JP6743363B2 - Printed matter - Google Patents

Description

The present invention relates to a printed material having a large number of grooves on its surface.

In various printed materials such as advertisements, magazines, and posters, it has been required in recent years to display a print image with higher definition and higher definition. In the field of printing technology, a method of outputting image data to a printing medium, printing It is considered to use all printing techniques such as a method of selecting a material used for a medium and a material of an 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 printed matter, so that the observer actually sees There was a problem in that it was observed as whitish as compared to the color of the printed image, which hinders the reading of characters and patterns.
In addition, depending on the intensity of light radiated on the surface of the printed matter, the irradiation direction, and the direction in which the observer observes the printed matter, the visibility of the printed image may be reduced due to the reflected light from the surface of the printed matter, or it may be difficult to see the image. There was a problem that could be.

For such a problem, a printed matter in which the surface of the printed matter is processed has been proposed for the purpose of reducing the reflection of light on the surface and improving the visibility of the printed image. For example, Patent Documents 1 and 2 disclose printed matter having a large number of fine irregularities called moth-eyes formed on the surface. Since fine irregularities are formed on the surface of the printed matter with regularity in shape and arrangement, the principle of the moth-eye structure eliminates abrupt changes in the refractive index with respect to incident light, resulting in imperfections at the material interface. It is possible to suppress the reflection of light due to the continuous change in the 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.

JP2012-152987A JP, 2014-71220, A

However, although it is possible to obtain the reflectance reduction effect by having fine irregularities on the surface of the printed matter, the shape and arrangement of the individual protrusions (protrusions) and recesses (grooves) have regularity. There is a case where the reflectance shows wavelength selectivity, and depending on the wavelength region, a sufficient reflectance reduction effect due to fine irregularities cannot be obtained, and the sharpness and 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 a main object of the present invention is to provide a printed matter capable of clearly displaying the color of a printed image and improving the visibility of the printed image. To do.

In order to solve the above problems, the present invention is a printed material having a transparent substrate and a printed layer formed on one surface of the transparent substrate, wherein the printed material is the transparent substrate described above. A large number of groove portions are formed on the outermost surface on the side opposite to the surface on which the printed layer is formed, and the groove portion has an octagonal plan view shape of the groove mouth portion which is a region surrounded by the side surfaces of the groove portion. The average area when approximated is in the range of 94000 nm ² or more and 131000 nm ² or less, and the dispersion of the maximum internal angle when the plan view shape of the groove mouth portion of the groove portion is approximated to an octagon is in the range of 600 or more and 1020 or less. The one of the groove portion, and the other groove portion having the center of gravity of the groove mouth portion at a position closest to the center of gravity when the shape of the groove mouth portion of the one groove portion in plan view is approximated to an octagon. Provided is a printed matter characterized in that the average distance between the centers of gravity is 500 nm or less and the dispersion of the distance between the centers of gravity is 8000 or more.

According to the present invention, since a large number of groove portions having a predetermined variation in shape and arrangement position are formed on the outermost surface on the side facing the surface on which the print layer of the transparent substrate of the printed matter is formed, It is possible to reflect the light a number of times in the groove portion, and it is possible to suppress the increase in the intensity of the light having the specific wavelength due to the interference. Further, in the groove portion, in addition to absorption of light due to multiple reflection of light, absorption of light into the printed matter due to Mie scattering also occurs, so that the reflectance can be reduced. Furthermore, a layer in which a large number of the above-mentioned groove portions are formed can exhibit a high haze value due to Mie scattering, thereby reducing the total reflection at the groove-formed surface or the laminate interface in the printed matter. It is possible to further increase the absorptance of light other than the light relating to the color tone of the printed matter.
As a result, the printed matter of the present invention can exhibit an excellent reflectance reduction effect for light in a wide wavelength range due to the groove portion having a predetermined variation, and it is possible to improve the visibility of the printed image. .. Further, the light incident on the printed matter, in particular, the reflection of light other than the light relating to the color tone of the printed matter is reduced, and since the absorptance of the light in the printed matter is increased, the color developability of the printed image in the printed layer is improved, It is possible to display colors clearly.

In the above invention, a transparent low reflection layer is formed on the surface of the transparent substrate facing the surface on which the printed layer is formed, and a large number of transparent low reflection layers are formed on the surface of the transparent low reflection layer facing the transparent substrate. It is preferable that the above-mentioned groove part is formed. When it is difficult to form the groove directly on the surface of the transparent substrate, by providing the transparent low reflection layer having the desired groove formed as the outermost surface layer of the printed matter, the above-mentioned groove portion having a predetermined variation is formed. This is because the effect can be achieved.

In the case of the above-mentioned invention, the transparent low-reflection layer has a transparent support layer and a low-reflection resin layer formed on one surface side of the transparent support layer and containing a transparent resin. It is preferable that a large number of the groove portions are formed on the surface facing the surface in contact with the transparent support layer. The groove portion of the transparent low reflection layer can be arranged in alignment with the position of the printing layer through the transparent base material, the visibility of the printed image can be improved, and the handling property during manufacturing is improved. Because. Furthermore, when it is difficult to form a transparent low-reflection layer having a groove directly on the surface of the transparent substrate because the transparent substrate has a curved surface, the adhesion of the transparent substrate is poor, or the like, it is desirable. This is because it can be a printed matter.

Further, in the case of the above invention, it is preferable that the transparent low reflection layer is a single layer formed of a transparent resin and is directly formed on the transparent substrate. Since the transparent low-reflection layer is a single layer formed of a transparent resin and the laminated interface is not 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 groove portions are directly formed on a surface of the transparent substrate facing the surface on which the print layer is formed. This is because it is possible to reduce the number of layers constituting the printed matter of the present invention, and it is possible to prevent reflection of light at the laminated interface.

In the above-mentioned invention, it is preferable to have a functional layer on at least the surface of the above-mentioned printing layer which faces the surface in contact with the above-mentioned transparent substrate. By providing at least a functional layer on the surface of the printing layer, it is possible to add a function according to the type of the functional layer and to improve the color reproducibility and the visibility of the printed image by the light control by the functional layer. .. Further, it is possible to protect the print layer by providing the functional layer on the surface of the print layer.

In the case of the above invention, it is preferable that the functional layer is a light shielding layer. Light is transmitted from the print layer side surface of the printed matter, so that the haze is conspicuous in the printed image displayed through the groove and the visibility is reduced, and the vivid color display is disturbed and the color reproducibility is reduced. This is because it is possible to prevent

In the printed matter of the present invention, the numerous groove portions formed on the outermost surface have a predetermined variation in shape and arrangement position, so that the reflectance reduction effect is exhibited for light in a wide wavelength range, so that the printed image It is possible to improve the visibility of the image and to display the color of the printed image clearly.

It is explanatory drawing explaining the groove part in this invention. It is explanatory drawing explaining the groove part in this 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 1st aspect of the printed matter of this invention. It is a schematic sectional drawing which shows the other example of the 1st aspect of the printed matter of this invention. It is a schematic sectional drawing which shows the other example of the 1st aspect of the printed matter of this invention. It is a schematic sectional drawing which shows the other example of the 1st aspect of the printed matter of this invention. It is a schematic sectional drawing which shows an example of the 2nd aspect of the printed matter of this invention. It is explanatory drawing explaining the transparent base material in the 2nd aspect of the printed matter of this invention.

Hereinafter, the printed material of the present invention will be described in detail.
The printed matter of the present invention is a printed matter having a transparent base material and a printed layer formed on one surface of the transparent base material, and the printed matter has the printed layer of the transparent base material formed thereon. A large number of groove portions are formed on the outermost surface on the surface side facing the surface, and the groove portion has an area when the plan view shape of the groove mouth portion which is a region surrounded by the side surfaces of the groove portion is approximated to an octagon. the average is in the range of 94000Nm ² more 131000Nm ² or less is in the maximum range variance of 600 1020 the following internal angle when the plan view shape of the groove opening portion of the groove close to the octagonal one of the Groove portion, the distance between the center of gravity of the other groove portion having the center of gravity of the groove mouth portion at the position closest to the center of gravity when the plan view shape of the groove mouth portion of the one groove portion is approximated to an octagon (hereinafter, The closest center of gravity position may be referred to as "), and the dispersion of the distance between the centers of gravity is 8000 or more.

According to the present invention, since a large number of grooves having predetermined variations in shape and arrangement position are formed on the outermost surface of the printed matter, the grooves have an excellent reflectance reduction effect for light in a wide wavelength range. Can be demonstrated. Note that variations in the shapes and arrangement positions of many groove portions may be simply referred to as “variations”.
That is, since a large number of grooves have the above-mentioned predetermined variation, the 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 prevent the strength from increasing.
Furthermore, since a large number of groove portions have the predetermined variation, the groove portions are formed by multiple reflections in the groove portions, especially in the groove mouth portion which is located in the outermost surface of the printed matter and is surrounded by the groove side surfaces. In addition to absorbing light into the layer in which the groove is formed, Mie scattering of the 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, thus increasing the reflectance. It is possible to further 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 scattered light can be absorbed in the layer in which the groove is formed. .. In addition, Mie scattering has a small wavelength dependence, so that light in the entire visible light region of 380 nm to 780 nm can be scattered, and scattered light can be absorbed in the layer in which the groove portion is formed. ..

As described above, since 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. Therefore, the plurality of grooves are formed on the outermost surface. The printed matter can improve the visibility of the printed image by reducing the reflected light.

Further, the printed matter usually displays a printed image by subtractive color mixing, and a part of the light incident on the printed matter is absorbed in the printed matter, and the color tone of the reflected light is not absorbed in the printed matter. It becomes the color tone of the printed image. The reduction of the light reflectance on the surface of the printed material means that the absorptance of the light to the printed material is high, and in particular, the absorptance of the light other than the light relating to the color tone of the printed material is high.
According to the present invention, the light having a wide wavelength range is absorbed in the printed matter due to the reflectance reduction effect produced by the variation of a large number of grooves. In addition, the layer in which a large number of the grooves are formed can exhibit a high haze value due to Mie scattering. As a result, total reflection at the surface where the groove is formed or at the laminated interface in the printed matter can be reduced, and the absorptance of light other than the light related to the color tone of the printed matter can be further increased.
In this way, the reflection of light incident on the printed matter, especially light other than the light relating to the color tone of the printed matter is reduced, and the absorptivity in the printed matter is increased. As a result, it becomes possible to display colors clearly.

In addition, the printed matter of the present invention has a feature that it has a high structural durability because it has grooves on the surface. In the case where the surface has a convex projection, if the projection is damaged or deformed by an external impact, it is expected that the reflectance reduction effect will be 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, damage or deformation of the groove portion is unlikely to occur, and a high reflectance reduction effect can be exhibited for a long period of time. .. Therefore, the printed matter of the present invention has high visibility for a long period of time and can display colors clearly.

Hereinafter, the printed matter of the present invention will be described by dividing it into the groove portions of the printed matter of the present invention and the embodiments of the printed matter of the present invention.

I. Groove Part The groove part according to the present invention is formed on the outermost surface of the transparent substrate facing the surface on which the print layer is formed, and has a predetermined variation in shape and arrangement position.

The groove portion in the present invention will be described with reference to the drawings. FIG. 1 is an explanatory diagram illustrating a groove portion in a printed material of the present invention. FIG. 2A is a schematic perspective view for explaining the groove portion in the present invention, and FIG. 2B is a schematic plan view of FIG. 2A.
As illustrated in FIG. 1, the numerous groove portions 1 provided on the outermost surface of the printed matter 10 of the present invention have predetermined variations in shape and arrangement position.
Here, the predetermined variation of a large number of grooves is defined by quantifying three parameters.
The first parameter depends on the size of the groove opening portion (hereinafter, may be simply referred to as the groove opening portion) which is a region surrounded by the side surface of the groove portion. As shown in FIG. 2( a ), the groove portions 1 and 1 ′ have groove mouth portions d and d′ which are regions surrounded by the side surfaces on the outermost surface of the printed matter 10. In the present invention, the fact that a large number of grooves have a predetermined variation means that the shape of the groove openings d and d′ of the grooves 1 and 1′ is approximated to an octagon, as shown in FIG. In this case, the average area S and S′ of the groove openings d and d′ in plan view 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 opening. In the present invention, the fact that a large number of grooves have a predetermined variation means that, as shown in FIG. 2B, the maximum internal angle dispersion is 600 or more when the shape of the groove openings d and d′ is approximated to an octagon. It is within the range of 1020 or less.
The third parameter depends on the positional relationship between the adjacent groove portions. In the present invention, a large number of groove portions have a predetermined variation when the shape of one groove portion 1 and the groove opening d of the one groove portion 1 is approximated to an octagon, as shown in FIG. 2B. At a position closest to the center of gravity O of the groove mouth portion d′, the average distance L between the center of gravity with another groove portion 1′ having the center of gravity O′ when the plan view shape of the groove mouth portion d′ is approximated to an octagon is 500 nm or less, It means that the dispersion of the distance L between the centers of gravity is 8000 or more.
That is, “having a plurality of groove portions having a predetermined variation” means that the first to third parameters have the above-described predetermined range (hereinafter, may be referred to as a predetermined value). ..

