JP2021160093A - Original plate for forming ink film, patterning method, pattern film forming method, and pattern film forming device - Google Patents

Abstract

To provide an original plate for forming an ink film that can achieve both of the durability of a lithographic plate and rewrite responsiveness and a patterning method therefor, and a pattern film forming method and a pattern film forming device using the original plate.SOLUTION: An original plate for forming an ink film has a substrate and a surface layer provided on the substrate, the surface layer having: a functional material part containing a stimulation-responsive compound that responds to an external stimulation to reversibly change in its affinity with water; and a convex support part that supports the functional material part.SELECTED DRAWING: Figure 2D

Description

The present invention relates to an ink film forming original plate and a pattern forming method thereof, a pattern film forming method using the original plate, and a pattern film forming apparatus.

Offset printing is one of the typical lithographic printing. In offset printing, a hydrophilic part and a hydrophobic part are provided on the surface of a lithographic plate, the hydrophilic part is moistened with water, and ink that is immiscible with water is applied on the surface of the lithographic plate to transfer the ink of the hydrophobic part to paper or the like. ..

In the conventional offset printing, a PS (Presented Plate) plate is used as an original plate (printing plate) for forming an ink film. This printing plate creates a difference between hydrophobicity and hydrophilicity by using a stimulus such as ultraviolet rays, and creates the difference to prepare a plate. In conventional printing plate production, even if one stimulus can produce a difference between hydrophobicity and hydrophilicity at first, the difference between hydrophobicity and hydrophilicity cannot be restored because there is only one stimulus. As a result, the PS plate creates a new plate each time a different image is printed. This has the problem that time is lost and the cost increases every time a planographic plate is made, and it also has an environmental disadvantage that the old plate is discarded every time a new plate is made. rice field.

In order to overcome such a disadvantage, a technique for rewriting a printing plate by two stimuli has been conventionally proposed. For example, Patent Document 1 proposes a pattern film forming method using first and second blankets having an ink film surface made of a single material (see FIG. 1-a).

On the other hand, in Patent Document 2, in order to improve the durability of the printing plate, an ink film having a surface layer containing a stimulus-responsive compound and a resin whose affinity with water changes reversibly in response to an external stimulus is formed. An original version has also been proposed (see Figure 1-b).

Japanese Unexamined Patent Publication No. 2016-175192 Japanese Unexamined Patent Publication No. 2019-119057

However, in the technique described in Patent Document 1, although the printing plate can be rewritten, there is a problem that the durability of the printing plate is inferior because the surface of the printing plate is made of a single material.

Further, the technique described in Patent Document 2 has a problem that the durability of the printing plate is improved, but since the resin is contained in a relatively large amount, structural conversion is difficult to occur and the responsiveness is deteriorated. rice field.

Therefore, the present invention provides an ink film forming original plate and a pattern forming method thereof, a pattern film forming method using the original plate, and a pattern film forming apparatus capable of achieving both durability and rewrite responsiveness of the printing plate. With the goal.

The present inventor has accumulated extensive research. As a result, in order to ensure the durability of the printing plate and to separate the hydrophilicity / hydrophobic control of the printing plate, the "support part" made of engineering plastics, metal oxides, etc. and the "functional material part" made of functional compounds It was found that durability and hydrophilic / hydrophobic control can be achieved at the same time by using a printing plate prepared by separately providing "". Based on such findings, the present invention has been completed.

According to the present invention, by producing a printing plate by separately providing a support portion for ensuring durability and a functional material portion for ensuring responsiveness, both durability and hydrophilic / hydrophobic control can be achieved. It is possible to provide an original plate for forming an ink film that has both durability and rewrite responsiveness.

A is a cross-sectional view schematically showing an original plate having a surface made of a "single material" of the prior art. FIG. B is a cross-sectional view schematically showing an original plate having a surface layer containing a stimulus-responsive compound and a resin of the prior art. C is a functional material portion containing a stimulus-responsive compound whose affinity with water changes reversibly in response to an external stimulus of the present invention, and a convex support portion that supports the functional material portion. It is sectional drawing which represented typically the original plate which has. (A) is a perspective view schematically showing a "structure (1)" having a rectangular parallelepiped (cube) shape, which is one of the basic structures of the support portion of the original plate, and (b) is a perspective view of (a). It is a plan view of the quadrangle (square) which looked at the "structure (1)" of the rectangular parallelepiped (cube) shape from above. In (a), a support portion formed by extending (or connecting) the structure (1) shown in FIGS. 2A and 2A and 2A in the vertical direction on the substrate to form a line shape is arranged, and the line shape is formed. It is a perspective view which represented typically the structure which arranged the support part in parallel at equal intervals in the lateral direction on a substrate. (B) is a plan view of the structure in which the support portion of (a) is arranged in a line shape as viewed from above. (C) is a cross-sectional view schematically showing the state of the cross-sectional structure of the original plate to which the substrate and the functional material portion are added in the cross-sectional view of the X-ray line of (b). The vertical direction on the substrate refers to the long axis direction on the substrate or one radial direction, and is hereinafter simply referred to as the vertical direction. Further, the horizontal direction on the substrate means a short axis direction on the substrate or a radial direction perpendicular to the "one radial direction" and perpendicular to the vertical direction, and is hereinafter simply referred to as a horizontal direction. (A) is a perspective view schematically showing a structure in which the support portions of the structure (1) shown in FIGS. 2A and 2A and 2B are arranged at equal intervals in the vertical direction and the horizontal direction on the substrate. Is. (B) is a plan view of the structure in which the substrate surface of the gap in which each of the support portions of (a) is arranged is arranged so as to be in a grid pattern, as viewed from above. (C) is a cross-sectional view schematically showing the state of the cross-sectional structure of the original plate to which the substrate and the functional material portion are added in the cross-sectional view of the X-ray line of (b). In (a), the support portions of the structure (1) shown in FIGS. 2A and 2A and 2B are arranged at equal intervals in the vertical direction and the horizontal direction on the substrate, and the structure (1) is described. It is a perspective view which schematically represented the checkered structure in which two kinds of quadrangles (squares or rectangles) of the bottom surface part of the support part and the exposed part of a substrate surface are alternately arranged. (B) is a plan view of the checkered structure of (a) seen from above. (C) is a cross-sectional view schematically showing the state of the cross-sectional structure of the original plate to which the substrate and the functional material portion are added in the cross-sectional view of the X-ray line of (b). (A) is one of the basic structures of the support portion of the original plate, which is a "structure (2)" in which the bottom surface of the triangular prism is a quadrangle and the top is the ridgeline of the triangular prism (hereinafter, also referred to as a lateral triangular prism shape). Is a perspective view schematically showing. (B) is a plan view of a triangle (equilateral triangle) when the "structure (2)" of the laterally inverted triangular prism shape of (a) is viewed from above. The triangular prism (regular prism) means a prism having two bottom surfaces of a triangle (equilateral triangle) and three side surfaces having a quadrangular surface. In (a), a support portion 13 is arranged in which the structure (2) shown in FIGS. 3A (a) and 3A (b) is vertically extended (or connected) on a substrate to form a line shape, and this line is arranged. FIG. 5 is a perspective view schematically showing a structure in which the shaped support portions 13 are arranged in parallel on the substrate 12 so that the ridgelines at the bottoms of the respective support portions 13 adjacent to each other in the lateral direction are substantially in contact with each other. (B) is a plan view of the structure in which the support portion of (a) is arranged in a line shape as viewed from above. (C) is a cross-sectional view schematically showing the state of the cross-sectional structure of the original plate to which the substrate and the functional material portion are added in the cross-sectional view of the X-ray line of (b). (A) is a perspective view schematically showing a structure in which the support portions of the structure (2) shown in FIGS. 3A and 3A and 3A (b) are arranged at equal intervals in the vertical direction and the horizontal direction on the substrate. Is. (B) is a plan view of the structure in which the substrate surface of the gap in which each of the support portions of (a) is arranged is arranged so as to be in a grid pattern, as viewed from above. (C) is a cross-sectional view schematically showing the state of the cross-sectional structure of the original plate to which the substrate and the functional material portion are added in the cross-sectional view of the X-ray line of (b). In (a), the support portions of the structure (2) shown in FIGS. 3A (a) and 3A (b) are arranged at equal intervals in the vertical direction and the horizontal direction on the substrate, and the structure (2) is formed. It is a perspective view which represented typically the checkered structure in which two kinds of quadrangles (squares or rectangles) of the bottom surface part of a support part and the exposed part of a substrate surface are arranged alternately. (B) is a plan view of the checkered structure of (a) seen from above. (C) is a cross-sectional view schematically showing the state of the cross-sectional structure of the original plate to which the substrate and the functional material portion are added in the cross-sectional view of the X-ray line of (b). In (a), the support portions of the structure (2) shown in FIGS. 3A (a) and 3A (b) are arranged in the vertical direction and the horizontal direction on the substrate with almost no gap, and in the vertical direction on the substrate. Is arranged so that the top ridge line is on this virtual line with respect to the vertical straight line (virtual line), and adjacent to this, the right side (or left side) of the virtual line is half the distance of the bottom square. It is a perspective view which schematically represented the structure of the so-called rectangular wave (square wave) shape which arranged (alternately) so that the top ridge line came to the position shifted to the side). Further, in (a), in the lateral direction on the substrate, the ridges (lines) on the bottom surfaces of the adjacent support portions 13 are arranged in a line shape so as to be parallel to each other. It is also a perspective view schematically showing the structure. (B) is a plan view of the structure arranged in the rectangular wave (square wave) shape of (a) as viewed from above. (C) is a cross-sectional view schematically showing the state of the cross-sectional structure of the original plate to which the substrate and the functional material portion are added in the cross-sectional view of the X-ray line of (b). (A) is a perspective view schematically showing a "structure (3)" in the shape of a quadrangular pyramid (regular quadrangular pyramid), which is one of the basic structures of the support portion of the original plate. (B) is a plan view of a quadrangle (square) when the "structure (3)" of the regular quadrangular pyramid shape of (a) is viewed from above. A quadrangular pyramid (regular quadrangular pyramid) is a pyramid having a quadrangular bottom surface. In (a), the structures (3) shown in FIGS. 4A (a) and 4A (b) are connected in the vertical direction on the substrate, and a so-called line-shaped support portion 13 is arranged, and the line-shaped support portion 13 is arranged. FIG. 5 is a perspective view schematically showing a structure in which the support portions 13 are arranged in parallel on the substrate 12 so that the ridgelines at the bottoms of the respective support portions 13 adjacent to each other in the lateral direction are substantially in contact with each other. (B) is a plan view of the structure in which the support portion of (a) is arranged in a line shape as viewed from above. (C) is a cross-sectional view schematically showing the state of the cross-sectional structure of the original plate to which the substrate and the functional material portion are added in the cross-sectional view of the X-ray line of (b). (A) is a perspective view schematically showing a structure in which the support portions of the structure (3) shown in FIGS. 4A and 4A and 4B are arranged at equal intervals in the vertical direction and the horizontal direction on the substrate. Is. (B) is a plan view of the structure in which the substrate surface of the gap in which each of the support portions of (a) is arranged is arranged so as to be in a grid pattern, as viewed from above. (C) is a cross-sectional view schematically showing the state of the cross-sectional structure of the original plate to which the substrate and the functional material portion are added in the cross-sectional view of the X-ray line of (b). In (a), the support portions of the structure (3) shown in FIGS. 4A (a) and 4A (b) are arranged at equal intervals in the vertical direction and the horizontal direction on the substrate, and the structure (3) is formed. It is a perspective view which represented typically the checkered structure in which two kinds of quadrangles (squares or rectangles) of the bottom surface part of a support part and the exposed part of a substrate surface are arranged alternately. (B) is a plan view of the checkered structure of (a) seen from above. (C) is a cross-sectional view schematically showing the state of the cross-sectional structure of the original plate to which the substrate and the functional material portion are added in the cross-sectional view of the X-ray line of (b). In (a), the support portions of the structure (3) shown in FIGS. 4A and 4A and 4B are arranged in the vertical direction and the horizontal direction on the substrate with almost no gap, and in the vertical direction on the substrate. Is arranged so that the top ridge line is on this virtual line with respect to the vertical straight line (virtual line), and adjacent to this, the right side (or left side) of the virtual line is half the distance of the bottom square. It is a perspective view which schematically represented the structure of the so-called rectangular wave (square wave) shape which arranged (alternately) so that the top ridge line came to the position shifted to the side). Further, in (a), in the lateral direction on the substrate, the ridges (lines) on the bottom surfaces of the adjacent support portions 13 are arranged in a line shape so as to be parallel to each other. It is also a perspective view schematically showing the structure. (B) is a plan view of the structure arranged in the rectangular wave (square wave) shape of (a) as viewed from above. (C) is a cross-sectional view schematically showing the state of the cross-sectional structure of the original plate to which the substrate and the functional material portion are added in the cross-sectional view of the X-ray line of (b). It is the schematic which shows the pattern film forming apparatus which concerns on one Embodiment of this invention. It is a figure which shows the image pattern used for evaluation. It is a figure which shows the intersection of the thin lines used for evaluation.

