capable of polymerizing and curing molecules, for example, all ultraviolet rays (UV-A, UV-B, UV-C), visible light, gamma rays , X-rays, electron beams and the like.

  The low reflection resin layer may contain any material as needed. Optional materials include, for example, refractive index modifiers, polymerization initiators, mold release agents, photosensitizers, antioxidants, polymerization inhibitors, crosslinkers, infrared absorbers, antistatic agents, viscosity modifiers, adhesion. An enhancer etc. can also be contained. As a refractive index regulator, the low refractive index material currently disclosed by Unexamined-Japanese-Patent No. 2013-142821 is mentioned, for example.

The thickness of the low reflection resin layer is not particularly limited, and can be appropriately set in consideration of the material to be used, the required strength, etc. For example, the range of 3 μm to 200 μm is preferable, and the range of 5 μm to 100 μm is particularly preferable. preferable.
The thickness of the low reflection resin layer refers to the average of the length from the interface between the low reflection resin layer and the transparent substrate to the surface on which the grooves of the low reflection resin layer are formed.

  The low reflection resin layer has transparency to visible light in order to enable visual recognition of the printed image in the underlying printing layer. Specifically, the light transmittance of the low reflection resin layer to the entire wavelength region of 380 nm to 780 nm of visible light is preferably 80% or more, more preferably 85% or more, and particularly preferably 90% or more. In the present specification, the light transmittance is a value measured by a spectrophotometer U-4100 manufactured by Hitachi High-Technologies Corporation.

  The refractive index of the low reflection resin layer is preferably such that the difference in refractive index with the transparent base material described later is within a desired range, and it depends on the type of transparent resin to be selected. It is preferably in the range of .40, and more preferably in the range of 1.40 to 1.70. In addition, the refractive index in this specification is measured by Shimadzu Corporation exact spectrometer GMR-1DA type | mold.

(B) Transparent base material A transparent base material has the above-mentioned low reflection resin layer on one surface.

The material used for the transparent substrate is not particularly limited as long as it exhibits the above-described light transmittance and can obtain a transparent substrate having a desired refractive index, and, for example, a thermoplastic resin, Resins, such as thermosetting resin and ionizing radiation curable resin, can be used.
Specifically, cellulose resins such as triacetyl cellulose; polyester resins such as polycarbonate, polyethylene terephthalate and polyethylene naphthalate; polyolefin resins such as polyethylene and polymethylpentene; acrylic resins; polyurethane resins and polyether monkeys Phone, polysulfone, polyether, polyether ketone, acronitrile, methacrylonitrile, cycloolefin polymer, cycloolefin copolymer, polyamide, polyimide, polystyrene, acrylonitrile-styrene copolymer, polyvinyl acetate, ethylene-vinyl acetate copolymer And vinyl chloride, polyvinylidene chloride, and polyether ether ketone.
Moreover, you may use inorganic materials, such as glass and ceramics, as a material of a transparent base material.

  The transparent substrate is, if necessary, a filler, a matting agent, a foaming agent, a flame retardant, a lubricant, an antistatic agent, an antioxidant, an ultraviolet absorber, a light stabilizer, a radical scavenger, a soft component (for example, rubber And the like may be included.

  As the transparent substrate, those of various aspects such as plate, sheet, film and the like can be used.

  The thickness of the transparent substrate is not particularly limited as long as it can support a low reflection resin layer and can exhibit desired light transmittance, but for example, a range of 0.025 mm to 20 mm is preferable.

  The transparent substrate is provided with transparency to visible light in order to make it possible to view the printed image in the underlying printing layer. Specifically, it is preferable that the light transmittance of the transparent substrate with respect to the entire wavelength region 380 nm to 780 nm of visible light is 80% or more, particularly 85% or more, and particularly 90% or more.

The refractive index of the transparent substrate is preferably about the same as the refractive index of the low reflection resin layer. When the difference in refractive index between the low reflection resin layer and the transparent substrate is large, a discontinuous interface of refractive index is formed at the interface between the low reflection resin layer and the transparent substrate, and light is reflected at the discontinuous interface. It is because the reflectance reduction effect by is impaired and the visibility of a printing image falls.
The refractive index difference (absolute value) between the low reflection resin layer and the transparent substrate is in the range of 0 to 0.5, particularly in the range of 0 to 0.2, and particularly in the range of 0 to 0.1 Is preferred.
In addition, although the refractive index of a transparent base material is determined in relationship with the refractive index of the low reflection resin layer mentioned above, it is preferable to exist in the range of 1.20-2.40, and in particular, 1.40-1 Within the range of .70 is preferred.

(C) Others The transparent low reflection layer of this specification may be formed by laminating a low reflection resin layer on a transparent substrate, and is formed by coextruding the resin of the transparent substrate and the low reflection resin layer It is also good.

The transparent low reflection layer of this specification may be formed on the printing layer via an adhesive layer, or may be formed directly on the printing layer by thermal lamination or the like.
The adhesive used for the adhesive layer is a known adhesive such as a pressure sensitive adhesive (pressure sensitive adhesive), a two-component curable adhesive, an ultraviolet curable adhesive, a thermosetting adhesive, a thermal melting adhesive and the like. Can be mentioned. Moreover, as a material of these adhesives, well-known resin, such as an acrylic resin, a urethane resin, a polyester resin, an epoxy resin, rubber | gum, is mentioned, for example.

  The thickness of the adhesive layer is not particularly limited as long as it can bond the transparent low reflection layer and the print layer with a desired strength and does not inhibit the visibility of the print image and the like in the print layer. It is preferable to set it in the range of 1000 μm.

  The adhesive layer is transparent to visible light in order to enable visual observation of a printed image in the underlying printing layer. Specifically, the light transmittance of the adhesive layer to the entire wavelength region of 380 nm to 780 nm of visible light is preferably 80% or more, more preferably 85% or more, and particularly preferably 90% or more.