In the present invention, since the large number of the groove portions have a predetermined variation, the reflectance reduction function exhibited by the groove portions can achieve the effect of the printed matter of the present invention.
The variation of the groove portion is defined by quantifying three parameters of “size of groove portion”, “shape of groove portion”, and “positional relationship of adjacent groove portions”, and each parameter has the above-mentioned predetermined value. As shown, many of the grooves can have a certain variation.
Hereinafter, the quantification method of each parameter and the value of each parameter defined by the above quantification method will be described.

A. Parameter Quantification Method The variation in the shape and arrangement position of the groove portion in the present invention is calculated and quantified by extracting a desired score from a large number of groove portions provided on the outermost surface of the printed matter on the printing layer side.
The groove portion is extracted by using a scanning electron microscope (SEM) or an atomic force microscope (AFM), and has a groove portion of a printed matter with a magnification of 10,000 times and a visual field range of 4 μm in length×4 μm in width. A method is used in which planar observation is performed from the surface side, the in-plane arrangement of the groove portions in the visual field range is detected by an image, and a desired score is extracted from the image.

Each parameter in the present invention is calculated with the minimum number of extraction points of the groove portion being 30 per one visual field range. The larger the number of extraction points of the groove, the more preferable, 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 is preferably 3 or more, particularly 5 or more, and particularly 10 or more per unit area (2500 mm ² ) of the surface having the groove of the printed matter.
By defining the number of extraction points and the number of detections of the visual field range within the above range, the three parameters can be quantified with higher accuracy, and the variation in the shape and arrangement position of the groove can be accurately defined. is there.

Each parameter is quantified by the following procedure.
(1) First, a scanning electron microscope (SEM) or an atomic force microscope (AFM) is used to detect the in-plane arrangement of grooves. A groove having a desired number of points is extracted from the detected in-plane array, and the planar view shape of the groove mouth portion, which is an area surrounded by the groove side surface, is detected for each groove. The plan-view shape of the groove portion can be detected from the contrast of black and white in the SEM image and from the contrast of light and dark in the AFM image.
The specific method of detecting the shape in plan view is not particularly limited. For example, the strength of the edge is calculated by calculating the gradient by the first derivative of the contrast in the image, and the edge locality is calculated from the direction of the gradient. It is possible to use a method of predicting a dynamic change and searching for a location where the gradient in that direction has a local maximum.

(2) Next, the planar view shape of the groove opening is approximated to an octagon for each groove from the SEM image and the AFM image. At this time, the line that is partially broken is complemented. As a complementary method, for example, a method of providing a certain threshold value to create a closed space can be used.
The approximation of the shape of the groove portion in plan view can be applied by a conventionally known method used when approximating the shape from an image and is not particularly limited, for example, template matching, generalized Hough transform, Douglas-Peucker method. Each method such as can be used.
Template matching prepares a template expressing a shape in advance, and while moving the template with respect to the image data to be image-recognized, examines the index of similarity such as a correlation coefficient to determine the shape included in the image data. It is a recognition technology. For the image approximation method by template matching, see, for example, “Takayuki Nakata, Yukaku, Naofumi Fujiwara: “Figure recognition using Log-Polar transformation in three-dimensional environment”, IEICE Transactions (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", The Japan Society for Precision Engineering, Vol.61, No.11, pp. .1604-1608 (November 1995)”.

The generalized Hough transform is a generalization of the Hough transform that determines a straight line that passes the most feature points in image data from infinitely existing straight lines, and is applied to a curve. Also, the shape of the image data can be recognized by 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)" and , “Akio Kimura, Takashi Watanabe: “Generalized Hough Transform extended as a method for detecting arbitrary figures invariant to affine transformation”, IEICE Journal (D-II), Vol. J84-D-II, No. 5 , pp.789-798 (2001.5)".

The Douglas-Peucker method is a method for recognizing shapes by line approximation. Regarding the 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, the area of the octagonal-approximation-shaped groove opening in plan view (hereinafter, sometimes referred to as the area of the groove opening) is calculated to define the size of the groove opening. .. The area of the groove portion is calculated from the comparison 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.
It is desirable to exclude outliers when obtaining the average value and variance of the area of the groove opening. The outlier means that the absolute value of the standardized score calculated by the following calculation formula is 3 or more.

(4) Next, for each groove, the maximum inner angle of the groove opening portion approximated to an octagon in plan view (hereinafter, sometimes referred to as the maximum inner angle of the groove portion) is extracted, and the variance is calculated by statistical processing. Ask. Existing spreadsheet software can be used for statistical processing. Further, when obtaining the variance of the maximum interior angle, it is desirable to exclude outliers. The outlier means that the absolute value of the standardized score calculated by the following calculation formula is 3 or more.
Standardized score = (maximum internal angle of each groove-average of maximum internal angle of groove)/standard deviation

(5) Next, for each groove portion, the center of gravity of the groove opening portion in a plan view shape that is approximated to an octagon (hereinafter may be referred to as the center of gravity of the groove portion) is calculated, and the position of the groove portion is defined. The center of gravity of the groove is defined by the following method. First, as described above, the planar view shape of the groove opening is approximated to an octagon, and a diagonal line is connected from one vertex of the octagon to divide it into six triangles, and the center of gravity of each triangle is obtained. Next, the center of gravity of each of the six triangles is connected to form a hexagon, and a diagonal line is connected from one vertex of the hexagon to form a triangle, and the center of gravity of each triangle is obtained. Next, the centers of gravity of the four triangles are connected to form a quadrangle. Then, the quadrangle is divided into two triangles by one diagonal, each centroid of the two triangles is obtained, and the two centroids are connected by a straight line. Similarly, the quadrilateral is divided by two diagonals into two triangles, and 2 Find each centroid of one triangle and connect the two centroids with a straight line. The intersection of the two straight lines becomes the center of gravity of the octagon, that is, the center of gravity of the groove.

(6) Next, the position of the center of gravity of the groove mouth of each groove is converted into coordinates. The origin and axis of the coordinates can be in any direction. For example, with the lower left in the SEM image or AFM image as the origin, the right direction parallel to the length direction of the seat surface from the origin is the x axis, and the upward direction (width direction of the seat surface) orthogonal to the x axis is the y axis. To do. By using the image as the coordinate plane in this manner, the position of the center of gravity of the groove opening of the groove 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 between one specific groove and a plurality of adjacent grooves, that is, the distance between the centers of gravity is calculated. The distance between the centers of gravity can be calculated by the following formula. Of the calculated distances between the centers of gravity, the minimum distance is defined as the “closest distance between the centers of gravity”.
Distance between the centers of gravity ^{_{= {(x 1 -x 2)}} 2 + (y 1 -y 2) 2} 1/2}
It should be noted that x ₁ and y ₁ in the equation are x-coordinates and y-coordinates indicating the center-of-gravity position of the groove mouth portion of one specific groove portion. Further, x ₂ and y ₂ are x-coordinates and y-coordinates indicating the barycentric position of the groove mouth portion of the groove portion adjacent to the specific one groove portion.
The distance between the centers of gravity can be calculated from the comparison between the pixel size of the scale of the SEM image or the AFM image and the number of pixels.

(7) The closest distance between the centers of gravity of the grooves is extracted by the above method, and the average value and the variance of the closest distances between the centers of gravity are calculated by statistically processing the existing spreadsheet software. It should be noted that it is desirable to exclude outliers when obtaining the average value and the variance of the distances between the closest centroids. The outlier means that the absolute value of the standardized score calculated by the following calculation 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 a value calculated from the average value, that is, the sum of the root mean square of the difference between the measured value and the average value of the measured values is divided by the extraction score. It is a value.

B. Parameters Next, each parameter that defines the variation in the shape and arrangement position of the groove portion in the present invention will be described.

1. Size of Groove Portion The size of the groove mouth portion is defined by the area when the plan view shape of the groove mouth portion is approximated to an octagon, that is, the area of the groove mouth portion. The area of the groove opening portion is a portion indicated by S and S′ in FIGS. 2B and 3A. FIG. 3 is a plane SEM image of a surface having grooves in the printed matter of the present invention, and the reference numerals not described in FIG. 3 are the same as those in FIGS. 1 and 2.

The average area of the groove opening 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 dominated by geometrical optics scattering is several μm or more, but the scattering at the groove opening exhibits different behaviors. In the present invention, the groove opening has an area within the above range, so Mie scattering is It is presumed that it will become dominant. If the average area of the groove is larger than the above range, geometrical optical scattering is dominant over Mie scattering, so that forward scattering is less likely to occur, and light absorption into the layer in which the groove is formed becomes small. In some cases, the desired reflectance reduction effect may not be obtained. On the other hand, when the average area of the groove opening is smaller than the above range, Rayleigh scattering becomes dominant, so that forward scattering is less likely to occur and light absorption into the layer in which the groove is formed may be small. ..

When the average area of the groove openings is within the above range, the dispersion of the area of the groove openings is preferably in the range of 4.08E+9 or more and 1.06E+10 or less. This is because it is possible to prevent the intensity of light of a specific wavelength from increasing due to interference. The unit of variance of the area of the groove opening is (nm ² ) ² .

2. Shape of Groove 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 opening means, for example, a portion indicated by θ _max in FIG.

The plan view shape of the groove portion has a larger variation in shape as the maximum inner angle increases, while it has a shape closer to a regular octagon as the maximum inner angle decreases, and thus the variation in shape decreases. Therefore, the greater the variance of the maximum internal angles calculated for each of the extracted groove portions, the greater the variation in the plan view shape of the groove mouth portion for each groove portion.
In the present invention, the dispersion of the maximum internal angle of the groove portion may be in the range of 600 or more and 1020 or less, and particularly preferably in the range of 640 or more and 980 or less, and particularly preferably in the range of 640 or more and 810 or less. If the dispersion of the maximum internal angle of the groove mouth portion is larger than the above range, manufacturing may make it difficult to design the groove portion.On the other hand, if it is smaller than the above range, the intensity of light of a specific wavelength may be increased due to interference. Because there is. The unit of dispersion of the maximum internal angle of the groove is the square of the degree [(°) ² ] .

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

3. Positional Relationship between Adjacent Grooves The position of a groove means the position of the center of gravity (center of gravity of the groove) when the plan view shape of the groove is approximated to an octagon, and is indicated by O or O′ in FIGS. 1 to 3. It is a part.
The positional relationship between adjacent groove portions is one groove portion and another groove portion having the center of gravity of the groove mouth portion at a position closest to the center of gravity when the shape of the one groove mouth portion in plan view is approximated to an octagon. It is defined by the distance between the centers of gravity, that is, the average of the distances between the closest centers of gravity.

The closest distance between the centers of gravity is calculated and quantified by the method described above, and the quantification will be further described with reference to the drawings. As shown in FIG. 3C, the closest distance between the centers of gravity is the closest to the center of gravity O when the plan view shape of the groove mouth of the groove 1A is approximated to an octagon among the grooves adjacent to the groove 1A. The groove portion 1B having the center of gravity O when the plan view shape of the groove mouth portion is approximated to an octagon is extracted, and the center-of-gravity distance L1 thereof is calculated as the closest center-of-gravity distance. Next, among the groove portions adjacent to the groove portion B, the groove portion 1C having the center of gravity O of the groove mouth portion at a position closest to the center of gravity O of the groove mouth portion of the groove portion 1B is extracted, and the distance L2 between the center of gravity is set as the closest distance between the center of gravity. calculate.
The average of the distances between the closest centers of gravity is calculated by repeating the above operation to calculate the sum of the distances between the closest centers of gravity of the number of extraction points of the groove portion, and dividing the sum by the number of extraction points.