The present invention has a functional material portion containing a stimulus-responsive compound whose affinity with water changes reversibly in response to an external stimulus, and a convex support portion that supports the functional material portion. , An original plate for forming an ink film. The ink film forming original plate having this structure can have both durability and rewrite responsiveness. The original plate for forming an ink film of the present invention is also hereinafter referred to as a "printing original plate" or an "original plate".

The reason why the above effect is obtained by the original version of the present invention is unknown, but the following mechanism can be considered. The following mechanism is speculative, and the present invention is not limited to the following mechanism.

When an original plate having a surface made of "single material" shown in FIG. 1A, such as the technique described in Patent Document 1 described above, is used, the responsiveness of hydrophilic / hydrophobic control is good, but rewriting and drawing are performed. By repeating the above steps, it was found that there is a problem in the durability of the original plate, in which the surface of the original plate is damaged and becomes brittle due to the deterioration of a single material, and the reproducibility of fine lines deteriorates.

When an original plate having a surface layer containing the stimulus-responsive compound shown in FIG. 1B and a resin, such as the technique described in Patent Document 2 described above, is used, the durability is improved, but the response of hydrophilic / hydrophobic control is improved. The problem of poor sexuality arose, and it was found that there was a trade-off between the durability of the original plate and the stimulus responsiveness.

On the other hand, as shown in FIG. 1C, the original version of the present invention includes a functional material portion containing a stimulus-responsive compound whose affinity with water changes reversibly in response to an external stimulus, and the above-mentioned functional material portion. It has a convex support portion that supports the functional material portion. By separately providing the support part that secures durability and the functional material part that secures responsiveness by hydrophilic / hydrophobic control, the durability of the support part and the responsiveness of the functional material part function. It was possible to separate and achieve both durability and rewrite responsiveness.

Hereinafter, the configuration of the original plate for forming an ink film of the present invention will be described in detail.

In addition, in this specification, "X to Y" indicating a range means "X or more and Y or less". Unless otherwise specified in the present specification, the operation and the measurement of physical properties are performed under the conditions of room temperature (range of 20 ° C. or higher and 25 ° C. or lower) / relative humidity of 40% RH or more and 50% RH or less.

[Original plate for forming ink film]
[Composition of original plate]
The original plate for forming an ink film of the present invention usually has a substrate 12 and a surface layer 15 provided on the substrate 12, as shown in the cross-sectional view of the original plate 11 of FIG. 1C. The surface layer 15 has a support portion 13 and a functional material portion 14. Specifically, a convex support portion 13 is provided on the substrate 12. The support portion 13 has a structure that supports the functional material portion 14 containing a stimulus-responsive compound whose affinity with water changes reversibly in response to an external stimulus. For example, in the cross-sectional example of the original plate 11 of FIG. 1C, the convex support portion 13 has a comb shape, and the functional material portion 14 is formed in each concave portion of the gap between the comb teeth (convex portions) 13. Is buried. As a result, the support portion 13 has a structure that supports the functional material portion 14.

(substrate)
The shape of the substrate is not particularly limited, and examples thereof include a flat plate shape and a cylindrical shape.

The material of the substrate is also not particularly limited, and is, for example, aluminum, an aluminum alloy (such as an alloy of aluminum and magnesium or / and silicon), a metal such as iron, copper, and stainless steel, and a metal oxide such as anodized aluminum and titanium oxide. , Polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyacrylonitrile, polyvinyl chloride, polycarbonate, polyamide and other thermoplastic resins, epoxy resin, phenolic resin and other thermocurable resins, styrene-butadiene rubber and other plastics Can be mentioned. These may be used individually by 1 type, or may be used in combination of 2 or more type.

The substrate may have either a single layer or a multi-layered form. Further, in the case of multiple layers, each layer may be composed of different materials.

(Surface layer)
Regarding the shape of the surface layer provided on the substrate, that is, the arrangement of the support portion and the functional material portion, the durability of the support portion and the responsiveness of the functional material portion can be functionally separated, and the durability and rewriting can be performed. It is not particularly limited as long as it can achieve both responsiveness and responsiveness.

(Arrangement of support part of surface layer)
As for the arrangement of the support portion of the surface layer, the rectangular parallelepiped (cubic) shaped structure (1) shown in FIGS. 2A and 2A and the laterally inverted triangular prism (regular triangular prism) shown in FIGS. ) Shaped structure (2) and the minimum basic structure of the support portion 13 of the quadrangular prism (regular prism) shaped structure (3) shown in FIGS. 4A (a) and 4A (b) are appropriately arranged. , Not limited to these.

(1) Arrangement Form of Line-Shaped Support Part Using Structure (1) As the line-shaped arrangement form using the structure (1), the structures (1) shown in FIGS. 2A and 2A are shown. , As shown in FIGS. 2B (a) and 2B (b), a support portion 13 which is vertically extended (or connected) on the substrate to form a line is arranged. Examples thereof include a form in which the line-shaped support portions 13 are arranged in parallel at equal intervals in the lateral direction on the substrate 12. As shown in FIG. 2B (c), the cross section of the XX line in FIG. 2B (b) of the line-shaped arrangement using this structure (1) is a quadrangular (square) -shaped (convex) support portion. 13 has a so-called comb shape (similar to FIG. 1C), which is arranged at equal intervals on the substrate with gaps. A concave functional material portion 14 is arranged in a gap between each quadrangular (square) -shaped (each comb tooth) 13. The cross-sectional structure of the original plate shown in FIG. 2B (c) is defined as the structure (A).