The adhesive layer preferably has a refractive index approximately equal to the refractive index of the transparent substrate and the refractive index of the printing layer. The reason is the same as the reason for reducing the difference in refractive index between the transparent substrate and the low reflection resin layer described above.
The refractive index difference (absolute value) between the adhesive layer and the transparent substrate and the printing layer is in the range of 0 to 0.5, particularly in the range of 0 to 0.2, and particularly in the range of 0 to 0.1 Is preferred.
The value of the refractive index of the adhesive layer is determined in relation to the refractive indices of the transparent substrate and the printing layer, but is within the range of 1.20 to 2.40, and more preferably within the range of 1.40 to 1.70. preferable.

(2) Second specification of the transparent low reflection layer The second specification of the transparent low reflection layer (hereinafter, this specification may have this specification) is formed of a transparent resin and formed directly on the printing layer Be done. That is, the transparent low reflection layer of the present specification is a single layer formed of a transparent resin.
In the transparent low reflection layer of this specification, a large number of grooves are formed on the surface facing the surface located on the printing layer side with a predetermined variation.

  Unlike the transparent low reflection layer of the first specification described above, the transparent low reflection layer of the present specification is a single layer, and therefore no laminated interface is formed in the transparent low reflection layer. Therefore, it is possible to prevent the reflection of light at the laminated interface in the transparent low reflection layer.

  The transparent resin constituting the transparent low reflection layer of this specification may be the same as the transparent resin described in the section “(1) First specification of transparent low reflection layer (a) low reflection resin layer” described above. it can. In addition, the transparent low reflection layer of this specification contains, as necessary, any of the materials described in the section "(1) First specification of transparent low reflection layer (a) low reflection resin layer" above. Also good.

The thickness of the transparent low reflection layer of this specification can be made equal to the thickness of the above-mentioned "(1) First specification of transparent low reflection layer (a) low reflection resin layer".
In addition, the light transmittance and refractive index of the transparent low reflection layer of the present specification are the same as the contents described in the section of “(1) First specification of transparent low reflection layer (a) low reflection resin layer” described above. be able to.

  As a method of forming the transparent low reflection layer of this specification, for example, a method of applying a transparent resin constituting the transparent low reflection layer directly on the printing layer, forming it, and forming a large number of grooves on the surface, etc. Be

2. Printed Layer The printed layer in this embodiment is formed on a substrate.
The print layer is a layer on which a print image displayed by single color, multicolor or full color by subtractive color mixing is printed.

  The material of the print layer is not particularly limited as long as it is a material capable of printing a desired print image capable of color display by color reduction mixing, and examples thereof include resin inks containing a binder resin and a colorant.

  The binder resin contained in the resin ink is appropriately selected from known binder resins such as thermoplastic resins, thermosetting resins, ionizing radiation curable resins, etc., according to the required physical properties, printability and the like. Can. For example, in addition to cellulose resins and acrylic resins, urethane resins, vinyl chloride-vinyl acetate copolymers, polyester resins, alkyd resins, etc. can be used alone or in mixtures of these. These resins may be used alone or in combination of two or more.

  The coloring agent contained in the resin ink may be an inorganic pigment, an organic pigment or dye, a metal pigment composed of flakes such as aluminum and brass, and a flake like foil such as titanium dioxide coated mica and basic lead carbonate Pearl luster (pearl) pigment etc. are mentioned.

  Moreover, the said resin ink may contain arbitrary materials, such as a crosslinking agent, a stabilizer, a plasticizer, a hardening agent, according to a material.

  The thickness of the printing layer is appropriately selected according to the printing method of the printing layer, and specifically, it is in the range of 0.01 μm to 2000 μm, in particular in the range of 0.3 μm to 800 μm, in particular 0.8 μm to 400 μm It is preferable to be within the range. If the thickness of the print layer is thicker than the above range, the printed matter may be thickened, so that the processability of the print may decrease. On the other hand, if the thickness is thinner than the above range, the print layer is uniformly formed on the substrate This is because it is difficult to do so, and rubbing and unevenness may easily occur.

  As a printing image in the above-mentioned printing layer, a picture, a photograph, a letter, a number, a pattern, a draft, a mark, etc. are mentioned, for example.

  The printing layer may be formed on the entire area of one surface of the substrate, or may be formed on a part of one surface.

  The printing layer can be formed using a general printing method, and can be appropriately selected according to the type of material used for forming the printing layer. Specifically, known printing methods such as gravure printing, silk screen printing, offset printing, gravure offset printing, inkjet printing and the like can be mentioned.

3. The substrate in the present embodiment is not particularly limited as long as it has a self-supporting property to an extent capable of forming a printing layer, and a paper substrate, a metal substrate used in a general printing method, A resin base, cloth, ceramic or the like can be used.

It is preferable that the said base material has high light-shielding property. It is because the haze of a printing image may become high and visibility may fall by the light which injects from the base material side of printed matter.
The light shielding property of the above-mentioned substrate depends on the specification and use of the printed matter, the expression color of the printed image in the printing layer, etc., but the light transmittance for all wavelength region 380 nm to 780 nm of visible light is 3% or less (optical density OD Preferably 1.5 or more).

The said base material may be surface-treated in order to improve adhesiveness with a printing layer. Depending on the material of the substrate, the ink may be repelled when printing the printed image directly on the surface to form the printing layer, which may make it difficult to form the printing layer.
As the surface treatment, known surface modification techniques such as corona discharge treatment, flame treatment, ozone treatment, ultraviolet light treatment, radiation treatment, roughening treatment, chemical treatment, plasma treatment, and grafting treatment are applied. be able to.

4. Other Configurations The printed matter of the present embodiment is not particularly limited as long as it has the transparent low reflection layer, the printing layer, and the base material described above, and may have any layer as needed. As an optional layer, for example, a primer layer (adhesion stable layer) formed between the transparent low reflection layer and the printing layer, a printing adhesive layer or a printing adhesive layer for bonding a printed material to an adherend, etc. Can be mentioned.