The average distance between the closest centers of gravity may be 500 nm or less, and preferably 420 nm or less, particularly 410 nm or less. If the average distance between the centers of gravity closest to each other is larger than the above range, adjacent grooves are not in close contact with each other, and there are many flat non-groove regions where no grooves are formed. As a result, the reflectance reduction effect may decrease.
The lower limit of the average distance between the closest centers of gravity is not particularly limited and can be set within a designable range in manufacturing, and is preferably 330 nm or more, for example.

When the average of the distances between the closest centers of gravity is within the above range, the dispersion of the distances between the closest centers of gravity may be 8,000 or more, and among them, it is preferably 11,000 or more, and particularly preferably 12,000 or more. If the distance between the centers of gravity closest to each other is smaller than the above range, a large number of grooves will be arranged with a uniform pitch width, and the intensity of light of a specific wavelength will increase due to interference, and the desired reflectance reduction effect will be exhibited. This is because it may be difficult to be done.
The upper limit of the dispersion is not particularly limited and can be set within a range that can be designed in production, and is preferably 20000 or less. The nearest unit of the 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-mentioned three parameters can be set to predetermined values, but 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 opening becomes large, so that geometrical optics scattering becomes dominant rather than Mie scattering, and forward scattering is less likely to occur. Absorption of light 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 the groove into a desired shape.
The depth of the groove portion is an average length from the surface of the layer in which the groove portion is formed to the tip of the groove bottom, and is a portion indicated by h ₁ in FIG.

The depth of the groove can be determined by, for example, using an atomic force microscope (AFM) to detect the maximum and minimum points of the depth of each groove, and from the detected maximum, a specific reference position (for example, the groove mouth surface The outermost surface position of the print layer including the inside is defined as “depth=0”.) The relative depth difference of each local maximum point position is acquired and made into a histogram, calculated from the frequency distribution by the histogram, and averaged. Is the value to be set. For the detection of the maximum point and the minimum point, various methods are applied, such as a method of sequentially comparing a plan view shape and an enlarged photograph of a cross-sectional shape corresponding thereto, a method of obtaining it by image processing of a plane view enlarged photograph, and the like. be able to.

Further, when the depth of the groove portion is within the above range, the aspect ratio of the depth to the maximum diameter of the groove opening portion in plan view may be a ratio capable of exhibiting a desired reflectance reduction effect. For example, the range of 0.3 to 30 is preferable, and the range of 0.8 to 3 is particularly preferable. When the aspect ratio is smaller than the above range, light reflection is less likely to occur in the groove portion, and the reflectance reduction effect may not be sufficiently exhibited. On the other hand, when 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 groove opening in the plan view means the widest portion when the shape of the groove opening in plan view is approximated to an octagon, that is, the maximum width passing through the center of gravity of the groove opening.

The groove portion has a concave pyramidal structure, and the shape of the groove portion can be shaped with high accuracy, so that there is a manufacturing advantage that productivity is improved.
Generally, in a printed matter in which fine concaves and convexes (grooves) such as a moth-eye structure are regularly arranged, in order to improve the reflectance reduction effect, the shape of the groove bottom is made into a multi-groove shape with a branched tip, and the surface area is Is used. However, such a shape may not be shaped accurately. On the other hand, in the present invention, since the reflectance is reduced by providing the grooves with a predetermined variation, it is not necessary to form the grooves in a multi-groove shape, and it is possible to accurately shape each groove. Of.
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 is pointed because the absorption of light into the layer in which the groove portion is formed due to Mie scattering becomes large.

The plan view shape of the groove is not particularly limited as long as it can be approximated to an octagon. For example, a circle, an ellipse, and other round shapes, as well as a pentagon, hexagon, octagon, dodecagon, and other polygons. The shape and the like can be mentioned.
In addition, the side surface shape of the groove may be linear or curved. Further, the side surface shape of the groove may be multi-stepped. Above all, it is preferable that the side surface of the groove is multi-stepped. This is because multiple reflections and Mie scattering are more likely to occur in the groove.

II. Embodiments Next, embodiments of the printed matter of the present invention will be described.
The printed material of the present invention has a transparent base material and a print layer formed on one surface of the transparent base material, and the printed matter of the surface side of the transparent base material opposite to the surface on which the print layer is formed. The surface is formed with a large number of groove portions having a predetermined variation described in the above section "I. Groove portion", and the surface of the transparent substrate facing the surface on which the print layer is formed, A first aspect in which a transparent low reflection layer is formed, and a large number of the groove portions are formed on a surface of the transparent low reflection layer facing the transparent base material, and a large number of the groove portions are formed on the transparent base material. The second aspect is directly formed on the surface opposite to the surface on which the print layer is formed.
Hereinafter, each aspect will be described.

A. First Aspect The first aspect of the printed matter of the present invention (hereinafter, this aspect may be referred to as the present aspect) will be described. The printed matter of the present aspect, on the surface facing the surface on which the printing layer of the transparent substrate is formed, a transparent low reflection layer is formed, on the surface facing the transparent substrate of the transparent low reflection layer, A large number of the groove portions are formed.
In this embodiment, the transparent low reflection layer is located on the outermost layer of the printed matter.

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

According to this aspect, when it is difficult to form the groove directly on the surface of the transparent substrate, by providing the transparent low-reflection layer having the desired groove formed as the outermost layer of the printed matter, a predetermined variation can be obtained. The effect of the present invention can be obtained by the groove portion having the.
Hereinafter, each component of the printed matter of this aspect will be described.

1. Transparent Low-Reflection Layer In the transparent low-reflection layer in this aspect, a large number of the above-mentioned grooves have a predetermined variation on the surface facing the transparent substrate (hereinafter, sometimes referred to as the surface of the transparent low-reflection layer). Has been formed.
The details of the groove portion formed on the surface of the transparent low reflection layer are the same as those described in the above “I. Groove portion”, and thus the description thereof is omitted here.

The transparent low reflection layer preferably exhibits low reflectance in the entire visible wavelength range. Specifically, the maximum reflectance of the transparent low reflection layer in the visible light region 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 upper limit value or less, it is possible to exhibit a low reflectance for the entire wavelength range of visible light, and the reflectance reduction effect by the groove portion is sufficiently exhibited. Therefore, it is possible to improve the visibility of the printed image. In addition, since the reflectance of the groove reduces the reflectance of the printed matter, the color development of the printed image is improved and the color can be displayed clearly.

The maximum reflectance is 8° incident light (wavelength region 380 nm) on the surface where the groove is formed (hereinafter, also referred to as groove forming surface), using Scanning Spectrophotometer UV-3100PC (manufactured by Shimadzu Corporation) as a measuring device. It can be a value obtained by measuring the total reflection for ˜780 nm). Specifically, the integrated reflectance in all directions when light with a wavelength of 380 nm to 780 nm in the visible light region is incident at 8° is obtained, and the highest reflectance among them can be obtained. The maximum reflectance of the transparent low reflection layer can be measured, for example, by using a black printing layer as the printing layer described later. The maximum reflectance in this specification is a value measured by the above method.

The transparent low reflection layer preferably has a high haze value. The higher the haze value, the greater the variation in the shape and arrangement position of the groove, and therefore, the excellent effect of reducing the reflectance of the entire transparent low-reflection layer can be achieved, and the coloring and visibility of the printed image on the printed matter can be improved. It can be done.
Further, the higher the haze value of the transparent low reflection layer, the more scattering of light due to Mie scattering, and the total reflection at the groove forming surface or the laminated interface in the printed matter can be reduced. As a result, the reflection of light incident on the printed matter, especially light other than the light relating to the color tone of the printed matter is reduced, and the absorptance in the printed matter is increased, so that the color developability of the printed image in the printed layer is further improved. This is because it becomes possible to display colors more clearly.
The above-mentioned effect exhibited by the transparent low reflection layer exhibiting a high haze value will be further described. With respect to the transparent low reflection layer exhibiting a high haze value, white light incident at an angle of total reflection is various. The light is scattered at an angle and is absorbed in the layer, but at this time, a part of the light having a smaller incident angle is incident on the printed layer, so that light having a predetermined wavelength is reflected and a predetermined color tone of the printed matter is obtained. The color development of can be enhanced.

The haze value of the transparent low reflection layer is preferably 70% or more, and more preferably 80% or more. The upper limit of the haze value is preferably 95% or less. When the haze value is smaller than the above range, the groove portion does not have a predetermined variation in shape and arrangement position, and light absorption into the transparent low reflection layer due to multiple reflections of light and Mie scattering becomes difficult to occur. This is because the reflectance reduction effect may not be exhibited in some cases. On the other hand, if the haze value is larger than the upper limit, it may be difficult to produce the groove having the desired shape.
The haze value is a value in the region where the groove portion of the transparent low reflection layer is formed, and can be measured by a method according to JIS K7361 using a haze meter (trade name: Haze Guard manufactured by Toyo Seiki Seisaku-sho, Ltd.). The haze value in this specification is a value measured by the above method.

The transparent low-reflective layer according to this embodiment is required to have a large number of groove portions formed on the surface thereof with a predetermined variation and to exhibit desired maximum reflectance and haze value. It can be different.
That is, as shown in FIG. 4, the transparent low-reflection layer in this embodiment has the transparent low-reflection layer 4 formed on the transparent support layer 11 and one surface side of the transparent support layer 11 and containing a transparent resin. A specification having a reflective resin layer 12 and a large number of groove portions 1 formed on the surface of the low reflective resin layer 12 facing the surface in contact with the transparent support layer 11 (hereinafter referred to as the first specification of the transparent low reflective layer). .), as shown in FIG. 5, the transparent low-reflection layer 4 is a single layer formed of a transparent resin, and is directly formed on the transparent substrate 2 (hereinafter, referred to as the transparent low-reflection layer 2 specifications).
The specifications of the transparent low reflection layer will be described below.

(1) First Specification of Transparent Low Reflection Layer The first specification of the above transparent low reflection layer (hereinafter, this specification may be referred to as this specification in some cases) is a transparent support layer and one of the above transparent support layers. The low reflection resin layer including a transparent resin is formed on the surface side, and a large number of the groove portions are formed on the surface of the low reflection resin layer facing the surface in contact with the transparent support layer.

The transparent low-reflection layer of this specification is formed by forming a low-reflection resin layer on a transparent support layer, forming a number of grooves on the surface of the low-reflection resin layer facing the surface in contact with the transparent support layer, and then forming the transparent It can be attached to the surface of the base material opposite to the surface on which the print layer is formed to provide a printed matter. Therefore, the groove portion of the transparent low-reflection layer can be arranged in alignment with the position of the printed layer through the transparent base material, and the visibility of the printed image can be improved, and the handleability during manufacturing is improved. Has the manufacturing advantage that Furthermore, even when it is difficult to form the transparent low reflection layer directly on the surface of the transparent substrate due to the reason that the transparent substrate has a curved surface, the adhesion of the transparent substrate is poor, or the like, It has an advantage that it can be a printed matter.

(A) Low-reflection resin layer The low-reflection resin layer contains a transparent resin. In order for a large number of grooves to exhibit a desired reflectance reduction effect, it is necessary to have a predetermined variation defined by quantification of the three parameters described in “I. Grooves” above. By shaping the groove portion on the surface of the low-reflection resin layer including the groove portion, the accuracy of the shape of each groove portion can be increased and a predetermined variation can be exhibited.

The transparent resin forming the low-reflection resin layer is not particularly limited as long as it can shape a large number of groove portions having the above-described predetermined variations, and examples thereof include acrylate-based, epoxy-based, polyester-based, etc. Ionizing radiation curable resin, acrylate-based, urethane-based, epoxy-based, polysiloxane-based and other thermosetting resins, acrylate-based, polyester-based, polycarbonate-based, polyethylene-based, polypropylene-based and other thermoplastic resins, and other materials, and Various curing forms of the shaping resin can be used.
The ionizing radiation means an electromagnetic wave or charged particles having energy capable of polymerizing and curing a molecule, and for example, all ultraviolet rays (UV-A, UV-B, UV-C), visible rays, gamma rays. , X-rays, electron beams and the like.