(2) Lattice-like arrangement form using the structure (1) As the lattice-like arrangement form using the structure (1), the support portion 13 of the structure (1) shown in FIGS. As shown in FIGS. 2C (a) and 2C (b), there is a form in which the above-mentioned is arranged at equal intervals in the vertical direction and the horizontal direction on the substrate. In this case, as shown in FIG. 2C (b), the planar shape of the substrate surface in the gap where each support portion 13 is arranged is a so-called lattice shape when viewed from above. As shown in FIG. 2C, the cross section of the X-ray line of FIG. 2C (b) showing the arrangement using this structure (1) has a quadrangular (square) -shaped (convex) support portion 13. It has a shape in which gaps are formed on the substrate 12 and arranged at equal intervals. A concave functional material portion 14 is arranged in a gap between the quadrangular (square) shapes 13. Therefore, the cross-sectional structure of the original plate shown in FIG. 2C (c) is also the structure (A). The grid shape means that a plurality of vertical lines and horizontal lines intersect (shape) like a so-called grid fringe. As shown in FIG. 2C (b), the substrate surface shape of the gap in which each support portion 13 is arranged has a grid shape in which a plurality of vertical lines and horizontal lines intersect at right angles, and a plurality of vertical lines. It also includes a diamond shape in which the line and the horizontal line intersect without being orthogonal. However, the checkered pattern, which will be described later, has a different arrangement.

(3) Checkered arrangement form using the structure (1) As the checkered arrangement form using the structure (1), the support portion 13 of the structure (1) shown in 2A (a) and (b) is used. As shown in FIGS. 2D (a) and 2D (b), the bottom surface portion of the support portion 13 and the substrate 12 of the structure (1) are arranged at equal intervals in the vertical direction and the horizontal direction on the substrate. An example is a checkered structure in which two types of squares (squares) on the exposed surface are arranged alternately. The cross section of the XX line in FIG. 2D (b) showing the checkered arrangement using this structure (1) is a quadrangular (square) -shaped (convex) support as shown in FIG. 2D (c). The portions 13 have a shape in which they are arranged at equal intervals on the substrate 12 with a gap. A concave functional material portion 14 is arranged in a gap between the quadrangular (square) shapes 13. Therefore, the cross-sectional structure of the original plate shown in FIG. 2D (c) is also the structure (A). The checkered shape is a kind of grid shape, and has a shape in which two types of quadrangles (squares or rectangles) are alternately arranged, that is, a portion where the surface of the substrate 12 is exposed and a portion where the bottom surface of the support portion 13 of the structure (1) is exposed. say.

(4) Line-shaped arrangement form using the structure (2) As the line-shaped arrangement form using the structure (2), the structures (2) shown in FIGS. 3A and 3B are shown in FIG. 3B (2). As shown in a) and FIG. 3B (b), a support portion 13 extending in the vertical direction (or being connected) on the substrate to form a line is arranged. Examples thereof include a form in which the line-shaped support portions 13 are arranged in parallel so that the ridgelines at the bottoms of the support portions 13 adjacent to each other in the lateral direction on the substrate 12 are substantially in contact with each other. As shown in FIG. 3B (c), the cross section of the line-shaped arrangement in FIG. 3B (b) using this structure (2) has a triangular (convex) support portion 13 as a substrate. It has a so-called triangular wavy shape (sawtooth shape) that is arranged on the top at equal intervals with almost no gaps. The functional material portion 14 is arranged in each concave portion of the gap between the triangular shapes (teeth of each saw) 13. The cross-sectional structure of the original plate shown in FIG. 4E (c) is defined as the structure (B). The triangular wavy shape (saw tooth shape) is a shape that is jagged like a saw tooth.

(5) Lattice-like arrangement form using the structure (2) As the lattice-like arrangement form using the structure (2), the support portion 13 of the structure (2) shown in FIGS. As shown in FIGS. 3C (a) and 3C (b), there is a form in which the above-mentioned is arranged at equal intervals in the vertical direction and the horizontal direction on the substrate. In this case, as shown in FIG. 3C (b), the planar shape of the substrate surface in the gap where each support portion 13 is arranged is a so-called lattice shape when viewed from above. As shown in FIG. 3C, the cross section of the X-ray line of FIG. 3C (b) showing the arrangement using this structure (2) is a triangular (equilateral triangle) -shaped (convex) support portion 13. Is arranged at equal intervals on the substrate 12 with a gap. A concave functional material portion 14 is arranged in a gap between the triangular (equilateral triangle) shapes 13. The cross-sectional structure of the original plate shown in FIG. 3C (c) is defined as the structure (C). The grid-like definition and the like are the same as the definition and the like in the above-mentioned (2) "lattice-like arrangement form using the structure (1)".

(6) Checkered Arrangement Form Using Structure (2) As a checkered arrangement form using structure (2), the support portion 13 of the structure (2) shown in FIGS. 3D (a) and 3D (b) are arranged at equal intervals in the vertical direction and the horizontal direction on the substrate, and the bottom surface portion of the support portion 13 and the substrate of the structure (2) are arranged. A checkered structure in which two types of quadrangles (squares) of 12 exposed surface portions are alternately arranged can be mentioned. The cross section of the XX line in FIG. 3D (b) showing the checkered arrangement using this structure (2) is a triangular (equilateral triangle) -shaped (convex) support as shown in FIG. 3D (c). The body portion 13 has a shape in which the body portion 13 is arranged at equal intervals on the substrate 12 with a gap. A concave functional material portion 14 is arranged in a gap between the triangular (equilateral triangle) shapes 13. Therefore, the cross-sectional structure of the original plate shown in FIG. 3D (c) is also the structure (C). The definition of the checkered shape, etc. is the same as the definition, etc. of the "checkered shape arrangement form using the structure (1)" in (3) above.

(7) Rectangular wave (square wave) -shaped arrangement form using the structure (2) The rectangular wave (square wave) -like arrangement form using the structure (2) is shown in FIGS. 3A and 3A and 3B. As shown in FIGS. 3E (a) and 3E (b), the support portion 13 of the structure (2) shown is arranged in the vertical direction and the horizontal direction on the substrate with almost no gap, and is on the substrate 12. In the vertical direction of, the top ridge line is placed on this virtual line with respect to the vertical straight line (virtual line), and adjacent to this, the right horizontal side of the virtual line (half the distance of the bottom square) ( Alternatively, there is a so-called rectangular wave (square wave) structure in which the top ridges are arranged (alternately) at positions shifted to the left side). In the horizontal direction on the substrate, the ridges (lines) on the bottom surfaces of the adjacent support portions 13 are arranged in a line shape so as to be parallel to each other. .. As shown in FIG. 3E (c), the cross section of the XX line in FIG. 3E (b) showing the arrangement in the shape of a rectangular wave (square wave) using this structure (2) is in the shape of a triangle (equilateral triangle). The support portion 13 (convex) has a shape in which the support portions 13 are arranged on the substrate 12 at equal intervals with almost no gap, that is, a so-called triangular wave shape (sawtooth shape). A concave functional material portion 14 is arranged in a gap between the triangular shapes (teeth of each saw) 13. Therefore, the cross-sectional structure of the original plate shown in FIG. 3E (c) is also the structure (B). ).

(8) Line-shaped arrangement form using the structure (3) As the line-shaped arrangement form using the structure (3), the support portion 13 of the structure (3) shown in FIGS. 4B (a) and 4B (b) show, a so-called line-shaped support portion 13 is arranged by connecting them in the vertical direction on the substrate, and the line-shaped support portion 13 is arranged. There is a structure in which the ridges of the bottoms of the support portions 13 adjacent to each other in the lateral direction on the substrate 12 are arranged in parallel so as to be substantially in contact with each other. As shown in FIG. 4B (c), the cross section of the XX line in FIG. 4B (b) having a line-like arrangement using this structure (3) has a triangular (convex) support portion 13 as a substrate. It has a so-called triangular wavy shape (sawtooth shape) that is arranged on the top at equal intervals with almost no gaps. A concave functional material portion 14 is arranged in a gap between the triangular shapes (teeth of each saw) 13. Therefore, the cross-sectional structure of the original plate shown in FIG. 4B (c) is also the structure (B).

(9) Lattice-like arrangement form using the structure (3) As the lattice-like arrangement form using the structure (3), the support portion 13 of the structure (3) shown in FIGS. As shown in FIGS. 4C (a) and 4C (b), there is a form in which the above-mentioned is arranged at equal intervals in the vertical direction and the horizontal direction on the substrate. In this case, as shown in FIG. 4C (b), the planar shape of the substrate surface in the gap where each support portion 13 is arranged is a so-called lattice shape when viewed from above. As shown in FIG. 4C, the cross section of the X-ray line of FIG. 4C (b) showing the arrangement using this structure (3) is a triangular (equilateral triangle) -shaped (convex) support portion 13. Is arranged at equal intervals on the substrate 12 with a gap. A concave functional material portion 14 is arranged in a gap between the triangular (equilateral triangle) shapes 13. Therefore, the cross-sectional structure of the original plate shown in FIG. 4C (c) is also the structure (C). The grid-like definition and the like are the same as the definition and the like in the above-mentioned (2) "lattice-like arrangement form using the structure (1)".