5. Others In the printed matter of the present embodiment, a large number of grooves may be formed at least at a position overlapping in plan view with the print layer, and in particular, a large number of grooves in a position overlapping in plan view with the entire area of the substrate surface on which the print layer is formed. Is preferably formed.

  In the printed matter of the present embodiment, the maximum reflectance in the visible light range of 380 nm to 780 nm is preferably 2.0% or less, and more preferably 1.5% or less. The reason for this has been described in the section “1. Transparent low reflection layer” described above, so the description here is omitted.

6. Uses The printed matter of this aspect can be used for advertisements, posters, magazines, books, catalogs, decorative panels, automobile interior materials, and the like.

7. Manufacturing Method The method for manufacturing a printed matter according to this aspect can form a transparent low reflection layer on a substrate on which a printing layer is formed, and form a large number of grooves having a predetermined variation on the surface of the transparent low reflection layer. The method is not particularly limited as long as it is a method that can be used, and can be appropriately selected according to the specification of the transparent low reflection layer.

(1) First Example of Production Method For example, the printed material of the present embodiment has a concave pyramidal structure formed on the surface using a transfer master plate provided with a large number of convex pyramidal structures having a predetermined variation. A transfer plate preparation step of forming a first soft mold and forming a second soft mold having a convex pyramidal structure using the first soft mold, the convex pyramidal structure of the second soft mold Applying the composition for the transparent low reflection layer on the surface on which the coating layer is formed, and after the print layer side surface of the substrate on which the printing layer is formed is disposed on the coating layer, and curing the coating layer It can form by passing through the shaping process which exfoliates the said 2nd soft mold.
The printed matter of the present embodiment formed through the above-described steps has the transparent low reflection layer of the second specification, and the variation in the shape and the arrangement position of the grooves is an inversion of the convex pyramidal structure of the transfer master plate. It corresponds to the variation of the shape and the arrangement position.

(A) Transfer plate preparation step This step forms a first soft mold having a concave pyramidal structure formed on the surface, using a transfer master plate provided with a large number of convex pyramidal structures having a predetermined variation. And forming a second soft mold having a convex pyramidal structure using the first soft mold.

  First, a transfer master provided with a large number of convex pyramidal structures having a predetermined variation is prepared. The above-mentioned convex pyramidal structure corresponds to the inverted shape of the groove described in the above-mentioned "I. groove", and has a predetermined variation defined by quantification of three parameters.

The material of the transfer master plate is not particularly limited as long as it can form a convex pyramidal structure having a predetermined variation, and metal, resin and the like can be mentioned, and metal is preferable among them.
Further, the method of producing the transfer master plate is not particularly limited as long as it is a method capable of forming a convex pyramidal structure having a predetermined variation in shape and arrangement position on the surface. The transfer master plate can be formed, for example, by blasting the surface of a stainless steel plate and performing electrolytic plating on the machined surface of the stainless steel plate while gradually reducing the current value. Examples of the electrolytic plating treatment include treatments by electrolytic nickel plating, electrolytic chromium plating, electrolytic tin plating and the like.
At this time, by adjusting the surface roughness of the blast, it is possible to adjust the size, the arrangement interval, and the directivity of the top of the convex conical structure. In addition, the height of the convex conical structure can be adjusted by adjusting the ratio of decreasing the current value in stages.

  Next, a first composition for forming a soft mold containing a curable resin is applied on the surface of the obtained transfer base sheet on which the above-mentioned convex conical structure is formed, and the coating layer is cured to obtain a first composition. Transfer mold the soft mold. At this time, a concave pyramidal structure which is an inverted shape of the convex pyramidal structure is formed on one surface of the first soft mold.

The curable resin contained in the composition for forming the first soft mold may be any resin that can accurately transfer the shape of the convex pyramidal structure of the transfer master, for example, a photocurable resin, an electron A linear curable resin, a thermosetting resin, a thermoplastic resin or the like is used. In addition, it may contain any of the materials described in the section “1. Transparent low reflection layer” described above as needed.
The application method of the first composition for soft mold formation is not particularly limited, and may be the same as the method generally used in the formation of the resin original plate.

  Next, a composition for forming a second soft mold containing a curable resin is applied on the surface of the first soft mold on which the concave pyramidal structure is formed, and the coating layer is cured to obtain a second soft mold. Transcript form. At this time, on one surface of the second soft mold, a convex pyramidal structure which is an inverted shape of the concave pyramidal structure of the first soft mold is formed.

  The second soft mold may be any resin that can accurately transfer the shape of the concave pyramidal structure of the first soft mold, and is formed using the same composition for soft mold formation as the first soft mold. It may be formed using a soft mold forming composition different in composition.

  When the composition for transparent low reflection layer used in the application step described later contains a photocurable or electron beam curable resin, the second soft mold preferably has optical transparency. When arranging the base material in which the printing layer was formed on the application layer of composition for transparent low reflection layers, it irradiates with light, an electron beam, etc. from the 2nd soft mold side, and hardens the above-mentioned application layer It is because it can.

(B) Application process This process is a process of applying composition for transparent low reflex layers to the surface in which the convex type pyramidal structure of the 2nd soft mold was formed.
The composition for transparent low reflection layer contains the transparent resin described in the section “1. Specification of transparent low reflection layer (2) transparent low reflection layer” described above.
The application method of the composition for transparent low reflection layer is not particularly limited, and a conventionally known application method can be applied.

(C) Forming step In this step, the printing layer side surface of the substrate on which the printing layer is formed is disposed on the coating layer of the composition for transparent low reflection layer formed in the coating step, and the coating layer is formed It is a process which exfoliates the above-mentioned 2nd soft mold after hardening.
A printing layer formed on the substrate by curing the coating layer with light, heat or the like in a state where the printing layer on the substrate and the coating layer on the second soft mold are in contact with each other. A transparent low reflection layer can be formed on the top, which has a large number of grooves having a predetermined variation.