The low reflection resin layer may include any material as needed. Examples of the optional material include a refractive index adjusting agent, a polymerization initiator, a release agent, a photosensitizer, an antioxidant, a polymerization inhibitor, a cross-linking agent, an infrared absorbing agent, an antistatic agent, a viscosity adjusting agent, and adhesion. It may also contain an improver and the like. Examples of the refractive index adjusting agent include low refractive index materials disclosed in JP-A-2013-142821.

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

The low reflection resin layer has a transparency to visible light so that the printed image on the printed layer can be visually recognized. Specifically, it is preferable that the low-reflecting resin layer has a light transmittance of 80% or more, particularly 85% or more, and particularly 90% or more in the whole visible wavelength range of 380 nm to 780 nm. In this 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 reflective resin layer is preferably such that the difference between the refractive index of the low reflective resin layer and the transparent support layer described later falls within a desired range, and although it depends on the type of the transparent resin selected, it is 1.20. The range of 2.40 is preferable, and the range of 1.40 to 1.70 is particularly preferable. The refractive index in this specification is a value measured with a precision spectrometer GMR-1DA type manufactured by Shimadzu Corporation.

(B) Transparent support layer The transparent support layer has the above-mentioned low-reflection resin layer on one surface, and the surface facing the one surface contacts or comes close to the transparent substrate.

The material used for the transparent support layer is not particularly limited as long as it shows a desired light transmittance and a transparent support layer having a desired refractive index can be obtained, and examples thereof include thermoplastic resins. Resins such as thermosetting resins and ionizing radiation curable resins 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, polyether monkeys. Phone, polysulfone, polyether, polyetherketone, acronitrile, methacrylonitrile, cycloolefin polymer, cycloolefin copolymer, polyamide, polyimide, polystyrene, acrylonitrile-styrene copolymer, polyvinyl acetate, ethylene-vinyl acetate copolymer , Vinyl chloride, polyvinylidene chloride, polyether ether ketone, and the like.
Further, as the material of the transparent support layer, an inorganic material such as glass or ceramics may be used.

The transparent support layer, 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, various additives such as rubber) may be included.

The transparent support layer may have various shapes such as a plate shape, a sheet shape and a film shape.

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

The transparent support layer has transparency to visible light so that the printed image on the printed layer can be visually recognized. Specifically, it is preferable that the transparent support layer has a light transmittance of 80% or more, particularly 85% or more, and particularly 90% or more for the entire visible light wavelength region of 380 nm to 780 nm.

The refractive index of the transparent support layer is preferably about the same as the refractive index of the low reflection resin layer. When the refractive index difference between the transparent support layer and the low reflection resin layer is large, a discontinuous interface of refractive index is formed at the laminated interface, and light is reflected at the discontinuous interface, so that the groove portion causes This is because the reflectance reduction effect is impaired and the visibility of the printed image is reduced.
The refractive index difference (absolute value) between the low-reflection resin layer and the transparent support layer is in the range of 0 to 0.5, particularly 0 to 0.2, and particularly 0 to 0.1. Is preferred. The refractive index of the transparent support layer is determined in relation to the refractive index of the low reflection resin layer, but is preferably in the range of 1.20 to 2.40, and particularly 1.40 to 1.70. The range of is preferable.

(C) Others The transparent low-reflection layer of this specification may be formed by laminating a low-reflection resin layer on a transparent support layer, or may be formed by co-extruding the resin of the transparent support layer and the low-reflection resin layer. ..

Further, the transparent low reflection layer of this specification may be formed on the surface of the transparent base material opposite to the surface on which the printed layer is formed via an adhesive layer, and may be directly formed on the transparent base material by thermal lamination or the like. It may be formed.
As the adhesive used in the adhesive layer, a known adhesive such as a pressure-sensitive adhesive (pressure-sensitive adhesive), a two-component curable adhesive, an ultraviolet curable adhesive, a thermosetting adhesive, or a hot-melt adhesive Is mentioned. Examples of the material of these adhesives include known resins such as acrylic resin, urethane resin, polyester resin, epoxy resin and rubber.

The thickness of the adhesive layer, the transparent low reflection layer and the printing layer can be bonded with a desired strength, the thickness does not impair the visibility of the printed image in the printing layer at the opposing position via the transparent substrate. There is no particular limitation so long as it is within the range of, for example, 1 μm to 1000 μm.

The adhesive layer has a transparency to visible light so that the printed image on the printed layer can be visually recognized. Specifically, it is preferable that the transparent substrate has a light transmittance of 80% or more, particularly 85% or more, and particularly 90% or more in the entire visible light wavelength range of 380 nm to 780 nm.

In addition, the refractive index of the adhesive layer is preferably about the same as the refractive index of the transparent substrate and the refractive index of the printed layer. That is, it is preferable that the difference between the refractive index of the adhesive layer and the refractive index of the transparent support layer and the refractive index of the transparent substrate is small. The reason is the same as the reason for reducing the difference in refractive index between the transparent base material and the low reflection resin layer described in the above section “(b) Transparent support layer”.
The refractive index difference (absolute value) between the adhesive layer and the transparent support layer and the refractive index difference (absolute value) between the adhesive layer and the transparent base material are each within a range of 0 to 0.5, and particularly 0. It is preferably in the range of 0.2, particularly preferably in the range of 0-0.1. 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 particularly within the range of 1.40 to 1.70. Is preferred.

(2) Second Specification of Transparent Low Reflection Layer The second specification of the transparent low reflection layer (hereinafter, this specification may be referred to as this specification in some cases) is a single layer formed of a transparent resin. In addition, the transparent low-reflection layer of this specification is formed directly on the surface of the transparent substrate that faces the surface on which the printed layer is formed, and a large number of grooves are formed on the surface with a certain variation. ing.

Since the transparent low-reflection layer of this specification is a single layer unlike the transparent low-reflection layer of the first specification described above, no laminated interface is formed in the transparent low-reflection layer. Therefore, it is possible to prevent reflection of light at the interface between the layers in the transparent low reflection layer.

The transparent resin constituting the transparent low-reflection layer of this specification can be the same as the transparent resin described in the above section “(1) First specification of transparent low-reflection layer (a) Low-reflection resin layer”. ..
In addition, the transparent low-reflection layer of this specification includes any material described in the above section “(1) First specification of transparent low-reflection layer (a) Low-reflection resin layer”, if necessary. 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 the refractive index of the transparent low reflection layer of this specification are the same as those of the low reflection resin layer described in the above-mentioned section "(1) First specification of transparent low reflection layer (a) Low reflection resin layer". It can be similar to the light transmittance and the refractive index.

As a method of forming the transparent low-reflection layer of this specification, for example, a transparent resin forming the transparent low-reflection layer is directly applied to the surface of the transparent substrate opposite to the surface on which the printed layer is formed and shaped. Thus, a method of forming a large number of grooves on the surface can be cited.

2. Printed Layer The printed layer in the present aspect is formed on the surface of the transparent substrate that faces the surface on which the transparent low-reflection layer is formed.
The print layer is a layer on which a print image displayed in a single color, a multicolor or a full color is printed by subtractive color mixture, and is directly formed on the surface of a transparent substrate by using ink or the like.

The material of the printing layer is not particularly limited as long as it can print a desired printed image that can be color-displayed by subtractive color mixing, and examples thereof include a resin ink containing a binder resin and a colorant.

The binder resin contained in the resin ink is a desired physical property, printability, etc. from known binder resins generally used for resin inks, such as thermoplastic resins, thermosetting resins, and ionizing radiation curable resins. It can be selected as appropriate. For example, in addition to cellulose resins and acrylic resins, urethane resins, vinyl chloride-vinyl acetate copolymers, polyester resins, alkyd resins and the like may be used alone or as a mixture containing them. These resins may be used alone or in combination of two or more.

As the colorant contained in the resin ink, a material generally used for printed matter can be used, for example, an inorganic pigment, an organic pigment, a dye, aluminum, a metal pigment made of a flaky foil piece such as brass, a titanium dioxide coating. Examples include pearlescent pigments composed of scale-like foil pieces such as mica and basic lead carbonate.
Further, it is possible to adjust the light-shielding property of the print layer according to the type of the colorant. Specific examples of the colorant used when forming the printed layer having a high light-shielding property include the colorant used in the light-shielding layer described in the section “4. Optional member” described later.

The resin ink may contain any material such as an ultraviolet absorber, a crosslinking agent, a stabilizer, a plasticizer and a curing agent.

The thickness of the printing layer is appropriately selected depending on the printing method of the printing layer, and specifically, it is within the range of 0.01 μm to 2000 μm, particularly within the range of 0.3 μm to 800 μm, and particularly 0.8 μm. It is preferably in the range of 400 μm. When the thickness of the printed layer is thicker than the above range, the printed matter becomes thicker, which may deteriorate the workability of the printed matter. On the other hand, when the thickness is thinner than the above range, the printed layer is uniformly formed on the transparent substrate. This is because it may be difficult to form, and rubbing and unevenness may occur easily.

Examples of the print image on the print layer include patterns, photographs, characters, numbers, patterns, drafts, and marks.

The printing layer may have a light-transmitting property or a light-blocking property, but preferably has a light-blocking property from the viewpoint of increasing the absorptance of light to the printed matter. When the printed layer is light-transmissive, a part of the light scattered by the groove is emitted from the printed layer, so that the absorptivity of light in the printed matter is reduced and the effect of the present invention due to the groove is reduced. There is. Further, when light is incident from the surface of the printed matter on the side of the printing layer, the light may pass through the printing layer, and haze may occur in the printed image to be visually recognized.
Specifically, the printing layer having a light-shielding property means that the printing layer has a light transmittance of 3% or less (at an optical density OD of 1.5 or more) in the entire visible wavelength region of 380 nm to 780 nm. Say that.

Even when the light-shielding property of the printing layer is less than the above range, the light-shielding property of the printing layer is provided by providing the light-shielding layer on the surface facing the surface of the printing layer in contact with the transparent substrate, as described later. Can be supplemented. As a result, it is possible to clearly display the printed image and suppress the occurrence of haze.

The printed layer may be formed on the entire surface of one surface of the transparent substrate, or may be formed on a partial area.
The printing layer can be formed by using a general printing method, and can be appropriately selected according to the type of material used for forming the printing layer and the like. Specific examples thereof include known printing methods such as gravure printing, silk screen printing, offset printing, gravure offset printing, and inkjet printing.

3. Transparent Base Material The transparent base material in the present embodiment is not particularly limited as long as it has desired light transmittance and self-supporting property, and a known transparent base material used for an antireflection article is used. Can be used. Examples of the material used for such a transparent substrate include a transparent resin and a transparent inorganic material.
Examples of the transparent resin include thermoplastic resins. Specifically, acetyl cellulose resins such as triacetyl cellulose; polyester resins such as polyethylene terephthalate and polyethylene naphthalate; olefin resins such as polypropylene, polyethylene and polymethylpentene; acrylic resins; polyurethane resins; polyether monkeys. Examples thereof include phones, polycarbonates, polysulfones, polyethers, polyether ketones, acronitriles, methacrylonitriles, cycloolefin polymers, cycloolefin copolymers and the like.
On the other hand, examples of the transparent inorganic material include soda glass, potassium glass, glass such as lead glass, ceramics such as PLZT, quartz, and fluorite.

The transparent substrate may have flexibility or may be rigid. Therefore, examples of the form include a film form, a sheet form, and a plate form.

The transparent base material has transparency to visible light in order to clearly display a printed image of the printed layer. Specifically, it is preferable that the transparent substrate has a light transmittance of 80% or more, particularly 85% or more, and particularly 90% or more in the entire visible light wavelength range of 380 nm to 780 nm.