(10) Checkered Arrangement Form Using Structure (3) As a checkered arrangement form using structure (3), the support portion 13 of the structure (3) shown in FIGS. 4A and 4A and 4A and 4A. 4D (a) and 4D (b) are arranged at equal intervals in the vertical direction and the horizontal direction on the substrate, and the bottom surface portion of the support portion 13 and the substrate of the structure (3) are arranged. A checkered structure in which two types of quadrangles (squares) of 12 exposed surface portions are alternately arranged can be mentioned. The cross section of the XX line in FIG. 4D (b) showing the checkered arrangement using this structure (3) is a triangular (equilateral triangle) -shaped (convex) support as shown in FIG. 4D (c). The body 13 has a shape in which the body 13 is arranged at equal intervals on the substrate 12 with a gap. A concave functional material portion 14 is arranged in a gap between the triangular (equilateral triangle) shapes 13. The cross-sectional structure of the original plate shown in FIG. 4D (c) is also the structure (C). The definition of the checkered shape, etc. is the same as the definition, etc. of the "checkered shape arrangement form using the structure (1)" in (3) above.

(11) Rectangular wave (square wave) -shaped arrangement form using the structure (3) Examples of the rectangular wave (square wave) -like arrangement form using the structure (3) are shown in FIGS. 4A and 4A and 4B. As shown in FIGS. 4E (a) and 4E (b), the support portion 13 of the structure (3) shown is arranged in the vertical direction and the horizontal direction on the substrate with almost no gap, and is on the substrate 12. In the vertical direction of, the top ridge line is placed on this virtual line with respect to the vertical straight line (virtual line), and adjacent to this, the right horizontal side of the virtual line (half the distance of the bottom square) ( Alternatively, there is a so-called rectangular wave (square wave) structure in which the top ridges are arranged (alternately) at positions shifted to the left side). In the horizontal direction on the substrate, the ridges (lines) on the bottom surfaces of the adjacent support portions 13 are arranged in a line shape so as to be parallel to each other. .. The cross section of the XX line in FIG. 4E (b) showing the arrangement in the shape of a rectangular wave (square wave) using this structure (3) is in the shape of a triangle (equilateral triangle) as shown in FIG. 4E (c). The support portion 13 (convex) has a shape in which the support portions 13 are arranged on the substrate 12 at equal intervals with almost no gap, that is, a so-called triangular wave shape (sawtooth shape). A concave functional material portion 14 is arranged in a gap between the triangular shapes (teeth of each saw) 13. Therefore, the cross-sectional structure of the original plate shown in FIG. 4E (c) is also the structure (B).

In FIGS. 2 to 4, the support portion 13 and the functional material portion 14 have substantially the same size so that it can be easily understood that the line shape, the grid shape, the checkered shape, and the rectangular wavy shape are formed. Alternatively, the functional material unit 14 expresses it slightly larger. However, in practice, it is preferable to satisfy the sizes a to d shown in the following formula, and the support portion 13 is smaller than the size shown in the figure. If it is arranged in a grid shape, a checkered shape, or a rectangular wavy shape, it shall be classified into that shape (see Examples).

(Forms of structures (A) to (C))
The master plate for forming an ink film of the present invention is perpendicular to the plane of the master plate along a line connecting the center points of the upper surface of the adjacent convex support portion 13, the center points of the top ridgeline, or the vertices. The cross section is
(A) A structure in which quadrangular (convex) support portions 13 are arranged at equal intervals on the substrate 12 with gaps, and concave functional material portions 14 are arranged in the gaps between the quadrangular portions 13. A),
(B) A structure in which triangular (convex) support portions 13 are arranged on the substrate 12 at equal intervals without gaps, and concave functional material portions 14 are arranged in gaps between the triangular shapes 13 (B). Or (c) triangular (convex) support portions 13 are arranged at equal intervals on the substrate 12 with gaps, and concave functional material portions 14 are arranged in the gaps between the triangular shapes 13. Has a structure (C)
In the structure (A), the length a of each support portion 13 and the length b of each functional material portion 14 on the uppermost surface portion of the cross section satisfy the following equations (FIGS. 2B (c) and 2C (FIG. 2C)). c), see FIG. 2D (c), etc.),
In the structure (B), the length c of each functional material portion 14 on the uppermost surface portion of the cross section satisfies the following formula (FIGS. 3B (c), 3E (c), 4B (c), 4E (FIG. 4B)). c) etc.),
In the structure (C), the length d of each functional material portion 14 on the uppermost surface portion of the cross section satisfies the following equation (FIGS. 3C (c), 3D (c), 4C (c), 4D (FIG. 4C)). c) etc.) is preferable.

By satisfying the above formula, the functional material portion 14 and the support portion 13 constituting the surface layer can be easily formed, and further, sufficient durability by the support portion and excellent responsiveness by the functional material portion can be obtained. The functions can be separated, and both durability and rewrite responsiveness can be achieved at the same time. Specifically, regarding the length b (c, d) of the functional material unit 14, the print plate of recent digital exposure has a minimum dot diameter of 10 μm at a resolution of 2400 dpi and a minimum dot diameter of 6 μm at a resolution of 4000 dpi. That is, the minimum image portion is about 6 μm. That is, the length a of the support portion 13 needs to be equal to or smaller than the minimum value of the length b of the image portion (functional material portion 14) (a ≦ b). Further, since the scale on which the ink is applied is the minimum diameter of the plate making (printing plate on which the image is formed), 6 μm to 10 μm is the minimum scale. Therefore, it is important to consider how much the support portion 13 can be scattered in 6 μm (a <6 μm). However, from the viewpoint of the accuracy of microfabrication, a is preferably 100 nm or more (100 nm ≦ a). Further, the relationship between the length a of the support portion 13 and the length b of the functional material portion 14 in the structure (A) is better as the length b of the functional material portion 14 is greater than or equal to a and the length b becomes narrower. (Too small), b is preferably 1 μm or more and a is less than 6 μm from the viewpoint of preventing the support portion 13 that does not respond from increasing due to the relatively large a. From the viewpoint of durability, improvement in responsiveness, and accuracy of microfabrication, both a and b are preferably 100 nm or more.

Further, the smaller the lengths c and d of the functional material portion 14 in the structures (B) and (C), the better the durability, but from the viewpoint of the accuracy of microfabrication, c and d are 100 nm or more. Is preferable.

From the above viewpoint, it is more preferable that the above a, b, c and d satisfy the following formula.

In addition, in FIGS. In this case, since the cross section is trapezoidal, in addition to the lengths c and d of the functional material portion 14, the length of the upper side of the trapezoid (= cross section) so as to satisfy the condition a in each case. The length) a of each support portion 13 on the uppermost surface portion may be appropriately selected.

In the ink film forming original plate, the functional material portion 14 and the support portion 13 are preferably arranged in a line when viewed from a flat surface (above the surface layer on the opposite side of the substrate) (the functional material portion 14 and the support portion 13 are arranged in a line shape). 2B (a), (b), 3B (a), (b), 4B (a), (b), etc.). This is because it is easy to make and sufficient durability can be ensured.

When the original plate for forming an ink film is viewed from a flat surface (above the surface layer on the opposite side of the substrate) to see a pattern on the surface of the substrate, the functional material portion 14 and the support portion 13 are formed. It is preferably arranged in a grid pattern (see FIGS. 2C (a), (b), 3C (a), (b), 4C (a), (b), etc.). This is because it is easy to make next to the above line shape and has excellent durability next to the checkered shape.

When the original plate for forming an ink film is viewed from a flat surface (above the surface layer on the opposite side of the substrate) to see a pattern on the surface of the substrate, the functional material portion 14 and the support portion 13 are formed. It is preferably arranged in a checkered pattern (see FIGS. 2D (a), (b), 3D (a), (b), 4D (a), (b), etc.). This is because it is easy to make next to the above grid pattern and has excellent durability.

In the ink film forming original plate, the functional material portion 14 and the support portion 13 are arranged in a rectangular wave (square wave) shape when viewed from a flat surface (above the surface layer on the opposite side of the substrate). (See FIGS. 3E (a), (b), 4E (a), (b), etc.). This is because it is easy to make next to the checkered shape and has excellent durability.

The above are the structural features of the original plate. Hereinafter, each of the constituent requirements of the original plate will be described.

<Support 13>
The convex support portion 13 constituting the surface layer is provided on the substrate 12. The convex support portion 13 can be manufactured by appropriately using a method such as a nanoimprint method, a photolithography method, or an etching method, depending on the properties and properties of the material. The material used for the support portion is preferably a material that can withstand long-term offset printing, and engineering plastics (also abbreviated as engineering plastics), photosensitive resins, metal oxides, and the like can be used. Engineering plastics is a general term for a group of high-performance plastics that overcomes the weaknesses of conventional general-purpose plastics such as strength and heat resistance. Although there is no clear definition of engineering plastics, it is generally regarded as a plastic having a heat resistance of 100 ° C. or higher, and this definition is also used in this specification. Examples of such engineering plastics include thermoplastic engineering plastics such as polycarbonate and polyamide. Examples of the photosensitive resin include thermoplastic resins such as polyimide. Examples of the metal oxide include anodized aluminum and titanium oxide. However, the material of the support portion is not limited to these.