  About the hardening method and hardening conditions of an application layer, it can select suitably according to the kind of transparent resin contained in the composition for transparent low reflex layers. When the transparent resin is an ionizing radiation curable resin, an ultraviolet curing method, an electron beam curing method, etc. can be mentioned, and when the transparent resin is a thermosetting resin, a heat curing method, an ordinary temperature curing method, etc. can be mentioned. Moreover, when using a thermoplastic resin for transparent resin, the cooling method etc. which make a cooling roll etc. contact are also mentioned.

(2) Other Examples of Manufacturing Method As another method of manufacturing the printed matter of the present embodiment, a method of separately manufacturing a transparent low reflection layer and bonding a transparent low reflection layer and a substrate on which a printing layer is formed is there. By this method, a printed matter having a transparent low reflection layer of the first specification can be manufactured.
Specifically, in the application step described in the above-mentioned section “(1) Production method”, low reflection is achieved on the surface of the second soft mold on which the convex pyramidal structure is formed. The composition for resin layer is applied. Next, in the shaping step described in the above-mentioned section "(1) Production method", the transparent base material is disposed on the coating layer of the composition for a low reflection resin layer, and the coating layer is formed. It cures and peels off the second soft mold. Thereby, a transparent low reflection layer is obtained in which a low reflection resin layer having a large number of grooves having a predetermined variation on the surface is formed on one surface side of the transparent substrate. The composition for a low reflection resin layer contains the transparent resin described in the section “1. First specification of the transparent low reflection layer (1) transparent low reflection layer” described above.
Then, the obtained transparent low reflection layer is bonded on the printing layer formed on the base material through an adhesive layer as a bonding process. Thereby, the printed matter which has a transparent low reflection layer of the 1st specification can be manufactured.

  In addition, as another manufacturing method of the printed matter having the transparent low reflection layer of the second specification of the present aspect, it is obtained after the transfer plate preparing step described in the above-mentioned "(1) first example of manufacturing method" section. A transfer roll preparation step of preparing a transfer roll by winding the second soft mold around a roll, and applying a composition for transparent low reflection layer to the surface of a printing layer formed on a substrate, and applying it by the transfer roll It is also possible to use a method comprising a shaping step of pressing the layer and simultaneously curing the coating layer to form a transparent low reflection layer.

  Furthermore, as another manufacturing method of the printed matter having the transparent low reflection layer according to the second specification of the present aspect, by plating the surface of the cylindrical cylinder, a large number of convex pyramidal structures having a predetermined variation are surfaced. Forming a roll original plate formed on the substrate, applying the transparent low reflection layer composition on the surface of the printing layer formed on the substrate, and pressing the coated layer with the roll original plate. It is also possible to use a method having a forming step of simultaneously curing the coating layer to form a transparent low reflection layer. The preparation method of the roll original plate can be the same as the preparation method of the transfer original plate described in the section of “(1) First example of manufacturing method” described above.

  In each of the manufacturing methods described above, the method of curing the composition for the transparent low reflection layer performed simultaneously with pressing may be any curing method suitable for the composition for the transparent low reflection layer, and should be appropriately selected according to the composition etc. Can. For example, when the composition for transparent low reflection layer contains an ultraviolet curable resin, a curing method by ultraviolet irradiation can be used.

B. Second Aspect Next, the second aspect of the printed matter of the present invention (hereinafter, this section may be referred to as the present aspect) will be described.
In the printed matter of the present embodiment, a large number of the grooves are formed on the surface of the printing layer.
Specifically, the printed matter of the present embodiment has a substrate and a printing layer formed on the substrate, and the above-described many grooves are formed on the surface of the printing layer with a predetermined variation. ing. In this aspect, the print layer is usually located on the outermost surface of the print layer side of the printed matter.

The printed matter of this aspect will be described with reference to the drawings. FIG. 6 is a schematic cross-sectional view showing an example of the printed matter of the present embodiment. As shown in FIG. 6, the printed matter 10 of this embodiment has the base material 2 and the printing layer 3 formed on the base material 2, and the surface of the printing layer 3 has a predetermined variation in shape and arrangement position And a plurality of grooves 1 having
In the printed matter of the present embodiment, the predetermined variation of a large number of grooves is defined by quantifying three parameters. The three parameters for causing a large number of groove portions to have a predetermined variation and the predetermined values thereof are the same as the contents described in the section of “I. groove portion” described above, and thus the description thereof is omitted here.

  In this aspect, the number of layers constituting the printed matter can be reduced, and light reflection at the laminated interface can be prevented. Further, since the printed matter can be made thin, it is possible to obtain a printed matter having high processability.

  Hereinafter, the printed matter of this aspect will be described. The details of the base material in this aspect, the details of the other configurations, the physical properties of the printed matter in this aspect, and the details of the application and the like may be the same as the contents described in the section of “A. Since it can be done, the explanation here is omitted.

1. Printed Layer The printed layer in this embodiment is formed on a substrate, and a large number of grooves are formed on the surface with a predetermined variation.
The printing layer in this embodiment is a layer on which a printing image displayed in single color, multicolor or full color by subtractive color mixing is printed.

(1) Structure of Printed Layer The printed layer in the present embodiment usually has a large number of grooves on the surface. The details of the grooves formed on the surface of the print layer are the same as the contents described in the section “I. Groove” above, and thus the description thereof is omitted here.

Moreover, it is preferable that the printing layer of this aspect has the base part 5 which supports many groove parts 1 so that it may illustrate in FIG. FIG. 7 is an explanatory view for explaining a print layer in this aspect, and is an enlarged view of a portion P of FIG.
The thickness of the base is not particularly limited as long as it can support a large number of grooves having shapes and variations and can form a desired print image, but for example, within the range of 0.3 μm to 100 mm. Among them, it is preferable to be in the range of 6 μm to 30 mm, particularly in the range of 9 μm to 15 mm. If the thickness of the base portion is less than the above range, it is difficult to form a large number of grooves so as to have a predetermined variation on the print layer, or it is difficult to form a desired print image by the print layer Because it can be On the other hand, when the thickness of the base portion exceeds the above range, the thickness of the entire printed matter is increased, and the processability is deteriorated, or the printed layer is easily cracked.