The refractive index of the transparent substrate is preferably about the same as the refractive index of the other adjacent layers. If there is a large difference in the refractive index between the adjacent other layer and the transparent substrate, a discontinuous interface with a refractive index will be formed at the interface, and light will be reflected at the discontinuous interface, causing reflection by the groove. This is because the rate reduction effect is impaired and the visibility of the printed image is reduced. The refractive index difference (absolute value) between the adjacent layer and the transparent substrate is in the range of 0 to 0.5, preferably in the range of 0 to 0.2, and particularly in the range of 0 to 0.1. preferable.
The “layer adjacent to the transparent substrate” here is a layer that is in direct contact with the transparent substrate. When the transparent low-reflection layer is directly formed on the transparent substrate, the transparent low-reflection layer has the first specification and thus the transparent support layer, and the second specification has the transparent low-reflection layer itself. When the transparent base material and the transparent low reflection layer are laminated via the adhesive layer, the “layer adjacent to the transparent base material” refers to the adhesive layer.
The refractive index of the transparent base material is determined in relation to the refractive index of the layer adjacent to the transparent base material, but is preferably in the range of 1.20 to 2.40, and particularly 1.40 to 1.40. The range of 1.70 is preferable.

The thickness of the transparent substrate may be a size capable of forming a printed layer on the surface and having desired mechanical strength as a printed matter, and can be appropriately designed according to the form, for example, It is preferably 10 μm or more and 50 μm, and more preferably 10 μm or more and 25 μm. When the thickness of the transparent substrate is smaller than the above range, it may be difficult to directly form a printing layer on the surface by various printing methods. On the other hand, if it is larger than the above range, the distance from the groove opening of the groove portion on the outermost surface of the printed matter to the printing layer becomes large, and the sensed distance may appear in the printed image to be visually recognized, which may reduce the visibility.

The structure of the transparent substrate is not limited to the structure composed of a single layer, and may have a structure in which a plurality of layers are laminated. When a plurality of layers are laminated, layers having the same composition may be laminated, or a plurality of layers having different compositions may be laminated. Above all, the transparent substrate is preferably a single layer because it does not have an interface in the layer.

Depending on the material of the transparent base material, when the printed image is printed directly on the surface of the transparent base material to form the printed layer, the transparent base material repels resin ink or the like, which makes it difficult to form the printed layer. There are cases. Therefore, the transparent substrate may be surface-treated in order to improve the adhesion to the printed layer. As the surface treatment, known surface modification techniques such as corona discharge treatment, flame treatment, ozone treatment, ultraviolet treatment, radiation treatment, roughening treatment, chemical treatment, plasma treatment, and grafting treatment are applied. be able to.
The surface treatment is preferably performed on at least the surface of the transparent substrate on which the printing layer is formed, and further preferably on the surface of the transparent low reflection layer. This is because it is possible to improve the adhesion between the transparent base material and the transparent low reflection layer.

4. Arbitrary Member Hereinafter, an arbitrary member assumed in the printed matter of this embodiment will be described.

(1) Functional Layer As shown in FIG. 6, the printed matter of the present embodiment has a function on at least the surface of the printed layer 3 facing the surface in contact with the transparent substrate 2 (which may be the printed layer surface). It may have a layer 14. Note that FIG. 6 shows an example in which a light shielding layer is used as the functional layer 14.
By providing at least a functional layer on the surface of the printing layer, it is possible to add a function according to the type of the functional layer and to improve the color reproducibility and the visibility of the printed image by the light control by the functional layer. .. Further, it is possible to protect the print layer by providing the functional layer on the surface of the print layer.

The functional layer provided on the surface of the printing layer can be appropriately selected according to the required function and the like, and examples thereof include a light-shielding layer, a conductive layer, an antistatic layer, a protective layer, an adhesive layer for printing and an adhesive layer for printing. To be

(A) Light-shielding layer The printed matter of this aspect preferably has a light-shielding layer as a functional layer. By providing a light-shielding layer on at least the print layer surface, light is transmitted from the print layer side surface of the printed matter, so that the haze is conspicuous in the printed image displayed through the groove portion, resulting in a decrease in visibility and a clear color. This is because it is possible to prevent a decrease in color reproducibility due to the display being hindered.

The light-shielding layer may be one that can block light incident from the surface of the printed matter on the side of the print layer. For example, a light-shielding resin layer, a metal film, or the like that is generally used as a light-shielding layer for a display device or the like. Can be used.

(I) Light-shielding resin layer The light-shielding resin layer usually contains a colorant and a binder resin.
Further, the color of the light-shielding resin layer is not particularly limited as long as it exhibits a color capable of sufficiently shielding ultraviolet rays and visible light, and for example, dark colors such as black, silver or white, blue, purple, and navy blue. Etc.

Examples of the colorant contained in the light-shielding resin layer include organic or inorganic dyes and pigments used in a general light-shielding layer, and can be appropriately selected according to the color of the light-shielding resin layer.
For example, if it is black, iron black, graphite, carbon black or the like can be used.
If it is white or silver, it is titanium white (titanium oxide) powder, aluminum powder, basic lead carbonate, basic lead sulfate, basic lead silicate, zinc white, zinc sulfide, lithopone, antimony trioxide, calcium carbonate. , Zinc oxide, barium sulfate and the like.
For dark colors, chromatic colorants such as azo dyes/pigments, anthraquinone dyes/pigments, phthalocyanine dyes/pigments, quinacridone dyes/pigments, dioxazine dyes/pigments, etc. Inorganic pigments such as pigments, yellow lead, chrome vermillion, navy blue, rouge, and others are listed.

Further, as the binder resin contained in the light-shielding resin layer, the same resin as the binder resin generally used when forming the light-shielding layer can be used, and is appropriately selected according to the method of forming the light-shielding resin layer. Is possible.
For example, when the light-shielding resin layer is formed by a printing method or an inkjet method, examples of the binder resin include polymethylmethacrylate resin, polyacrylate resin, polycarbonate resin, polyvinyl alcohol resin, polyvinylpyrrolidone resin, and hydroxyethyl cellulose. Examples thereof include resins, carboxymethyl cellulose resins, polyvinyl chloride resins, melamine resins, phenol resins, alkyd resins, epoxy resins, polyurethane resins, polyester resins, maleic acid resins, polyamide resins and the like.
On the other hand, when the light-shielding resin layer is formed by a photolithography method, the binder resin may be, for example, an acrylate-based, methacrylate-based, polyvinyl cinnamate-based, or cyclized rubber-based reactive vinyl group. The photosensitive resin etc. which it has are mentioned.

The light-shielding resin layer contains a photopolymerization initiator, a sensitizer, a coatability improver, a development improver, a cross-linking agent, a polymerization inhibitor, a plasticizer, a flame retardant and other optional additives, if necessary. You may stay.

(Ii) Metal film As the metal film, for example, a single layer of chromium, a multilayer film of chromium oxide (CrO _x ) and chromium, a chromium oxide (CrO _x ), a chromium nitride (CrN _y ) and a multilayer film of chromium, chromium and A multilayer film of chromium oxynitride (CrN _y O _x ) or the like can be used. Here, x and y are arbitrary numbers. Examples of the metal used for the metal film include the material of the metal film disclosed in JP-A-2014-142610.

(Iii) Others The light-shielding layer may be a single layer or a multilayer body formed by stacking a plurality of layers. This is because the light-shielding property can be further improved by using a multilayer body.

The light-shielding layer preferably has a light transmittance of 3% or less (optical density OD is 1.5 or more) in the entire wavelength range of visible light of 380 nm to 780 nm.

The thickness of the light shielding layer is not particularly limited as long as it can obtain a desired light shielding property, and is appropriately adjusted according to the type of the light shielding layer and the like.

It suffices that the light-shielding layer is provided at least on the surface facing the surface of the printing layer that is in contact with the transparent base material.
When the printing layer is formed on the entire area of the surface facing the surface in contact with the transparent substrate, as shown in FIG. 6A, the surface facing the surface in contact with the transparent substrate 2 of the printing layer 3. The light shielding layer 14 can be provided over the entire area.
Further, when the print layer is formed in a part of the area on the surface opposite to the surface in contact with the transparent base material, it contacts the transparent base material 2 of the print layer 3 as shown in FIG. 6B. The light shielding layer 14 may be provided only on the surface facing the surface. In this case, in the area where the printed layer of the printed matter is not formed, since the transparent low reflection layer exhibits a high haze value due to the haze function exhibited by the groove portion, since it exhibits white, the color of the area other than the printed layer of the printed matter is displayed. The (base color) can be white. Further, as shown in FIG. 6C, the entire surface of the printed matter 10 including the surface of the printed layer 3 on the side of the printed layer 3 has a light blocking property 14, that is, the light blocking layer 14 covers the printed layer 3. It may be formed on the entire surface of the surface of the transparent base material 2 on which the print layer 3 is formed. In this case, the area where the printed layer of the printed matter is not formed can be the color of the light shielding layer.

Further, when the printing layer has a light-transmitting property, the color of the printing layer and the color of the light-shielding layer are overlapped with each other, so that the printed image of the printing layer can be displayed in various ways. By overlapping with the color of the light-shielding layer, the print image can be displayed in gradation and the design of the print image can be further improved.

The method of forming the light shielding layer is appropriately selected according to the type of the light shielding layer and the like. If the light-shielding layer is a light-shielding resin layer, examples of the method for forming the light-shielding layer include a printing method, an inkjet method, and a photolithography method. On the other hand, if the light-shielding layer is a metal film, examples of the method for forming the light-shielding layer include a sputtering method and a vapor deposition method.

(B) Conductive layer The printed matter of the present embodiment may have a conductive layer as a functional layer. This is because the antistatic property of the conductive layer can prevent the printed matter from being charged with static electricity, and prevent troubles such as unnecessary adhesion at the time of sticking due to the static electricity generated in the printed matter.

The conductive layer may be transparent or opaque, but is preferably opaque from the viewpoint of light shielding properties. The material of the conductive layer is not particularly limited and may be the same as a general conductive layer, and examples thereof include simple metals, alloys, conductive oxides, and conductive polymer materials. In addition, a binder resin may be included if necessary. As a specific material for the conductive layer, various materials described in, for example, JP-A-2004-017456 can be used.

The conductive layer may be formed in a pattern on the surface of the printed layer, or may be formed so as to cover the entire surface of the printed layer. When the printed layer is formed on a part of one surface of the transparent substrate, the conductive layer may be formed on the entire surface of the transparent substrate including the surface of the printed layer.

The surface resistance value of the surface of the conductive layer may be any size as long as it can exhibit antistatic performance, and it depends on the thickness of the conductive layer, but is preferably in the range of 0.01 Ω/□ to 1000 Ω/□, for example. The surface resistance is a value measured by a four-terminal measurement method using Loresta-GP and MCP-T600 (manufactured by Mitsubishi Chemical).

The conductive layer can be formed using a general conductive layer forming method such as vacuum deposition or various printing methods depending on the material.

(C) Antistatic Layer The printed matter of this embodiment may have an antistatic layer as a functional layer because it has the same effect as the above-mentioned conductive layer. The antistatic layer is a layer containing an antistatic agent, and a layer that is generally used for a laminate for antireflection purposes can be applied. Specifically, the antistatic layer described in JP 2011-203745 A or the like can be used. The antistatic layer is preferably opaque from the viewpoint of light shielding properties.

(D) Other functional layers Examples of other functional layers include an adhesive layer for printing or an adhesive layer for printing to be attached to an adherend, and a protective layer from the viewpoint of scratch resistance of the printed layer.

(2) Other arbitrary members The printed matter of this embodiment may have a primer layer (adhesion stabilizing layer) between the transparent substrate and the transparent low reflection layer and/or the printed layer. This is because the adhesion between the transparent substrate and the printed layer and/or the transparent low reflection layer can be improved. Examples of the material for the primer layer include a fluorine-based coating agent and a silane coupling agent.

5. Others In the printed matter of this aspect, a large number of groove portions may be formed at positions overlapping at least the print layer of the printed matter in plan view, and groove portions are also formed at positions overlapping in plan view with the area where the print layer is not formed. It may have been done.
For example, as shown in FIGS. 4 and 5, in the printed matter 10 of the present embodiment, the printing layer 3 is formed on the entire area of one surface of the transparent substrate 2, and the surface of the transparent substrate 2 on which the printing layer 3 is formed. The transparent low reflection layer 4 having the groove portion 1 on the surface may be formed on the entire area of the surface opposed to.