(Preparation of support portion 13)
The convex support portion 13, particularly the support portion 13 having a fine concavo-convex structure (see FIGS. 2 to 4) can be manufactured by a known method such as a nanoimprint method, a photolithography method, an etching method, or the like.

(Manufacturing by nanoimprint method)
The support portion 13 having a fine concavo-convex structure can be manufactured by a nanoimprint method in which a transfer pattern of fine concavo-convex formed on a mold is transferred to a resin composition containing a thermoplastic resin such as polycarbonate or polyamide. This method also includes the nanoimprint method by the thermocompression bonding method shown below.

Specifically, it can be produced by a known method described in JP-A-2018-094864 and the like. For example, the nanoimprint method by the thermocompression bonding method can be performed using a small thermal imprint apparatus manufactured by Toray Engineering Co., Ltd. Using the device, the polycarbonate plate is heated to a predetermined temperature (preferably 140 ° C. or higher and 180 ° C. or lower, for example 150 ° C.), and the fine uneven pattern surface of the mold is brought into contact with the predetermined pressure (preferably 3 MPa or more and 10 MPa or less, for example 5 MPa). ) Is thermocompression bonded and held for a predetermined time (preferably 20 seconds or more and 60 seconds or less, for example, 30 seconds). After cooling to a predetermined temperature (preferably 30 ° C. or higher and 50 ° C. or lower, for example, 40 ° C.), the polycarbonate plate can be taken out from the mold to obtain a polycarbonate plate on which finely processed irregularities are transferred. As the mold, the polycarbonate plate has, for example, a concave-convex portion so as to have the structure of the support portion (see FIGS. 2 to 4) described in the examples.

(Manufactured by photolithography)
The support portion 13 having a fine concavo-convex structure can be manufactured by using a photolithography method on a photosensitive resin composition.

Specifically, it can be produced by a known method described in JP-A-2017-3877. For example, the photosensitive resin composition is applied onto the surface of the shine surface or the matte surface of the copper foil by a spin coating method to obtain a photosensitive resin composition coating film. Next, the photosensitive resin composition coating film dried in an infrared hot air dryer at a predetermined temperature (preferably 70 ° C. or higher and 100 ° C. or lower, for example 90 ° C.) and for a predetermined time (preferably 3 minutes or more and 10 minutes or less, for example 5 minutes). A photomask is placed on the surface, and a 2 kW ultra-high pressure mercury lamp irradiator (for example, JP-2000-EXC manufactured by ORC Manufacturing Co., Ltd.) is used to irradiate the image with an exposure amount at which an image can be obtained. 10 mass% tetramethylammonium hydroxide methanol aqueous solution / 1,4-dioxane in a predetermined ratio (preferably (1/1) or more (4/1) or less (mass ratio), for example 2/1 (mass ratio)) ) Is immersed in the coating film after irradiation or ultrasonically treated, washed with pure water, and dried with an infrared lamp to obtain a support portion 13 having a desired fine concavo-convex structure. Can be done. As the photomask, the photosensitive resin composition coating film has, for example, a pattern having the structure of the support portion (see FIGS. 2B, 2C, and 2D) described in the examples. ..

(Made by etching)
The support portion 13 having a fine concavo-convex structure can be manufactured by using a dry etching method after forming a resist pattern on a substrate containing a metal oxide such as aluminum anodized aluminum or titanium oxide.

Specifically, it can be produced by a known method described in JP-A-8-78396 and JP-A-2001-188346. For example, a photosensitive resin composition coating film is applied to an anodized aluminum substrate by a spin coating method, and a resist pattern is formed using a light exposure apparatus. Then, using a dry etching apparatus, using an etching gas (preferably fluorine gas, chlorine gas, bromine gas, silicon gas, etc., for example CF ₄ ), a predetermined gas flow rate (preferably 50 sccm or more and 100 sccm or less, for example 75 sccm). Dry etching is performed under the conditions of a predetermined pressure (preferably 2 mTorr or more and 5 mTorr or less, for example 2.5 mTorr) and a predetermined output (preferably 1800 W or more and 3000 W or less, for example 2500 W) to process the desired pattern. Then, after ashing the resist pattern by oxygen plasma ashing, the resist pattern is completely removed by immersing it in an organic resist stripping agent and washing with pure water, and the support portion 13 having a desired fine uneven structure is obtained. Can be obtained. As the resist pattern, for example, the anodized aluminum substrate uses a pattern having the structure of the support portion (see FIGS. 2B, 2C, and 2D) described in the examples.

<Functional material section 14>
The functional material portion 14 constituting the surface layer is provided in a concave portion between adjacent convex support portions 13 provided on the substrate 12 (see FIGS. 2 to 4). The functional material unit 14 may include a stimulus-responsive compound (hereinafter, also simply referred to as a stimulus-responsive compound) whose affinity changes reversibly in response to an external stimulus. The functional material section 14 is preferably free of resin because it is excellent in responsiveness due to hydrophilic / hydrophobic control.

(Stimulus-responsive compound)
A stimulus-responsive compound is a compound that reversibly changes its properties in response to an external stimulus. In the present invention, a stimulus-responsive compound whose affinity with water changes reversibly in response to an external stimulus is used.

In addition, the fact that the affinity with water changes reversibly in response to an external stimulus means that the compound given the external stimulus changes reversibly between hydrophilicity and hydrophobicity in response to the external stimulus. To do.

Here, "reversibly changing between hydrophilicity and hydrophobicity" means that, specifically, the existence state of the molecule changes in response to an external stimulus, and the hydrophilicity and hydrophobicity change. That is. The above-mentioned state of existence of a molecule refers to a state of molecular structure and a state of aggregation of molecules. For example, in the case of a photoresponsive compound, the hydrophilicity and hydrophobicity can be controlled depending on whether or not the hydroxy group is oriented on the surface by changing the molecular structure in response to light, and the temperature-responsive compound. If so, the hydrophilicity and the hydrophobicity can be controlled by changing the agglomeration state of the molecule in response to the temperature.

The external stimulus is not particularly limited, and examples thereof include light, temperature change, pressure, electric field, and pH.

Examples of stimulus-responsive compounds are photo-responsive compounds whose affinity with water changes reversibly in response to light, and temperature-responsive compounds whose affinity with water changes reversibly in response to temperature changes. Examples thereof include compounds, electric field-responsive compounds whose affinity with water changes reversibly in response to an electric field, and pH-responsive compounds whose affinity with water changes reversibly in response to pH.

As the stimulus-responsive compound, a synthetic product or a commercially available product may be used. In addition, the stimulus-responsive compound can be used alone or in combination of two or more. Among them, a photoresponsive compound is preferable from the viewpoints that the change rate of affinity with water is fast, it is difficult to diffuse due to temperature change, digital processing is easy with light, and patterning is easy.

Hereinafter, a photoresponsive compound which is a suitable stimulus-responsive compound will be described.

(Photoresponsive compound)
The photoresponsive compound according to the present invention is a compound that undergoes stereoisomerization or structural isomerization (cis-trans isomerization, photoopening reaction, etc.) by light irradiation, and its affinity with water is reversibly changed. .. Specific examples of such a compound include a compound having an azobenzene structure containing a hydrophilic group, a compound having a spiropyran structure containing a hydrophilic group, a compound having a stelvene structure containing a hydrophilic group, and a hydrophilic group. Examples thereof include a compound having a diarylethene structure, a compound having an azomethine structure having a hydrophilic group, and a compound having a heterocyclic structure having a hydrophilic group. These compounds may be in the form of macromolecules or crosslinked polymers of the macromolecules.

Among these, from the viewpoint of thermal stability after cis-trans isomerization, a compound having the structure of the following chemical formula (I), which causes cis-trans isomerization by light irradiation, is preferable.

In the above chemical formula (I), R _{1 to} R ₅ are independently selected from the group consisting of a hydrogen atom, an alkyl group, an alkoxy group, a halogen group, a hydroxy group and a carboxy group, and R ₆ is a group. , A substituent having at least one cyclic structure.

Further, it is preferable to have a hydrophilic group from the viewpoint that the change rate of affinity with water is fast. Examples of the hydrophilic group include a hydroxy group, a carboxy group, a mercapto group, a sulfonic acid group, a sulfate group, a phosphoric acid group, an amino group and the like. These hydrophilic groups may be used alone or in combination of two or more. Among them, the hydrophilic group is preferably a hydroxy group from the viewpoint of a rapid change rate of affinity with water.

Hereinafter, the chemical formula (1) the compound having an azobenzene structure, the chemical formula (2) the compound having a stelvene structure, the chemical formula (3) the compound having an azomethine structure, the chemical formula (4) the compound having a heterocyclic structure, and the chemical formula (1) described in Examples are described below. 5) Each description of the crosslinked compound of the polymer is shown.

(Chemical formula (1): compound having an azobenzene structure)
Specifically, the compound having an azobenzene structure containing a hydrophilic group is preferably a compound represented by the following chemical formula (1).

In the above chemical formula (1), R ¹ and R ² are independently hydrophilic groups, and R ³ and R ⁴ are independently alkyl or alkoxy groups having 1 to 18 carbon atoms. , M1 and m2 are independently integers from 0 to 4, where m1 + m2 are integers from 1 to 8.

^{R 1} and R ² in the above chemical formula (1) are independently hydrophilic groups. Examples of hydrophilic groups are as described above. When m1 + m2 is an integer of 2 to 8, the plurality of hydrophilic groups may be the same or different from each other.