The thickness of the base refers to the average value of the length from the surface of the print layer in contact with the substrate to the tip of the groove bottom (the length of the portion indicated by h ₂ in FIG. 7). After measuring the height (h ₁ + h ₂ ) from the surface in contact with the substrate of the print layer to the surface having the groove opening of the groove using (Thickness tester H-102 for film made by Tester Sangyo Co., Ltd.), It can be calculated by subtracting the depth h ₁ of.

(2) Material of Printed Layer The material of the printed layer in this aspect can print a desired printed image capable of color display by subtractive color mixing, and can form a large number of grooves having a predetermined variation on the surface. Any material may be used, and among these, a resin ink containing a binder resin and a colorant is preferable.

As binder resin contained in the said resin ink, the printing layer which comprises a printing image can be formed in the base-material surface of printed matter, and many groove parts have predetermined | prescribed dispersion | variation in the surface of the printing layer formed. As long as it is a resin material which can be shaped like, it will not be limited in particular. Among them, the binder resin is preferably a curable resin. It is because it becomes possible to form a desired groove part precisely on the printing layer surface.
As the curable resin, for example, the curable resin described in the section of “A. First embodiment 1. Transparent low reflection layer (1) First specification of transparent low reflection layer (a) low reflection resin layer” Can be mentioned.

  The coloring agent can be the same as the coloring agent described in the section “A. First embodiment 2. Printing layer” described above, and therefore the description thereof is omitted here.

  The above-mentioned resin ink includes the aforementioned "A. First embodiment 1. Transparent low reflection layer (1) First specification of transparent low reflection layer (a) Low reflection resin layer" and "A. First embodiment 2. Printed layer" You may contain any material mentioned by the term of "."

(3) Others The print image in the print layer is the same as the content described in the section “A. First aspect” described above, and thus the description thereof is omitted here.

  The thickness of the printing layer in this aspect may be appropriately designed as long as it can provide the depth of the groove portion and the height of the base portion described above.

  The method of forming the printing layer in this aspect can be appropriately selected depending on the shape of the groove formed on the surface of the printing layer, the material of the printing layer, the use of the printed matter, etc. For example, It can be formed using the method described in the section.

2. Other Configurations The printed matter of the present embodiment is not particularly limited as long as it has a printed layer formed such that a large number of grooves have a predetermined variation, and a substrate, and as necessary, the printed matter And an optional layer such as an adhesive layer for printing or an adhesive layer for printing for laminating an adherend to an adherend.

3. Others In the printed matter of the present embodiment, as illustrated in FIG. 6, the printing layer may be formed on the entire area of one side of the substrate, and although not shown, may be formed on a part of the substrate surface .
The maximum reflectance of the printed matter of the present embodiment is the same as the printed matter described in the section “A. First embodiment” described above, and thus the description thereof is omitted here.

4. Manufacturing method The manufacturing method of the printed matter of this aspect is not particularly limited as long as it is a method capable of forming a large number of grooves on the surface of the printing layer so as to have a predetermined variation.
For example, the transfer plate preparation step described in the section “A. First embodiment 7. Production method (1) First example of production method (a) Transfer plate preparation step”, printing including resin ink on a substrate A printing step of printing the layer composition to form a printing layer, and pressing the surface of the second soft mold on which the convex pyramidal structure is formed on the printing layer on the base material by pressure The printed material of this aspect can be manufactured by passing through a shaping process of peeling the second soft mold after loading the load and curing the printing layer.
The transfer plate preparation step and the shaping step can be the same as the contents described in the section of “A. First embodiment 7. Manufacturing method (1) First example of manufacturing method” described above.

In the printing step, as a method of printing the composition for printing layer, a printing layer capable of forming a desired print image can be formed on a substrate, and desired on the surface in a shaping step. It is not particularly limited as long as it is a method capable of forming a layer capable of forming a groove. For example, the method described in the above-mentioned section “A. First embodiment 2. Printing layer” can be used.
The materials contained in the composition for printing layer are the same as those described in the section of “1. Printing layer” described above, and thus the description thereof is omitted here.

  The present invention is not limited to the above embodiment. The above embodiment is an exemplification, and it has substantially the same configuration as the technical idea described in the claims of the present invention, and any one having the same function and effect can be used. It is included in the technical scope of the invention.

  Hereinafter, the present invention will be described in more detail by way of Examples and Comparative Examples.

1. Preparation of Single-Colored Printed Matter A single-colored printed matter was obtained by the following method.

Example 1-1
(Preparation of transfer master)
It was blasted to a stainless steel plate and finished so that the arithmetic mean surface roughness (hereinafter referred to as Sa) in three-dimensional surface roughness measurement would be 0.35 μm. Electrolytic chromium plating was performed on the surface under the following conditions to obtain a transfer master plate A having a large number of convex pyramidal structures A on the plate surface. The inverted shape and the variation of the convex pyramidal structure A correspond to the shape and the variation of the groove portion A formed on the surface of the obtained printed matter.