Further, when the printed layer is formed on a part of one surface of the transparent substrate, the printed matter of this embodiment has the printed layer 3 of the transparent substrate 2 as illustrated in FIG. 7A. The transparent low reflection layer 4 having the groove portion 1 may be formed at a position facing the printed surface 3 in a plan view on a surface opposite to the printed surface. As shown in FIG. The transparent low reflection layer 4 having the groove portion 1 may be formed on the entire area of the surface facing the surface on which the printed layer 3 is formed. The printed matter shown in FIG. 7( b) has high visibility and a printed area (X area in FIG. 7( b )) in which a printed image having a clear color is displayed and the haze of the transparent low reflection layer 4. It may have a white non-printed area (Y area in FIG. 7B). Moreover, when the above-mentioned light-shielding layer is provided on the entire surface of the transparent substrate including the surface of the printing layer, the non-printing region can exhibit the color of the light-shielding layer.

The printed matter of this aspect preferably has a maximum reflectance of 2.0% or less in the visible light region of 380 nm to 780 nm, and more preferably 1.5% or less. The reason and the measuring method are the same as those described in the above section “1. Transparent low-reflection layer”, and therefore the description thereof is omitted here.
In the printed matter of this aspect, when the groove is formed on a part of the surface of the printed matter, the maximum reflectance is the maximum reflectance of the printed matter of the aspect in the region where the groove is formed.

6. Uses The printed matter of this aspect can be used, for example, in advertisements, posters, magazines, books, catalogs, decorative boards, automobile interior materials, and the like. In particular, a dashboard for an automobile interior material is effective because the use of the printed material of this embodiment can suppress the reflection on the windshield.

7. Manufacturing method In the manufacturing method of the printed matter of this aspect, a printing layer is formed by printing on one surface of the transparent base material, and a transparent low reflection layer is formed on the surface of the transparent base material opposite to the surface on which the printing layer is formed. The method is not particularly limited as long as it is a method capable of forming a large number of grooves having a predetermined variation on the surface of the transparent low reflection layer, and may be appropriately selected according to the specifications of the transparent low reflection layer. You can

(1) First Example of Manufacturing Method In the printed matter of the present aspect, for example, a large number of concave pyramidal structures are formed on the surface by using a transfer original plate including a large number of convex pyramidal structures having a predetermined variation. Forming a first soft mold, and using the first soft mold to form a second soft mold having a large number of convex pyramidal structures on the surface thereof, a transfer plate preparing step of the second soft mold, A coating step of coating the composition for a transparent low reflection layer on the surface on which the convex pyramidal structure is formed, a transparent substrate is placed on the coating layer and the coating layer is cured, and then the second soft mold is formed. By performing a shaping step of peeling off the transparent low reflection layer, and a printing step of forming a printing layer on the surface of the transparent substrate facing the surface on which the transparent low reflection layer is formed, Can be formed.
The printed matter of the present embodiment formed through the above-mentioned steps has a transparent low-reflection layer of the second specification, and variations in the shape and arrangement position of the groove portion are caused by reversing the convex cone-shaped structure of the transfer original plate. Corresponds to variations in shape and arrangement position.

(A) Transfer plate preparation step This step is a first soft mold in which a large number of concave conical structures are formed on the surface using a transfer original plate having a large number of convex conical structures having a predetermined variation. And forming a second soft mold having a large number of convex pyramidal structures on the surface by using the first soft mold.

First, a transfer original plate provided with a large number of convex conical structures having a predetermined variation is prepared. The convex pyramidal structure corresponds to the inverted shape of the groove described in the above section “I. Groove”, and the inverted shape of the convex pyramidal structure is defined by quantification of three parameters. It has a certain variation.

The material of the transfer original plate is not particularly limited as long as it can form a convex pyramidal structure having a predetermined variation, and examples thereof include metals and resins. Among them, from the viewpoint of durability, metal is used. Is preferred.

The method for producing the above-mentioned transfer original plate is not particularly limited as long as it is a method capable of having a convex pyramidal structure having a predetermined variation in shape and arrangement position on the surface, for example, blasting the surface of a stainless plate, It can be formed by subjecting the processed surface of the stainless steel plate to electrolytic plating treatment such as electrolytic nickel plating, electrolytic chromium plating, and electrolytic tin plating while gradually reducing the current value.
At this time, by adjusting the surface roughness of the blast, it is possible to adjust the size and arrangement interval of the convex conical structures and the directionality of the top. Further, the height of the convex pyramidal structure can be adjusted by adjusting the rate of decreasing the current value stepwise.

Next, a first soft mold-forming composition containing a curable resin is applied onto the surface of the obtained transfer raw material on which the convex pyramidal structure is formed, and the application layer is cured to form the first composition. Transfer forming the soft mold. At this time, a large number of concave conical structures, which are the inverted shapes of the convex conical structures, are 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 as long as it can accurately transfer the shape of the convex pyramidal structure of the transfer original plate. A linear curable resin, a thermosetting resin, a thermoplastic resin or the like is used. Further, it may contain any material described in the above section “2. Transparent low reflection layer”, if necessary.

The method of applying the composition for forming the first soft mold is not particularly limited, and can be the same as the method generally used when forming the resin original plate.

Next, a second soft mold-forming composition containing a curable resin is applied on the surface of the obtained first soft mold on which the concave pyramidal structure is formed, and the application layer is cured to give a second Transfer forming the soft mold. At this time, on one surface of the second soft mold, a large number of convex pyramidal structures which are the inverted shapes of the concave pyramidal structures of the first soft mold are formed.

The second soft mold may be any resin that can accurately transfer the shape of the concave conical structure of the first soft mold, and is formed using the same soft mold forming composition as the first soft mold. Alternatively, it may be formed by using a composition for forming a soft mold having a different composition.

When the composition for transparent low reflection layer used in the coating step described later contains a photo-curable or electron beam-curable resin, the second soft mold preferably has a light-transmitting property. This is because the coating layer can be cured by irradiating light or an electron beam from the second soft mold side.

(B) Coating Step This step is a step of coating the composition for transparent low reflection layer on the surface of the second soft mold on which the convex pyramidal structure is formed.
The composition for transparent low reflection layer contains the transparent resin described in the above section "1. Transparent low reflection layer (2) Second specification of transparent low reflection layer". The method for applying the composition for transparent low reflection layer is not particularly limited, and a conventionally known application method can be applied.

(C) Shaping step This step is a step of disposing the transparent base material on the coating layer and curing the coating layer, and then peeling off the second soft mold to form the transparent low reflection layer.
In this step, by curing the coating layer in a state where one surface of the transparent substrate and the coating layer are in contact with each other, one surface of the transparent substrate has a large number of particles having a predetermined variation. A transparent low reflection layer having a groove can be formed.

The method for curing the coating layer and the curing conditions can be appropriately selected according to the type of the transparent resin contained in the composition for transparent low reflection layer. When the transparent resin is an ionizing radiation curable resin, an ultraviolet curing method and an electron beam curing method can be used. When the transparent resin is a thermosetting resin, a heat curing method and a room temperature curing method can be used. When a thermoplastic resin is used as the transparent resin, a cooling method in which a cooling roll or the like is brought into contact with the transparent resin can also be used.

(D) Printing Step This step is a step of printing a print layer on the surface of the transparent substrate opposite to the surface on which the transparent low reflection layer is formed. The printed layer is formed by printing a printed image on one surface of the transparent substrate with a resin ink and drying the printed image. The printing method can be appropriately selected according to the composition of the resin ink used and the like. The resin ink to be used and the printing method have been described in the above section “2. Printing layer”, and therefore description thereof is omitted here.

The timing of performing the printing step is not particularly limited, and the printing steps may be performed in the order of the steps described above. The printing step is performed first, and the print layer is printed on one surface of the transparent substrate, and then the transparent substrate is formed. You may perform the shaping process which forms a transparent low reflection layer on the surface which has a printing layer of a material.

(2) Second Example of Manufacturing Method As a second example of the manufacturing method of the printed matter of the present aspect, the transfer plate preparing step described in the above section “(1) First example of manufacturing method” and the second example A transfer roll preparation step of wrapping a soft mold around a roll to prepare a transfer roll, and applying a composition for a transparent low reflection layer on one surface of a transparent substrate, pressing the coating layer with the transfer roll, and curing at the same time. And a printing step described in the above section “(1) First example of manufacturing method”.
The printed matter of the present aspect formed through the above-described steps may have a transparent low reflection layer of the second specification.

The curing method in the shaping step can be appropriately selected according to the composition of the composition for transparent low reflection layer. For example, when the composition for transparent low reflection layer contains an ultraviolet curable resin, ultraviolet irradiation is performed simultaneously with pressing. By performing the above, the transparent low reflection layer can be formed. The same applies to "(3) Third example of manufacturing method" described later.

The timing of performing the printing step is not particularly limited, and the printing steps may be performed in the order of the steps described above. After the printing layer is formed by printing on one surface of the transparent base material by the printing step, the transparent substrate is then formed. You may perform the shaping process which forms a transparent low reflection layer on the surface which has a printing layer of a material. The same applies to "(3) Third example of manufacturing method" described later.

(3) Third Example of Manufacturing Method As a third example of the manufacturing method of the printed matter of the present embodiment, the surface of a cylindrical cylinder is plated, and a large number of convex pyramidal structures having a predetermined variation are formed on the surface. A transfer plate preparation step of preparing the formed roll original plate, applying a composition for a transparent low reflection layer on one surface of a transparent substrate, and pressing the roll original plate at the same time to cure the coating layer to form a transparent low reflection layer And a printing step described in the section “(1) First example of manufacturing method” described above.
The printed matter of this aspect formed through the above-described steps may have a transparent low reflection layer of the second specification.

(4) Fourth Example of Manufacturing Method As a fourth example of the manufacturing method of the printed matter of the present aspect, a method of separately manufacturing a transparent low-reflection layer and laminating the transparent low-reflection layer with a transparent substrate can be mentioned. .. By this method, it is possible to manufacture a printed matter having the first specification transparent low reflection layer.
Specifically, the transfer plate preparation step described in the above-mentioned "(1) First example of manufacturing method" and the surface of the second soft mold on which the convex pyramidal structure is formed, A coating step of coating the composition for a low-reflection resin layer, and curing the coating layer with the transparent support layer disposed on the coating layer to peel off the second soft mold, and one surface of the transparent support layer. On the side, a shaping step of forming a transparent low reflection layer in which a low reflection resin layer having a large number of grooves on the surface is formed, and the transparent low reflection layer is formed on one surface of the transparent substrate via an adhesive layer. A method including a laminating step of laminating and a printing step of forming a printing layer on the surface of the transparent substrate opposite to the surface on which the transparent low reflection layer is laminated by printing. The laminating step and the printing step can be performed in any order.
The composition for low reflection resin layer contains the transparent resin described in the above section “1. Transparent low reflection layer (1) First specification of transparent low reflection layer”.

B. Second Aspect Next, a second aspect of the printed matter of the present invention (hereinafter, this term may be referred to as the present aspect) will be described. In the printed matter of this aspect, a large number of the groove portions are directly formed on the surface of the transparent substrate facing the surface on which the printed layer is formed.

The printed matter of this aspect will be described with reference to the drawings. FIG. 8 is a schematic sectional view showing an example of the printed matter of this embodiment. As shown in FIG. 8, the printed matter 10 of the present embodiment has a transparent base material 2 and a printed layer 3 formed directly on one surface of the transparent base material 2, and the printed layer 3 of the transparent base material 2 is formed. A large number of groove portions 1 having predetermined variations in shape and arrangement position are directly formed on the surface facing the formed surface.
In the printed matter according to the present aspect, the predetermined variation that a large number of grooves have is defined by quantifying three parameters. The three parameters and the predetermined values for causing a large number of groove portions to have a predetermined variation are the same as those described in the above-mentioned section "I. Groove portion", and therefore the description thereof is omitted here.

According to this aspect, it is possible to reduce the number of layers constituting the printed matter, and it is possible to prevent light reflection at the laminated interface. Moreover, since the printed matter can be made thin, the printed matter can have high workability.

Hereinafter, the printed matter of this aspect will be described. The details of the printed layer, the optional member, the physical properties of the printed matter, the display mode based on the structure of the printed matter, the use, and the like in this aspect are the same as the details described in the above section “A. First aspect”. Therefore, the description thereof is omitted here.

1. Transparent Base Material In the transparent base material in the present embodiment, a large number of groove portions are formed directly on the surface facing the surface on which the print layer is formed, with a predetermined variation.