^{R 3} and R ⁴ in the above chemical formula (1) are independently an alkyl group having 1 to 18 carbon atoms or an alkoxy group having 1 to 18 carbon atoms.

Examples of alkyl groups having 1 to 18 carbon atoms include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group and n. Linear alkyl groups such as -nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group; isopropyl group, Isobutyl group, sec-butyl group, t-butyl group, isoamyl group, t-pentyl group, neopentyl group, 1-methylpentyl group, 4-methyl-2-pentyl group, 3,3-dimethylbutyl group, 2-ethylbutyl Group, 1-methylhexyl group, t-octyl group, 1-methylheptyl group, 2-ethylhexyl group, 2-propylpentyl group, 2,2-dimethylheptyl group, 2,6-dimethyl-4-heptyl group, 3 , 5,5-trimethylhexyl group, 1-methyldecyl group, 1-hexylheptyl group and other branched alkyl groups; and the like.

Examples of alkoxy groups having 1 to 18 carbon atoms include methoxy group, ethoxy group, n-propoxy group, n-butoxy group, n-pentyloxy group, n-hexyloxy group, n-heptyloxy group and n-octyl. Oxy group, n-nonyloxy group, n-decyloxy group, n-undecyloxy group, n-dodecyloxy group, n-tridecyloxy group, n-tetradecyloxy group, n-pentadecyloxy group, n-hexa Linear alkoxy groups such as decyloxy group: isopropoxy group, t-butoxy group, 1-methylpentyloxy group, 4-methyl-2-pentyloxy group, 3,3-dimethylbutyloxy group, 2-ethyl Butyloxy group, 1-methylhexyloxy group, t-octyloxy group, 1-methylheptyloxy group, 2-ethylhexyloxy group, 2-propylpentyloxy group, 2,2-dimethylheptyloxy group, 2,6- Branched alkoxy groups such as dimethyl-4-heptyloxy group, 3,5,5-trimethylhexyloxy group, 1-methyldecyloxy group, 1-hexylheptyloxy group; and the like.

As a more specific example of the compound having an azobenzene structure containing a hydrophilic group, a compound represented by the following chemical formula (1a) is preferably mentioned.

(Chemical formula (2): compound having a stilbene structure)
Specifically, the compound having a stilbene structure containing a hydrophilic group is preferably a compound represented by the following chemical formula (2).

In the above chemical formula (4), R ^{5 to} R ¹⁰ are independently hydrogen atoms, alkoxy groups having 1 to 6 carbon atoms, or hydrophilic groups, and at this time, at least one of ^{R 5 to} R ^{10 is used.} Is a hydrophilic group.

Examples of alkoxy groups having 1 to 6 carbon atoms include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, sec-butoxy group, t-butoxy group and n-. Examples thereof include a pentyloxy group, an isopentyloxy group, a sec-pentyloxy group, a t-pentyloxy group and an n-hexyloxy group.

Examples of hydrophilic groups are as described above.

As a more specific example of the compound having a stilbene structure containing a hydrophilic group, the compound represented by the following chemical formula (2a) (isorapontigenin, 3,4', 5-trihydroxy-3'-methoxy-trans -Stilbene) is preferably mentioned.

(Chemical formula (3): compound having an azomethine structure)
The compound having an azomethine structure of the present invention is a compound represented by the following chemical formula (3) that is reversibly fluidized and non-fluidized by light irradiation.

In the chemical formula (3), X is NR ₂₀ , O or S.

Z ₁ and Z ₂ are independently N or CH, and Z ₁ ≠ Z ₂ .

R ₁₁ and R ₁₂ are independently hydrogen atom, halogen atom, alkyl group, alkoxy group, acyl group, alkoxycarbonyl group, cyano group, nitro group or hydroxy group, respectively.

Each of R ₁₃ and R ₁₄ independently has a group represented by the chemical formula (3a), a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an acyl group, an alkoxycarbonyl group, a cyano group, a nitro group or a hydroxy group. Is.

At this time, _{either one of R 13} and R ₁₄ is a group represented by the chemical formula (3a).

R ₂₀ is a hydrogen atom, a halogen atom, an alkyl group, an alkoxycarbonyl group or a hydroxy group.

In the chemical formula (3a), R _{15 to} R ₁₉ are independently hydrogen atom, halogen atom, alkyl group, alkoxy group, acyl group, alkoxycarbonyl group, cyano group, nitro group or hydroxy group.

At this time, _{at least one of R 15 to} R ₁₉ is an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, an acyl group having 2 to 19 carbon atoms, or an alkoxycarbonyl group having 2 to 19 carbon atoms. Is.

Examples of alkyl groups having 1 to 18 carbon atoms are as described above. Further, examples of the alkoxy group having 1 to 18 carbon atoms are also as described above. Examples of acyl groups having 2 to 19 carbon atoms are saturated or unsaturated linear or branched acyl groups, such as acetyl groups, propanoyl groups (propionyl groups), butanoyl groups (butyryl groups), isobutanoyl groups (isobutanoyl groups). Isobutyryl group), pentanoyl group (valeryl group), isopentanoyl group (isovaleryl group), sec-pentanoyl group (2-methylbutyryl group), tert-pentanoyl group (pivaloyl group), hexanoyl group, heptanoil group, octanoyl group, tert -Octanoyl group (2,2-dimethylhexanoyl group), 2-ethylhexanoyl group, nonanoyl group, isononanoyl group, decanoyyl group, isodecanoyl group, undecanoyl group, lauroyl group, myristoyl group, palmitoyl group, stearoyl group, behenoyl group , Undecylenoyl group, oleoil group and the like.

Examples of alkoxycarbonyl groups having 2 to 19 carbon atoms are linear or branched, and are, for example, methoxycarbonyl group, ethoxycarbonyl group, n-butoxycarbonyl group, n-hexyloxycarbonyl group, n-heptyloxy. Carbonyl group, n-octyloxycarbonyl group, n-nonyloxycarbonyl group, n-decyloxycarbonyl group, n-undecyloxycarbonyl group, n-dodecyloxycarbonyl group, n-tridecyloxycarbonyl group, n-tetra Linear alkoxycarbonyl groups such as decyloxycarbonyl group, n-pentadecyloxycarbonyl group, n-hexadecyloxycarbonyl group: 1-methylpentyloxycarbonyl group, 4-methyl-2-pentyloxycarbonyl group, 3 , 3-Dimethylbutyloxycarbonyl group, 2-ethylbutyloxycarbonyl group, 1-methylhexyloxycarbonyl group, t-octyloxycarbonyl group, 1-methylheptyloxycarbonyl group, 2-ethylhexyloxycarbonyl group, 2-propyl Pentyloxycarbonyl group, 2,2-dimethylheptyloxycarbonyl group, 2,6-dimethyl-4-heptyloxycarbonyl group, 3,5,5-trimethylhexyloxycarbonyl group, 1-methyldecyloxycarbonyl group, 1- Examples thereof include branched alkoxycarbonyl groups such as hexylheptyloxycarbonyl groups.

As a more specific example of the compound having an azomethine structure, a compound represented by the following chemical formula (3b) is preferably mentioned.

(Chemical formula (4): compound having a heterocyclic structure)
Examples of the compound having a heterocyclic structure include a compound in which one of the compounds represented by the chemical formula (1) has a benzene ring replaced with a pyrazole ring. The pyrazole ring may or may not be substituted.

As a specific example of the compound having a heterocyclic structure, a compound represented by the following chemical formula (4) is preferably mentioned.

(Chemical formula (5): Crosslinked polymer)
Further, as an example of the photoresponsive compound in the form of a polymer, a crosslinked product of a polymer represented by the following chemical formula (5) is preferably mentioned.

In the above chemical formula (5), x is the number of repeating units, and is not particularly limited as long as it is in the polymer region, but is in the range of, for example, 200 to 1000.

The photoresponsive compound may be used alone or in combination of two or more. Further, as the photoresponsive compound, a commercially available product or a synthetic product may be used.

<Example of synthesis method>
As an example of a method for synthesizing a photoresponsive compound, an example of a method for synthesizing a compound having an azobenzene structure containing a hydrophilic group will be described below.

For example, as a method for synthesizing a compound having an azobenzene structure represented by the above chemical formula (1a), a method represented by the following reaction formula A can be mentioned. 2-Chloro-4-aminophenol and sodium nitrite are reacted under cooling to synthesize a diazonium salt, which is then reacted with 2-chlorophenol, and then n-bromohexane is reacted to synthesize intermediate B. Is synthesized. Next, the obtained intermediate B can be reacted with an aqueous sodium hydroxide solution under high temperature and high pressure and treated with an acid to obtain an azobenzene compound (azobenzene derivative (1)) represented by the above chemical formula (1a). can.

Further, a compound having a stilbene structure represented by the above chemical formula (2a) (isorabontigenin, Japanese name: 3,4', 5-trihydroxy-3'-methoxy-trans-stilbene) may be synthesized. However, a commercially available product may be used. Examples of commercially available products include "Product Code: I0804" manufactured by Tokyo Chemical Industry Co., Ltd.