<Conditions of electrolytic chromium plating>
Using a plating bath containing the following composition and using a graphite electrode as the anode, the current density is reduced by 3.0 A / dm ² every one minute from 80 A / dm ² to a final value of 20 A / dm ² A black chromium plating film was formed on a stainless steel plate by electrolytic plating.
<< Composition of plating bath >>
・ Chromium chloride: 200 g / dm ³ (0.75 mol / dm ³ )
Ammonium chloride: 30 g / dm ³ (0.56 mol / dm ³ )
-Oxalic acid: 3 g / dm ³ (0.024 mol / dm ³ )
Barium carbonate: 5 g / dm ³ (0.025 mol / dm ³ )
· Boric acid: 30 g / dm ³ (0.49 mol / dm ³ )
Barium fluoride: 10 g / dm ³ (0.057 mol / dm ³ )

(Production of first soft mold)
A composition for forming an ultraviolet-curable soft mold having the following composition is coated on the plate surface on which the convex pyramidal structure A of the transfer master plate A is formed, and a 0.2 mm thick polycarbonate (PC) film (pan The film was sandwiched with a light film (manufactured by Teijin Chemicals Ltd.), and UV irradiation was performed at a wavelength of 365 nm and an irradiation energy of 170 mJ / cm ² from the PC film side. The convex pyramidal structure A of the transfer master plate A was transferred, and after the composition for soft mold formation was cured, the transfer master plate A was peeled off to obtain a first soft mold.

<Composition for forming a soft mold>
-Urethane acrylate ... 35% by mass
・ 1,6-Hexanediol diacrylate ... 35% by mass
-Pentaerythritol triacrylate ... 10% by mass
・ Vinylpyrrolidone ... 15% by mass
・ 1-hydroxycyclohexyl phenyl ketone ... 2% by mass
-Benzophenone 2% by mass
・ Polyether modified silicone oil ... 1% by mass

(Production of second soft mold)
The same composition for soft mold formation as in the first soft mold is coated on the surface of the first soft mold on which the inverted shape of the convex pyramidal structure A is formed, and a polycarbonate (PC) film with a thickness of 0.2 mm (Panlite film, manufactured by Teijin Chemicals Co., Ltd.) was cured by UV irradiation with a wavelength of 365 nm and irradiation energy of 170 mJ / cm ² from the PC film side. Thereafter, the first soft mold was peeled off to obtain a second soft mold on the surface of which a convex pyramidal structure A ′ having the same shape as the convex pyramidal structure A was formed.

(Production of single color print)
Gravure printing was used on the resin base material, and the entire surface was color code No. The print layer was formed by using a pattern consisting of the black print layer of 582 as a print image. In addition, the color of a printing layer specified the color code by DIC. The same applies to multicolor printed matter described later.

On the surface of the obtained second soft mold on which the convex pyramidal structure A 'is formed, the composition for the ultraviolet curable transparent low reflection layer having the following composition is applied, and black printing is performed on the applied surface. The resin base on which the black print layer was formed was disposed such that the layer was disposed.
The composition for the transparent low reflection layer is cured by UV irradiation with a wavelength of 365 nm and irradiation energy of 170 mJ / cm ² from the PC film side of the second soft mold, and then the second soft mold is peeled off and the outermost surface A single-color print having a large number of grooves A is obtained.

<Composition for transparent low reflection layer>
-Urethane acrylate ... 35% by mass
・ 1,6-Hexanediol diacrylate ... 35% by mass
-Pentaerythritol triacrylate ... 10% by mass
・ Vinylpyrrolidone ... 15% by mass
・ 1-hydroxycyclohexyl phenyl ketone ... 2% by mass
-Benzophenone 2% by mass
・ Polyether modified silicone oil ... 1% by mass

Example 2-1
It blast-processed to the stainless steel board and was referred to as Sa = 0.3 micrometer. Electrolytic chromium plating was performed on the surface under the following conditions to obtain a transfer master B having a large number of convex pyramidal structures B on the printing plate surface. The inverted shape and the variation of the convex pyramidal structure B corresponded to the shape and the variation of the groove B in the obtained printed matter.

<Conditions of electrolytic chromium plating>
Using the same plating bath and the anode as in Example 1, was reduced by 2.0A / dm ² per minute current density from 80A / dm ^2, and finally the 20A / dm ^2, electrolytic plating on stainless steel plate Thus, a black chromium plating film was formed.

  A single-color print having a large number of grooves B on the outermost surface was obtained in the same manner as in Example 1-1 except that the transfer master plate B was used instead of the transfer master plate A.

Example 3-1
It blast-processed to the stainless steel board and was referred to as Sa = 0.25 micrometer. Electrolytic chromium plating was performed on the surface under the following conditions to obtain a transfer master C having a large number of convex pyramidal structures C on the plate surface. The inverted shape and the variation of the convex pyramidal structure C corresponded to the shape and the variation of the groove portion C in the obtained printed matter.

<Conditions of electrolytic chromium plating>
Using the same plating bath and anode as in Example 1, reducing the current density from 80 A / dm ² to 1.5 A / dm ² every one minute to make the final 20 A / dm ^2, and electroplating on a stainless steel plate Thus, a black chromium plating film was formed.

  A single-color printed matter provided with a large number of groove portions C on the outermost surface was obtained in the same manner as in Example 1-1 except that the transfer master plate C was used instead of the transfer master plate A.

Example 4-1
It blast-processed to the stainless steel board and was referred to as Sa = 0.3 micrometer. Electrolytic chromium plating was performed on the surface under the following conditions to obtain a transfer master D having a large number of convex pyramidal structures D on the printing plate surface. The inverted shape and the variation of the convex pyramidal structure D corresponded to the shape and the variation of the groove D in the obtained printed matter.

<Conditions of electrolytic chromium plating>
Using the same plating bath and anode as in Example 1, reducing the current density from 80 A / dm ² to 1.0 A / dm ² every one minute to make it finally 20 A / dm ² and electroplating on a stainless steel plate Thus, a black chromium plating film was formed.

  A single-color printed matter having a large number of groove portions D on the outermost surface was obtained in the same manner as in Example 1-1 except that the transfer master plate D was used instead of the transfer master plate A.

Example 5-1
It blast-processed to the stainless steel board and was referred to as Sa = 0.3 micrometer. Electrolytic chromium plating was performed on the surface under the following conditions to obtain a transfer master plate E having a large number of convex pyramidal structures E on the plate surface. The inverted shape and the variation of the convex pyramidal structure E corresponded to the shape and the variation of the groove portion E in the obtained printed matter.