Since the transparent base material in this embodiment has a large number of groove portions formed with a predetermined variation, the maximum reflectance and the maximum reflectance described in the above-mentioned “A. First embodiment 1. Transparent low reflection layer” and The haze value can be indicated.

(1) Structure of transparent base material The transparent base material in this embodiment has a large number of groove portions on the surface facing the surface on which the printed layer is formed. The details of the groove formed on the surface of the transparent substrate are the same as those described in the above-mentioned section "I. Groove", and thus the description thereof is omitted here.

In this embodiment, the transparent base material preferably has a base portion 5 that supports a large number of groove portions 1, as illustrated in FIG. 9. 9: is explanatory drawing explaining the transparent base material in this aspect, and is an enlarged view of P part of FIG.

The thickness of the base portion is not particularly limited as long as it can support a large number of groove portions having a predetermined variation and can have a self-supporting property as a printed material by a transparent base material, but it is 0.3 μm to It is preferably in the range of 100 mm, particularly in the range of 6 μm to 30 mm, and particularly preferably in the range of 9 μm to 15 mm. If the thickness of the base is less than the above range, it may be difficult to form many grooves on the surface of the transparent substrate, or the mechanical strength of the printed material may be poor. Because. On the other hand, when the thickness of the base portion exceeds the above range, the thickness of the entire printed matter becomes large, the workability is deteriorated, and cracks are easily generated in the transparent substrate.

The thickness of the base is an average value of the length from the surface of the transparent base material in contact with the printed layer to the tip of the groove bottom of the groove (the length of the portion indicated by h ₂ in FIG. 7). The height (h ₁ +h ₂ ) from the surface of the transparent base material in contact with the printed layer to the surface having the groove opening is measured using a film thickness meter (film thickness meter H-102 manufactured by Tester Sangyo Co., Ltd.). After the measurement, it can be calculated by subtracting the depth h _{1 of the} groove.

(2) Material of transparent base material The material of the transparent base material in this embodiment can be the same as the resin material of the transparent base material described in the above section "A. First embodiment 3. Transparent base material". .. Further, the transparent base material may include any of the additives described in the above section “A. First aspect 3. Transparent base material”, if necessary.

2. Other Configurations The printed matter according to the present aspect has a large number of groove portions formed on one surface of a transparent substrate so as to have a predetermined variation, and has a printed layer on the surface facing the one surface. It is not particularly limited as long as it is provided, and any member can be included as necessary. The arbitrary member may be the same as the arbitrary member described in the above section "A. First mode".

3. Others In the printed matter of the present aspect, a large number of groove portions may be formed on the outermost surface of the printed matter at least at positions overlapping with the printing layer in plan view, and the groove portions are provided at positions overlapping with the area where the printing layer is not formed in plan view. May be formed. The display mode of each structure of the printed matter of the present mode is the same as the content described in the above-mentioned “A. First mode”, and thus the description thereof is omitted here.

4. Manufacturing Method The method for manufacturing the printed matter of the present aspect is not particularly limited as long as it is a method capable of directly forming a large number of groove portions on one surface of the transparent substrate so as to have a predetermined variation.

(1) First Example of Manufacturing Method As another example of the manufacturing method of the printed matter of the present aspect, for example, a transfer original plate provided with a large number of convex pyramidal structures having predetermined variations is used, Transfer plate preparation step of forming a soft mold in which the concave pyramidal structure is formed, and using the soft mold to form an electroformed mold having a large number of convex pyramidal structures on the surface, the electroforming A shape that presses the surface on which the convex pyramidal structure is formed against the surface of the transparent substrate while heating the mold to form a large number of groove portions having a predetermined variation on one surface of the transparent substrate. Examples of the method include a step and a printing step of forming a printing layer on the surface of the transparent substrate opposite to the surface on which the groove is formed.
In manufacturing by such a hot embossing method, the shaping step and the printing step can be performed in any order.
The method for producing the transfer original plate provided with the convex pyramidal structure and the printing process can be the same as those described in the above section “A. First aspect 7. Manufacturing method”.

(2) Second Example of Manufacturing Method As another example of the manufacturing method of the printed matter of the present aspect, for example, the transfer plate preparing step and the heat melting described in the above-mentioned “(1) First example of manufacturing method”. By pressing the electroformed mold to the composition for a transparent substrate, the transparent substrate molding step of molding a transparent substrate having a large number of grooves having a predetermined variation on one surface, and the above-mentioned " A method including the printing step described in the section (1) First example of manufacturing method” can be mentioned. In the manufacturing by such a chill roll embossing method, the printing process is performed after the transparent substrate molding process.

(3) Third Example of Manufacturing Method Further, as another example of the method for manufacturing the printed matter of the present embodiment, for example, the transfer plate preparing step described in the above-mentioned “(1) First example of manufacturing method”, The electroformed mold is mounted inside the mold as a stamper, and the composition for a transparent substrate that is heated and melted is filled into the mold and after holding pressure, the mold is peeled off, and one surface is predetermined. The method includes a transparent base material forming step of forming a transparent base material on which a large number of groove portions having variations of 1) are formed, and a printing step described in the above-mentioned "(1) First example of manufacturing method". .. In manufacturing by such an injection molding method, the printing process is performed after the transparent substrate molding process.

In the transfer plate preparation step, nickel or the like is used as the metal used for forming the electroformed mold. Further, the pressing condition by the electroforming mold, the injection molding condition and the like are not particularly limited as long as the transparent substrate having a desired shape can be molded.
The composition for transparent base material contains the resin material described in the above section "1. Transparent base material".

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

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples.

1. Preparation of Monochromatic Printed Material A monochromatic printed matter was obtained by the following method.

[Example 1-1]
(Preparation of transfer master)
The stainless steel plate was blasted and finished so that the arithmetic average surface roughness (hereinafter sometimes abbreviated as Sa) in the three-dimensional surface roughness measurement was 0.35 μm. Electrolytic chromium plating was applied to the surface under the following conditions to obtain a transfer original plate A having a large number of convex pyramidal structures A on the plate surface. The inverted shape and variation of the convex pyramidal structure A of the transfer original plate A and the shape and variation of the groove portion A in the obtained printed matter were in agreement.

<Conditions for electrolytic chrome plating>
Using a plating bath containing the following compositions, with graphite electrodes as an anode, the current density of 80A / dm ² from every 1 minute (1 per step. Hereinafter, similarly to.) One by 3.0A / dm ² It was reduced to a final size of 20 A/dm ^2, and a black chrome plated 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: 3g / dm 3 (0.024mol /} 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 ).

(Preparation of the first soft mold)
A UV-curable soft mold-forming composition having the following composition was applied onto the surface of the transfer original plate A on which the convex pyramidal structure A was formed, and a polycarbonate (PC) film (pan) having a thickness of 0.2 mm was used. It was sandwiched between a light film and Teijin Kasei Co., Ltd., and UV irradiation was performed from the PC film surface side at a wavelength of 365 nm and an irradiation energy of 170 mJ/cm ² . After transferring the convex conical structure A of the transfer master A and curing the composition for forming a soft mold, the transfer master A is peeled off and the convex shape of the convex conical structure A of the transfer master A is reversed on one side. To obtain a first soft mold in which a large number of concave pyramidal structures A are shaped.

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

(Preparation of second soft mold)
The same soft mold forming composition as the first soft mold is applied to the surface of the first soft mold on which the concave pyramidal structure A is formed, and a polycarbonate (PC) film (Panlite film, having a thickness of 0.2 mm) is formed. It was sandwiched by Teijin Kasei Co., Ltd., and UV irradiation was performed from the PC film surface side at a wavelength of 365 nm and an irradiation energy of 170 mJ/cm ² . After curing the composition for forming a soft mold, the first soft mold is peeled off, and a second convex pyramidal structure A′, which is an inverted shape of the concave pyramidal structure A, is formed on the surface of the second soft mold. I got a soft mold.

(Production of monochromatic printed matter)
A 0.2 mm thick transparent substrate (polycarbonate (PC) film, product name: Panlite film, manufactured by Teijin Kasei Co., Ltd.) was gravure-printed over the entire surface, and the entire surface was color code No. The print layer was formed by using the pattern of the black print layer of 582 as a print image. The color of the print layer was designated by a color code manufactured by DIC. The same applies to the 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 ultraviolet curable transparent low reflection layer having the following composition is applied, and the transparent substrate is applied on the applied surface. The surface of the material facing the surface on which the black print layer was formed was placed on the coated surface side.
UV irradiation from the PC film surface side of the soft mold at a wavelength of 365 nm and an irradiation energy of 170 mJ/cm ² is performed to cure the composition for the transparent low reflection layer, and then the soft mold is peeled off to obtain a large number of grooves A on the outermost surface. A single-color printed matter having

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

[Example 2-1]
A stainless plate was blasted to have Sa=0.3 μm. Electrolytic chromium plating was performed on the surface under the following conditions to obtain a transfer original plate B having a large number of convex pyramidal structures B on the plate surface. The inverted shape and variation of the convex pyramidal structure B of the transfer original plate B and the shape and variation of the groove portion B in the obtained printed matter were in agreement.

<Conditions for electrolytic chrome 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 To form a black chrome plating film.

A monochromatic 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 original plate B was used instead of the transfer original plate A.

[Example 3-1]
A stainless plate was blasted to have Sa=0.25 μm. Electrolytic chromium plating was performed on the surface under the following conditions to obtain a transfer original plate C having a large number of convex pyramidal structures C on the plate surface. The inverted shape and variation of the convex pyramidal structure C of the transfer original C and the shape and variation of the groove portion C in the obtained printed matter were in agreement.

<Conditions for electrolytic chrome plating>
Using the same plating bath and the anode as in Example 1, to reduce the current density from 80A / dm ² per minute by 1.5A / dm ^2, and finally the 20A / dm ^2, electrolytic plating on stainless steel plate To form a black chrome plating film.

A monochromatic print having a large number of grooves C on the outermost surface was obtained in the same manner as in Example 1-1, except that the transfer original plate C was used instead of the transfer original plate A.

[Example 4-1]
A stainless plate was blasted to have Sa=0.3 μm. Electrolytic chromium plating was performed on the surface under the following conditions to obtain a transfer original plate D having a large number of convex pyramidal structures D on the plate surface. The inverted shape and variation of the convex pyramidal structure D of the transfer original plate D and the shape and variation of the groove portion D in the obtained printed matter were in agreement.

<Conditions for electrolytic chrome plating>
Using the same plating bath and the anode as in Example 1, to reduce the current density from 80A / dm ² per minute by 1.0A / dm ^2, and finally the 20A / dm ^2, electrolytic plating on stainless steel plate To form a black chrome plating film.

A monochromatic printed matter having a large number of grooves D on the outermost surface was obtained in the same manner as in Example 1-1, except that the transfer original plate D was used instead of the transfer original plate A.

[Example 5-1]
A stainless plate was blasted to have Sa=0.3 μm. Electrolytic chromium plating was applied to the surface under the following conditions to obtain a transfer original plate E having a large number of convex pyramidal structures E on the plate surface. The inverted shape and variation of the convex pyramidal structure E of the transfer original plate E and the shape and variation of the groove portion E in the obtained printed matter were in agreement.

<Conditions for electrolytic chrome 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 To form a black chrome plating film.

A monochromatic 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 original plate E was used instead of the transfer original plate A.

[Example 6-1]
A stainless plate was blasted to have Sa=0.3 μm. Electrolytic chromium plating was performed on the surface under the following conditions to obtain a transfer original plate F having a large number of convex pyramidal structures F on the plate surface. The inverted shape and variation of the convex pyramidal structure F of the transfer original plate F and the shape and variation of the groove portion F in the obtained printed matter were in agreement.

<Conditions for electrolytic chrome plating>
Using the same plating bath and the anode as in Example 1, to reduce the current density from 80A / dm ² per minute by 0.5A / dm ^2, and finally the 20A / dm ^2, electrolytic plating on stainless steel plate To form a black chrome plating film.

A monochromatic 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 original plate F was used in place of the transfer original plate A.