For example, as a method for synthesizing a compound having an azomethine structure represented by the above chemical formula (3b), a method represented by the following reaction formula D can be mentioned. In dimethylformamide, the raw materials 2-methyl-4-nitrophenol and 1-iodohexane are heated under reflux using potassium carbonate to react, and the reaction solution is washed with water, concentrated, and purified to obtain Intermediate C. obtain. Subsequently, the reaction is carried out by stirring and reacting under palladium carbon (Pd / C catalyst) in a mixed solvent of ethanol and tetrahydrofuran while encapsulating hydrogen gas, and the catalyst is removed from the reaction solution and concentrated to obtain intermediate D. .. Subsequently, in ethanol, the mixture is heated under reflux with 5-bromo-2-flualdehyde, reacted, concentrated, and purified to obtain Intermediate E. Finally, by reacting with an aqueous sodium hydroxide solution under high temperature and high pressure and treating with an acid, a compound having an azomethine structure represented by the above chemical formula (3b) can be obtained.

For example, as a method for synthesizing a compound having a heterocyclic structure represented by the above chemical formula (4), a method represented by the following reaction formula E can be mentioned. 5-Amino-o-cresol and sodium nitrite are reacted under cooling to synthesize a diazonium salt, which is then reacted with 5-hydroxy-1-methyl-1H-pyrazole to obtain the above chemical formula (4). A compound having the represented heterocyclic structure can be obtained.

For example, as a method for synthesizing a crosslinked polymer represented by the above chemical formula (5), a method represented by the following reaction formula C can be mentioned. Intermediate D is synthesized by synthesizing a diazonium salt in the same manner as in Reaction Scheme A, reacting it with 2-chlorophenol to obtain intermediate C, and then reacting it with n-bromohexanol. Next, the intermediate D and the acrylated product are reacted in the presence of triethylamine to form an acrylate monomer (intermediate E) containing an azobenzene structure, and then the chloro group is converted into a hydroxy group to obtain the intermediate F. .. The obtained intermediate F is subjected to a polymerization reaction using 2,2'-azobisisobutyronitrile (AIBN) as a polymerization initiator to carry out a polymerization reaction, whereby the azobenzene compound represented by the above chemical formula (5) (azobenzene derivative (azobenzene derivative (azobenzene derivative)). Polymer 2)) can be obtained.

As described above, it is preferable that the functional material unit 14 does not contain the resin from the viewpoint of maintaining the fast stimulus responsiveness, but the functional material portion 14 contains the resin as long as the amount does not impair the fast stimulus responsiveness. You may.

(resin)
The resin is not particularly limited, and either a thermoplastic resin or a thermosetting resin can be used.

Examples of thermoplastic resins include polyolefin resins such as polyethylene and polypropylene, cyclic polyolefin resins, polyethylene terephthalates, polyester resins such as polybutylene terephthalate, polyvinyl chloride resins, vinylidene chloride resins, polytetrafluoroethylene resins, and polystyrenes. Resins, polyether resins, polyvinyl acetate resins, acrylonitrile-butadiene-styrene (ABS) resins, acrylonitrile-styrene (AS) resins, acrylic resins, styrene acrylic resins, polyamide resins, polyacetal resins, polycarbonate resins, modified polyphenylene ether resins, Polybutylene terephthalate resin, polyethylene terephthalate resin, polyphenylene sulfide resin, polysulfone resin, polyether sulfone resin, amorphous polyarylate resin, liquid crystal polymer, polyether ether ketone resin, thermoplastic polyimide resin, polyamideimide resin, and both of them. Examples include polymers.

Examples of thermosetting resins include solid epoxy resin, silicone resin, silicone modified resin, formaldehyde resin, phenol resin, melamine resin, urea resin (urea resin), benzoguanamine resin, unsaturated polyester resin, alkyd resin, and diallyl. Phtalate resin, polyurethane resin, thermosetting polyimide resin, crosslinked acrylic resin (for example, crosslinked polymethylmethacrylate resin), crosslinked polystyrene resin, and polyamic acid resin (resin that is imidized by heating to form a polyimide structure). And so on.

The above resins can be used alone or in combination of two or more. Further, for example, a hybrid resin in which two or more kinds of polymerization segments (resin segments) are bonded to each other, such as a resin having a vinyl polymerization segment (vinyl resin segment) and a polyester polymerization segment (polyester resin segment), may be used. ..

Among these, a thermoplastic resin is preferable, and a styrene acrylic resin, a polycarbonate resin, a polyethylene terephthalate resin, and a polyolefin resin are more preferable from the viewpoint that the affinity of the stimulus-responsive compound with water is more likely to change.

As the resin, a synthetic product or a commercially available product may be used. Examples of commercially available resins include VS-1063 (weight average molecular weight: 5,500), US-1071 (weight average molecular weight: 10,000), X-1 (weight average molecular weight: 18) manufactured by Seikou PMC Co., Ltd. , 000), YS-1274 (weight average molecular weight: 19,000), VS-1047 (weight average molecular weight: 10,000), RS-1191 (weight average molecular weight: 6,500) and the like.

The weight average molecular weight of the resin is not particularly limited, but is preferably 5,000 to 30,000, more preferably 8,000 to 20,000.

In addition, in this specification, the value measured by gel permeation chromatography (GPC) is adopted as the weight average molecular weight.

The content of the resin is preferably 0% by mass or more and 25% by mass or less, and 0% by mass or more and 10% by mass or less, based on the total mass of the stimulus-responsive compound and the resin contained in the functional material portion 14. Is more preferable. Within such a range, the strength of the functional material portion 14 can be improved while maintaining a fast stimulus responsiveness.

The content of the stimulus-responsive compound in the functional material unit 14 is preferably 75 to 100% by mass, more preferably 90 to 100% by mass, with the total mass of the functional material unit 14 as 100% by mass. preferable. Within such a range, the strength of the functional material portion 14 can be improved, and a fast stimulus responsiveness can be maintained.

(Other ingredients)
The functional material unit 14 according to the present invention may further contain an antioxidant, a plasticizer, metal oxide particles and the like as long as the effects of the present invention are not impaired.

[Adhesive layer]
In the original plate for forming an ink film of the present invention, the functional material portion 14 is arranged on the contact surface with the support portion 13 or on the substrate 12 on the bottom surface of the recess between the support portions 13 via an adhesive layer (not shown). It may be made up of.

The adhesive used for forming the adhesive layer (hereinafter, also referred to as an adhesive for forming an adhesive layer) is not particularly limited, and is a curable composition containing a curable resin and, if necessary, a polymerization initiator, a solvent and the like. Is preferable.

The curable resin may be an active energy ray (for example, ultraviolet rays, visible rays, X rays, electron beams, etc.) curable type or thermosetting type, but is preferably an active energy ray curable type, and more preferably ultraviolet rays. It is a curable type. The curable resin can be used alone or in combination of two or more. Further, as the curable resin, a commercially available product or a synthetic product may be used.

As the ultraviolet curable resin, for example, an ultraviolet curable urethane acrylate resin, an ultraviolet curable polyester acrylate resin, an ultraviolet curable epoxy acrylate resin, an ultraviolet curable polyol acrylate resin, an ultraviolet curable epoxy resin and the like are preferably used. Of these, ultraviolet curable urethane acrylate resin and ultraviolet curable polyol acrylate resin are preferable.

Examples of the ultraviolet curable polyol acrylate resin include ethylene glycol (meth) acrylate, polyethylene glycol di (meth) acrylate, glycerin tri (meth) acrylate, trimethyl propantri (meth) acrylate, pentaerythritol tri (meth) acrylate, and pentaerythritol. Examples thereof include tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and alkyl-modified dipentaerythritol penta (meth) acrylate. As the ultraviolet curable polyol acrylate resin, a commercially available product may be used, and examples of the commercially available product include Sartomer (registered trademark) SR295, 350, 399 (manufactured by Sartmer).

As the polymerization initiator, known photopolymerization initiators, thermal polymerization initiators and the like can be appropriately selected and used according to the type of curable resin to be used. As the adhesive for forming the adhesive layer, either a commercially available product or a synthetic product may be used.

When the adhesive is cured by irradiating it with active energy rays, the irradiation conditions (type of light source, irradiation intensity, irradiation time, etc.) can be appropriately selected. As the light source, a known light source such as a low-pressure mercury lamp, a high-pressure mercury lamp, a xenon lamp, or a metal halide lamp can be used. The irradiation intensity is not particularly limited, but is preferably in the range of ^{10 mW / cm 2} or more and 200 mW / cm ^{2 or less, for example.} The irradiation time is also not particularly limited, but is preferably in the range of, for example, 1 minute or more and 10 minutes or less. Even when the adhesive is cured by heating, the heating temperature and heating time can be appropriately adjusted.

The thickness (dry thickness) of the adhesive layer is not particularly limited, but is preferably in the range of 0.5 μm or more and 3 μm or less.

(Thickness of surface layer)
The thickness (dry thickness) h of the surface layer (see FIG. 2B (c), etc.) is not particularly limited, but is preferably in the range of 3 μm or more and 200 μm or less, and more preferably in the range of 5 μm or more and 100 μm or less. preferable. When the surface layer thickness (dry thickness) h is 5 μm or more, it is preferable in terms of plate durability and responsiveness of the functional material portion, and when the surface layer thickness (dry thickness) h is 100 μm or less. If there is, it is preferable in terms of coating uniformity on the plate surface.