<Conditions of electrolytic chromium plating>
Using the same plating bath and the anode as in Example 1, was reduced by 2.0A / dm ² per minute current density from 80A / dm ^2, and finally the 20A / dm ^2, electrolytic plating on stainless steel plate Thus, a black chromium plating film was formed.

  A single-color printed matter having a large number of groove portions E on the outermost surface was obtained in the same manner as in Example 1-1 except that the transfer master plate E was used instead of the transfer master plate A.

Example 6-1
It blast-processed to the stainless steel board and was referred to as Sa = 0.3 micrometer. Electrolytic chromium plating was performed on the surface under the following conditions to obtain a transfer master plate F having a large number of convex pyramidal structures F on the plate surface. The inverted shape and the variation of the convex pyramidal structure F corresponded to the shape and the variation of the groove portion F in the obtained printed matter.

<Conditions of electrolytic chromium plating>
Using the same plating bath and anode as in Example 1, the current density is decreased by 0.5 A / dm ² every one minute from 80 A / dm ² to 20 A / dm ² finally, and electrolytic plating is performed on a stainless steel plate. Thus, a black chromium plating film was formed.

  A single-color printed matter having a large number of grooves F on the outermost surface was obtained in the same manner as in Example 1-1 except that the transfer master plate F was used instead of the transfer master plate A.

[Example 7-1]
It blast-processed to the stainless steel board and was referred to as Sa = 0.25 micrometer. Electrolytic chromium plating was performed on the surface under the following conditions to obtain a transfer master plate G having a large number of convex pyramidal structures G on the plate surface. The inverted shape and the variation of the convex pyramidal structure G corresponded to the shape and the variation of the groove G in the obtained printed matter.

<Conditions of electrolytic chromium plating>
Using the same plating bath and the anode as in Example 1, was reduced by 5.0A / dm ² per minute current density from 80A / dm ^2, and finally the 20A / dm ^2, electrolytic plating on stainless steel plate Thus, a black chromium plating film was formed.

  A single-color print having a large number of grooves G on the outermost surface was obtained in the same manner as in Example 1-1 except that the transfer master plate A was used instead of the transfer master plate A.

Comparative Example 1-1
It blast-processed to the stainless steel board and was referred to as Sa = 0.3 micrometer. Electrolytic chromium plating was performed on the surface under the following conditions to obtain a transfer master plate H having a large number of convex pyramidal structures H on the plate surface. The inverted shape and the variation of the convex pyramidal structure H corresponded to the shape and the variation of the groove portion H in the obtained printed matter.

<Conditions of electrolytic chromium plating>
Using the same plating bath and anode as in Example 1, reducing the current density from 80 A / dm ² to 0.4 A / dm ² every one minute to make the final 20 A / dm ² , electroplating on a stainless steel plate Thus, a black chromium plating film was formed.

  A single-color print including a large number of grooves H on the outermost surface was obtained in the same manner as in Example 1-1 except that the transfer master plate A was used instead of the transfer master plate A.

Comparative Example 2-1
It blast-processed to the stainless steel board and was referred to as Sa = 0.3 micrometer. Electrolytic chromium plating was performed on the surface under the following conditions to obtain a transfer master plate I having a large number of convex pyramidal structures I on the plate surface. The inverted shape and the variation of the convex pyramidal structure I corresponded to the shape and the variation of the groove portion I in the obtained printed matter.

<Conditions of electrolytic chromium plating>
Using the same plating bath and anode as in Example 1, reducing the current density from 80 A / dm ² to 6.0 A / dm ² every one minute to make the final 20 A / dm ² , electroplating on a stainless steel plate Thus, a black chromium plating film was formed.

  A single-color printed matter having a large number of grooves I on the outermost surface was obtained in the same manner as in Example 1-1 except that the transfer master plate I was used instead of the transfer master plate A.

Comparative Example 3-1
It blast-processed to the stainless steel board and was referred to as Sa = 0.3 micrometer. Electrolytic chromium plating was performed on the surface under the following conditions to obtain a transfer master plate J having a large number of convex pyramidal structures J on the plate surface. The inverted shape and the variation of the convex pyramidal structure J corresponded to the shape and the variation of the groove portion J in the obtained printed matter.

<Conditions of electrolytic chromium plating>
Using the same plating bath and anode as in Example 1, the current density is reduced by 2.0 A / dm ² every 80 minutes from 1 A ² per minute to a final 10 A / dm ² and electrolytic plating on a stainless steel plate Thus, a black chromium plating film was formed.

  In the same manner as in Example 1-1 except that the transfer master plate J was used instead of the transfer master plate A, a single-color print including a large number of groove portions J on the outermost surface was obtained.

Comparative Example 4-1
It blast-processed to the stainless steel board and was referred to as Sa = 0.5 micrometer. Electrolytic chromium plating was performed on the surface under the following conditions to obtain a transfer master plate K having a large number of convex pyramidal structures K on the plate surface. The inverted shape and the variation of the convex pyramidal structure K corresponded to the shape and the variation of the groove portion K in the obtained printed matter.

<Conditions of electrolytic chromium plating>
Using the same plating bath and the anode as in Example 1, was reduced by 1.8A / dm ² per minute current density from 80A / dm ^2, and finally the 20A / dm ^2, electrolytic plating on stainless steel plate Thus, a black chromium plating film was formed.

  In the same manner as in Example 1-1 except that the transfer master plate K was used instead of the transfer master plate A, a single-color print having a large number of groove portions K on the outermost surface was obtained.

2. Preparation of Multicolor Printed Matter A multicolored printed matter was prepared by the following method.

[Example 1-2]
A multi-color printed matter having a large number of groove portions on the outermost surface was obtained in the same manner as in Example 1-1 except that a printing layer having the following printing image was formed on a resin substrate using a gravure printing method.
(Printed layer)
In the print image of the print layer, the background is color code No. No. 582 black printed layer, white, color code no. 125 yellow printed layers, color code no. 564 red printed layer, color code no. 649 green print layer, color code no. It was set as the pattern in which alphabets A to Z are displayed with a size of 20 pt using 578 blue print layers.