[Example 7-1]
A stainless plate was blasted to have Sa=0.25 μm. Electrolytic chromium plating was performed on the surface under the following conditions to obtain a transfer original plate G having a large number of convex pyramidal structures G on the plate surface. The inverted shape and variation of the convex pyramidal structure G of the transfer original plate G and the shape and variation of the groove portion G in the obtained printed matter were in agreement.

<Conditions for electrolytic chrome 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 To form a black chrome plating film.

A monochromatic print having a large number of groove portions G on the outermost surface was obtained in the same manner as in Example 1-1, except that the transfer original plate G was used instead of the transfer original plate A.

[Comparative Example 1-1]
A stainless plate was blasted to have Sa=0.3 μm. Electrolytic chromium plating was applied to the surface under the following conditions to obtain a transfer original plate H having a large number of convex pyramidal structures H on the plate surface. The inverted shape and variation of the convex pyramidal structure H of the transfer original plate H and the shape and variation of the groove portion H in the obtained printed matter were in agreement.

<Conditions for electrolytic chrome plating>
Using the same plating bath and anode as in Example 1, the current density was reduced from 80 A/dm ² by 0.4 A/dm ² per minute to finally 20 A/dm ^2, and electrolytic plating was performed on a stainless steel plate. To form a black chrome plating film.

A monochromatic print having 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 original plate H was used instead of the transfer original plate A.

[Comparative Example 2-1]
A stainless plate was blasted to have Sa=0.3 μm. Electrolytic chromium plating was performed on the surface under the following conditions to obtain a transfer original plate I having a large number of convex pyramidal structures I on the plate surface. The inverted shape and variation of the convex pyramidal structure I of the transfer original plate I and the shape and variation of the groove portion I in the obtained printed matter were in agreement.

<Conditions for electrolytic chrome plating>
Using the same plating bath and anode as in Example 1, the current density was reduced from 80 A/dm ² by 6.0 A/dm ² every minute to finally reach 20 A/dm ^2, and electrolytic plating was performed on a stainless steel plate. To form a black chrome plating film.

A monochromatic print having a large number of groove portions I on the outermost surface was obtained in the same manner as in Example 1-1, except that the transfer original plate I was used instead of the transfer original plate A.

[Comparative Example 3-1]
A stainless plate was blasted to have Sa=0.3 μm. Electrolytic chromium plating was performed on the surface under the following conditions to obtain a transfer original plate J having a large number of convex pyramidal structures J on the plate surface. The inverted shape and variation of the convex pyramidal structure J of the transfer original plate J and the shape and variation of the groove portion J in the obtained printed matter were in agreement.

<Conditions for electrolytic chrome 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 10A / dm ^2, electrolytic plating on stainless steel plate To form a black chrome plating film.

A monochromatic printed matter having a large number of grooves J on the outermost surface was obtained in the same manner as in Example 1-1, except that the transfer original plate J was used instead of the transfer original plate A.

[Comparative Example 4-1]
A stainless plate was blasted to have Sa=0.5 μm. Electrolytic chromium plating was applied to the surface under the following conditions to obtain a transfer master K having a large number of convex pyramidal structures K on the plate surface. The inverted shape and variation of the convex pyramidal structure K of the transfer original plate K and the shape and variation of the groove portion K in the obtained printed matter were in agreement.

<Conditions for electrolytic chrome 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 To form a black chrome plating film.

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

2. Preparation of multicolored printed matter Multicolored printed matter was prepared by the following method.

[Example 1-2]
A multicolor having a large number of grooves A on the outermost surface in the same manner as in Example 1-1, except that a gravure printing method was used to form a print layer having the following pattern on the entire surface of the transparent substrate. I got a print. The background of the print image of the print layer is the color code No. 582, which is composed of a black print layer, is white, and has a color code No. 125 yellow print layer, color code No. 564 red print layer, color code No. 649 green printing layer, color code No. Using the blue print layer of 578, a pattern in which alphabets A to Z are displayed in a size of 20 pt is used.

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

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

[Example 4-2]
A multicolor 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 original plate D was used in place of the transfer original plate A.

[Example 5-2]
A multicolor printed matter having 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 original plate E was used instead of the transfer original plate A.

[Example 6-2]
A multicolor printed matter having a large number of groove portions F on the outermost surface was obtained in the same manner as in Example 1-2 except that the transfer original plate F was used instead of the transfer original plate A.

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

[Comparative Example 1-2]
A multicolor 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 original plate H was used instead of the transfer original plate A.

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

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

[Comparative Example 4-2]
A multicolor printed matter having a large number of groove portions K on the outermost surface was obtained in the same manner as in Example 1-2 except that the transfer original plate K was used in place of the transfer original plate A.

3. Preparation of Multicolor Printed Material with Light-Shielding Layer A multicolored printed material with light-shielding layer was prepared by the following method.

[Example 1-3]
Aluminum was used as a vapor deposition source on the surface of the printing layer side of the multicolored print obtained in Example 1-2, and the following vapor deposition conditions were obtained by a vacuum vapor deposition method using an electron beam (EB) heating method while supplying oxygen gas. Then, an aluminum oxide vapor deposition film (light-shielding layer) having a film thickness of 50 nm and a light transmittance of 2% at a wavelength of 550 nm was formed to obtain a multicolor printed matter with a light-shielding layer.
(Deposition conditions)
・Deposition source: aluminum ・Degree of vacuum in deposition chamber: 2×10 ^-4 mbar
・Electron beam power: 25 kW
・Deposition time: 120 seconds

[Example 2-3]
An aluminum oxide vapor deposition film (light-shielding layer) was formed on the surface of the printing layer of the multicolored print obtained in Example 2-2 by the same method as in Example 1-3 to obtain a multicolored print with a light-shielding layer.

[Example 3-3]
An aluminum oxide vapor deposition film (light-shielding layer) was formed on the surface of the printing layer of the multicolored print obtained in Example 3-2 by the same method as in Example 1-3 to obtain a multicolored print with a light-shielding layer.

[Example 4-3]
An aluminum oxide vapor deposition film (light-shielding layer) was formed on the surface of the printing layer of the multicolored print obtained in Example 4-2 by the same method as in Example 1-3 to obtain a multicolored print with a light-shielding layer.

[Example 5-3]
An aluminum oxide vapor deposition film (light-shielding layer) was formed on the surface of the printing layer of the multicolored print obtained in Example 5-2 by the same method as in Example 1-3 to obtain a multicolored print with a light-shielding layer.

[Example 6-3]
An aluminum oxide vapor deposition film (light-shielding layer) was formed on the surface of the printing layer of the multicolored print obtained in Example 6-2 by the same method as in Example 1-3 to obtain a multicolored print with a light-shielding layer.

[Example 7-3]
An aluminum oxide vapor deposition film (light-shielding layer) was formed on the surface of the printing layer of the multicolored print obtained in Example 7-2 by the same method as in Example 1-3 to obtain a multicolored print with a light-shielding layer.

[Comparative Example 1-3]
An aluminum oxide vapor deposition film (light-shielding layer) was formed on the surface of the printing layer of the multicolored print obtained in Comparative Example 1-2 by the same method as in Example 1-3 to obtain a multicolored print with a light-shielding layer.

[Comparative Example 2-3]
An aluminum oxide vapor deposition film (light-shielding layer) was formed on the surface of the printing layer of the multicolored print obtained in Comparative Example 2-2 by the same method as in Example 1-3 to obtain a multicolored print with a light-shielding layer.

[Comparative Example 3-3]
An aluminum oxide vapor deposition film (light-shielding layer) was formed on the surface of the printing layer of the multicolored print obtained in Comparative Example 3-2 by the same method as in Example 1-3 to obtain a multicolored print with a light-shielding layer.

[Comparative Example 4-3]
An aluminum oxide vapor deposition film (light-shielding layer) was formed on the surface of the printing layer of the multicolored print obtained in Comparative Example 4-2 by the same method as in Example 1-3 to obtain a multicolored print with a light-shielding layer.

[Evaluation 1]
SEM observation was performed on the monochromatic printed materials and the multicolor printed materials obtained in Examples 1 to 7 and Comparative Examples 1 to 4 under the following conditions. The points shown in Table 1 were extracted from the large number of grooves formed on the surface of the printed matter, and the average of the area of the groove opening, the maximum inner angle of the groove opening, and the distance between the closest centers of gravity of the adjacent grooves was calculated from the plan view SEM image. The dispersion was calculated. The quantification of each parameter using the plan-view SEM image was performed by the method described in the above section "I. Groove part".
(conditions)
・SEM: Field emission scanning electron microscope S-4500 (manufactured by Hitachi High-Technologies Corporation)
-Observation method: Top-View (from the side having the groove portion)
-Pretreatment: Pt-Pd spatter-Observation magnification: x10k
・Field of view: Vertical 4μm x Horizontal 4μm

[Evaluation 2]
The maximum reflectances of the monochromatic prints obtained in Examples 1-1 to 7-1 and Comparative Examples 1-1 to 4-1 were measured under the following conditions.
(conditions)
・Measuring device: Scanning Spectorophotometer UV-3100PC (manufactured by Shimadzu Corporation)
・Measurement method: Total reflection for 8° incident light (wavelength range 380 nm to 780 nm)

[Evaluation 3]
Multicolor prints obtained in Examples 1-2 to 7-2 and Comparative Examples 1-2 to 4-2, as well as Examples 1-3 to 7-3 and Comparative Examples 1-3 to 4-3. With respect to the multicolor printed matter with the light-shielding layer, the color was visually confirmed, and the visibility of the printed image was evaluated. The evaluation method is based on the sharpness of the color of the multicolor printed matter of Comparative Examples 1-2 to 4-2 as a reference (Δ), and whether the color of each example is clear compared with the reference or not is determined according to the following criteria. did.
◎…The color is the clearest and the visibility is the best compared to the standard.
○ ... The color is very clear 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 and Table 2. In Tables 1 and 2, μ represents average and σ ² represents variance.

As shown in the examples, by forming the groove portion having a predetermined variation on the outermost surface of the printed matter, the color became clear and the visibility could be improved.
Further, from Examples 1-3 to 7-3, by further providing the light shielding layer on the surface of the printing layer side, the color of the printed image in the printing layer became clearer and the visibility was further improved.

DESCRIPTION OF SYMBOLS 1... Groove 2... Transparent base material 3... Printed layer 4... Transparent low reflection layer 10... Printed matter 11... Transparent support layer 12... Low reflection resin layer 14... Functional layer (light-shielding layer)

Claims (7)

A transparent substrate,
A printed matter having a print layer formed on one surface of the transparent substrate,
The printed matter, a large number of groove portions are formed on the outermost surface of the surface side facing the surface on which the printed layer of the transparent substrate is formed,
The groove part has an average area in the range of 94000 nm ² or more and 131000 nm ² or less when the plan view shape of the groove opening part, which is a region surrounded by the side surfaces of the groove part, is approximated to an octagon,
When the planar view shape of the groove opening of the groove is approximated to an octagon, the variance of the maximum internal angle is in the range of 600 (°) ² or more and 1020 (°) ² or less,
Distance between the centers of gravity of the one groove portion and the other groove portion having the center of gravity of the groove mouth portion at a position closest to the center of gravity when the shape of the groove mouth portion of the one groove portion in plan view is approximated to an octagon. Is 500 nm or less, and the dispersion of the distance between the centers of gravity is 8000 nm ² or more. A transparent low reflection layer is formed on a surface of the transparent substrate which faces the surface on which the printed layer is formed,
The printed matter according to claim 1, wherein a large number of the groove portions are formed on a surface of the transparent low reflection layer facing the transparent base material. The transparent low reflection layer, a transparent support layer, and a low reflection resin layer formed on one surface side of the transparent support layer, containing a transparent resin,
The printed matter according to claim 2, wherein a large number of the groove portions are formed on a surface of the low-reflection resin layer facing a surface in contact with the transparent support layer. The transparent low reflection layer is a single layer formed of a transparent resin,
The printed matter according to claim 2, which is directly formed on the transparent substrate. The printed matter according to claim 1, wherein a large number of the groove portions are directly formed on a surface of the transparent substrate that faces a surface on which the print layer is formed. The printed matter according to any one of claims 1 to 5, wherein a functional layer is provided on at least a surface of the printed layer that faces a surface of the printed layer that contacts the transparent substrate. The printed matter according to claim 6, wherein the functional layer is a light shielding layer.