[Example 2-2]
A multicolor printed matter having a large number of grooves B on the outermost surface was obtained in the same manner as in Example 1-2 except that the transfer master plate B was used instead of the transfer master plate A.

[Example 3-2]
A multicolor printed matter having a large number of grooves C on the outermost surface was obtained in the same manner as in Example 1-2 except that the transfer master plate A was used instead of the transfer master plate A.

Example 4-2
A multi-color printed matter having a large number of grooves D on the outermost surface was obtained in the same manner as in Example 1-2 except that the transfer master plate D was used instead of the transfer master plate A.

Example 5-2
A multi-color printed matter provided with a large number of groove portions E on the outermost surface was obtained in the same manner as in Example 1-2 except that the transfer master plate E was used instead of the transfer master plate A.

Example 6-2
A multi-color printed matter having a large number of grooves F on the outermost surface was obtained in the same manner as in Example 1-2 except that the transfer master plate F was used instead of the transfer master plate A.

[Example 7-2]
A multicolor printed matter having a large number of grooves G on the outermost surface was obtained in the same manner as in Example 1-2 except that the transfer master plate A was used instead of the transfer master plate A.

Comparative Example 1-2
A multi-color printed matter having a large number of grooves H on the outermost surface was obtained in the same manner as in Example 1-2 except that the transfer master plate H was used instead of the transfer master plate A.

Comparative Example 2-2
A multi-color printed matter provided with a large number of grooves I on the outermost surface was obtained in the same manner as in Example 1-2 except that the transfer master plate I was used instead of the transfer master plate A.

Comparative Example 3-2
A multicolor printed matter having a large number of grooves J on the outermost surface was obtained in the same manner as in Example 1-2 except that the transfer master plate A was used and the transfer master plate J was used instead.

Comparative Example 4-2
A multi-color printed matter having a large number of grooves K on the outermost surface was obtained in the same manner as in Example 1-2 except that the transfer master plate A was used instead of the transfer master plate A.

[Evaluation 1]
SEM observation was performed on the following conditions about the single color printed matter and multi-color printed matter obtained by Examples 1-7 and Comparative Examples 1-4. Scores shown in Table 1 are extracted from a large number of grooves formed on the surface of the printed matter, and the area of the groove opening, the maximum internal angle of the groove opening, and the distance between nearest gravity centers of adjacent grooves are averaged from the planar view SEM image. I asked for the variance. In addition, about quantification of each parameter using a planar view SEM image, the method demonstrated by the term of the above-mentioned "I. groove part" was used.
(conditions)
SEM: Field emission scanning electron microscope S-4500 (manufactured by Hitachi High-Technologies Corporation)
· Observation method: Top-View (from the side with the groove)
Pretreatment: Pt-Pd sputtering Observation magnification: 10 k
・ Field of view range: 4 μm long × 4 μm wide

[Evaluation 2]
The maximum reflectance was measured under the following conditions using the monochromatic printed matter obtained in Examples 1-1 to 7-1 and Comparative Examples 1-1 to 4-1.
(conditions)
・ Measurement device: Scanning Spectrophotometer UV-3100PC (made by Shimadzu Corporation)
・ Measurement method: Total reflection for 8 ° incident light (wavelength range 380 nm to 780 nm)

[Evaluation 3]
The color of the multicolor printed matter obtained in Examples 1-2 to 7-2 and Comparative Examples 1-2 to 4-2 was visually confirmed, and the visibility of the printed image was evaluated. The evaluation method was based on the following criteria, based on the clearness of the color of the multicolor printed matter of the comparative example as a reference (Δ), and whether the color of the multicolored printed matter of the example was clear as compared to the reference.
... ... The color is very sharp compared to the standard, and the visibility is very good.
○ ... The color is clearer than the standard and the visibility is good.
... ... standard.

The results of evaluations 1 to 3 are shown in Table 1. In Table 1, μ is an average, and σ ² is a dispersion.

  From the above results, by forming the groove portion having a predetermined variation on the outermost surface of the printed matter, the color becomes clear, and the visibility of the printed image can be improved.

DESCRIPTION OF SYMBOLS 1 ... Groove part 2 ... Base material 3 ... Printing layer 4 ... Transparent low reflection layer 10 ... Printed matter 11 ... Transparent base material 12 ... Low reflection resin layer

Claims (5)

A substrate,
A printed material having a printing layer on the substrate,
The outermost surface of the printed matter on the printed layer side has a plurality of grooves.
The maximum reflectance is 2.0% or less when light of a wavelength range of 380 nm to 780 nm is irradiated at an incident angle of 8 °,
The groove has an average area of 94000 nm ² or more and 131000 nm ² or less when the planar view shape of the groove mouth portion which is a region surrounded by the side surface of the groove is approximated to an octagon ,
The dispersion of the maximum internal angle when the planar view shape of the groove mouth portion of the groove portion is approximated to an octagon is within a range of 600 (°) ² or more and 10 20 (°) ² or less,
Between the center of gravity of one groove portion and another groove portion having the center of gravity of the groove portion at a position closest to the center of gravity when the planar view shape of the groove portion of the groove portion is approximated to an octagon Printed matter whose average of distance is 500 nm or less . Having a transparent low reflection layer on the print layer,
The printed matter according to claim 1, further comprising a plurality of the grooves on the surface of the transparent low reflection layer. The transparent low reflection layer has a transparent base and a low reflection resin layer on one side of the transparent base,
The low reflection resin layer has a transparent resin,
The printed matter according to claim 2, wherein a plurality of the groove portions are provided on the surface of the low reflection resin layer opposite to the surface in contact with the transparent base material. The transparent low reflection layer has a transparent resin,
The printed matter according to claim 2, wherein the transparent low reflection layer and the print layer are in contact with each other.   The printed matter according to claim 1, comprising a plurality of the grooves on the surface of the print layer.