[Manufacturing method of original plate for forming ink film]
The method for producing the original plate for forming an ink film is not particularly limited, and for example, after preparing a surface layer forming solution containing a stimulus-responsive compound, the recesses between the convex support portions 13 formed on the substrate 12 are formed. A method of providing the surface layer 15 by forming the functional material portion 14 by applying the solution and drying it can be mentioned. The convex support portion 13 formed on the substrate 12 can be appropriately manufactured by the nanoimprint method, photolithography method, or the like described above. Further, the substrate 12 is as described in the above-mentioned original plate for forming an ink film.

The solvent used for the surface layer forming solution is not particularly limited, and is, for example, an aliphatic solvent such as n-pentane, n-hexane, n-heptane, n-octane, cyclohexane, methylcyclohexane; methylethylketone, acetone, etc. Ketone solvents such as cyclohexanone; ether solvents such as diethyl ether, isopropyl ether, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether, anisole, phenetol; ethyl acetate, Ester solvents such as butyl acetate and ethylene glycol diacetate; aromatic solvents such as toluene and xylene; cellosolvent solvents such as methyl cellosolve, ethyl cellosolve and butyl cellosolve; alcohol solvents such as methanol, ethanol, propanol and isopropyl alcohol; Ether-based solvents such as tetrahydrofuran and dioxane; Halogen-based solvents such as dichloromethane and chloroform; Nitrile-based solvents such as acetonitrile and propionitrile; N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N, N-dimethyl Examples thereof include polar solvents such as formamide and N, N-dimethylacetamide. These solvents can be used alone or in combination of two or more.

Examples of the method of applying the surface layer forming solution to the recesses between the convex support portions 13 formed on the substrate 12 include a rotary coating method; a dipping method; a dripping method; a roll coater, a rod coater, and a curtain coater. Methods using a liquid film coating device such as a slide coater, a doctor knife, a screen coater, a slot coater, an extrusion coater, a blade coater, a gravure coater, and an inkjet coater; and the like.

An original plate for forming an ink film can be obtained by applying a surface layer forming solution, air-drying if necessary, and then drying using a vacuum dryer or the like. The drying temperature when a vacuum dryer is used is not particularly limited, but is preferably in the range of 25 ° C. or higher and 40 ° C. or lower. The drying time is also not particularly limited, but is preferably in the range of 1 hour or more and 4 hours or less.

When the original plate provided with the adhesive layer is manufactured, the functional material portion 14 is in contact with the support portion 13 or the bottom surface of the recess between the support portions 13 is manufactured by the method described in the above section [Adhesive layer]. After providing the adhesive layer on the substrate 12, the surface layer 15 may be formed by providing the functional material portion 14 in the recess between the support portions 13.

[Pattern film forming apparatus and pattern film forming method]
The present invention also provides a pattern film forming apparatus (printing apparatus) using the original plate of the present invention. The device forms an ink film forming original plate, a writing means for applying an external stimulus to the surface layer of the original plate to form a pattern composed of a hydrophilic portion and a hydrophobic portion, and an ink film on the pattern. By relatively pressing and separating the ink film surface of the blanket against the ink film forming means and the original plate on which the ink film is formed, the ink film surface of the blanket is placed on the hydrophobic portion of the pattern. By relatively pressing and pulling the object to be printed against the first transfer means for transferring only the ink film formed in the above and the blanket having the transferred ink film, the ink is applied to the surface of the object to be printed. It is preferable to have a second transfer means for transferring the film.

The present invention also provides a pattern film forming method (printing method) using the above-mentioned original plate. In this method, an external stimulus is applied to the surface layer of the original plate for forming an ink film of the present invention to form a pattern consisting of a hydrophilic portion and a hydrophobic portion, and a first writing step and an ink film are formed on the pattern. By the step of forming and the surface of the blanket for the ink film being relatively pressed against the original plate on which the ink film was formed and pulled apart, the surface of the blanket for the ink film is formed on the hydrophobic portion of the pattern. A step of transferring only the transferred ink film and a step of transferring the ink film to the surface of the printed body by relatively pressing and pulling the printed material against the blanket having the transferred ink film. , It is preferable to have.

Hereinafter, each means (or process) constituting the pattern film forming apparatus (or method) according to the present invention will be described with reference to FIG. 5 as appropriate. However, the pattern film forming apparatus used in the present invention is not limited to the following forms and illustrated examples. FIG. 5 shows an example in which the blanket 3 is used, but the present invention is not limited to this, and the ink is adhered directly from the ink roller 5 to the original plate 1 mounted on the plate cylinder 2 without using the blanket 3. After forming the film, the ink film may be directly transferred to the object to be printed. Further, although an example of supplying ink from above the printed object 8 will be described below, ink may be supplied from below the printed object 8.

FIG. 5 is a schematic view showing a pattern film forming apparatus 10 according to an embodiment of the present invention. The pattern film forming apparatus 10 includes an ink film forming original plate 1, a plate cylinder 2, a blanket 3, an impression cylinder 4, an ink roller 5, a water roller 6, and a monochromatic laser light source 7 as a writing means.

In the pattern film forming method according to the embodiment of the present invention, light (external stimulus, arrow in FIG. 5) emitted from the monochromatic laser light source 7 is applied to the surface layer of the original plate 1 mounted on the plate cylinder 2. A pattern consisting of hydrophilic and hydrophobic sites is formed.

After the water supplied from the water roller 6 adheres to the hydrophilic portion formed on the surface layer of the original plate 1, the ink supplied from the ink roller 5 is attached to the plate cylinder 2 at the contact point with the plate cylinder 2. It adheres to the surface layer of the original plate 1. As a result, an ink film is formed on the original plate 1. The formed ink film is transferred to the surface of the blanket 3 for the ink film at the contact point with the blanket 3. The ink film adhering to the blanket 3 is transferred to the printed body 8 at the contact point with the printed body 8 arranged on the impression cylinder 4. A printed matter is obtained by drying the object to be printed 8 as needed. The rotation speed of the ink roller, each body, and the blanket is not particularly limited, and can be appropriately set according to the properties of the ink and the object to be printed.

[Writing means (first writing step, second writing step)]
When the surface layer of the original plate 1 contains a photoresponsive compound, the writing means may be a known light source such as a light emitting diode (LED) or a monochromatic laser light source. When the surface layer of the original plate 1 contains a temperature-responsive compound, the writing means may be an infrared lamp, a monochromatic laser light source, or the like. The writing means may be installed alone or in combination of two or more.

By partially applying an external stimulus from the writing means to the ink film forming original plate 1 provided on the plate cylinder 2, a pattern consisting of a hydrophilic portion and a hydrophobic portion is formed on the surface layer of the original plate 1. .. In the present specification, "partially applying an external stimulus" means applying an external stimulus to either the image portion or the non-image portion of the image pattern to be written.

As described above, the stimulus-responsive compound according to the present invention is preferably a photo-responsive compound or a temperature-responsive compound. That is, the external stimulus applied by the writing means is preferably light or a temperature change.

When the surface layer of the original plate 1 contains a photoresponsive compound, the external stimulus is light. At that time, the wavelength region of the light emitted from the writing means (preferably a monochromatic laser light source) is preferably in the range of 200 nm or more and 400 nm or less, and more preferably in the range of 280 nm or more and 400 nm or less. In such a wavelength region, it is possible to irradiate a finer region with light, and it is possible to reproduce small characters and fine images more clearly. Further, since the energy received by the surface layer is not too large, the surface layer is less likely to deteriorate and can withstand repeated rewriting operations.

The amount of irradiation light at the time of writing is preferably in the range of ^{, for example, 1 J / cm 2} or more and 10 J / cm ^{2 or less.} Within this range, small characters and fine images can be clearly written, and writing can be performed without overloading the surface layer.

If the surface layer of the original contains a temperature-responsive compound, the external stimulus is a temperature change. As described above, since the temperature-responsive compound used in the present invention has a critical dissolution temperature, the surface layer is subjected to a temperature change so as to pass through this critical dissolution temperature, and the surface layer of the original plate 1 is hydrophilic. A pattern consisting of sites and hydrophobic sites is formed. At this time, the writing means used is preferably a monochromatic laser light source that emits light having a wavelength in the range of 700 nm or more and 900 nm or less. Partial heating is performed by this writing means to form the above pattern.

When various light sources are used as the writing means, it is preferable to irradiate the light emitted from the light source in a pin spot shape so that only the stimulus-responsive compound to which an external stimulus is applied changes the affinity with water. Examples of such a method include an irradiation method in which light from a light source is guided by an optical fiber. However, it is also possible to adopt an irradiation method by projecting an image pattern or the like as long as the required amount of light can be supplied.

By performing the writing step (first writing step) as described above, a pattern composed of a hydrophilic part and a hydrophobic part is formed on the surface layer of the original plate 1. Therefore, the present invention also provides a pattern forming method comprising a first writing step of applying an external stimulus to the surface layer of the original plate of the present invention to form a pattern consisting of a hydrophilic part and a hydrophobic part. do. As described above, the external stimulus applied in the forming method is preferably light or a temperature change. Further, as described above, the external stimulus applied in the forming method is preferably light having a wavelength in the region of 280 nm or more and 400 nm or less.

The writing means may be activated at least when printing different printed matter by changing the image pattern, and may not be used when printing a plurality of the same printed matter. That is, since the pattern formed on the surface layer is maintained as it is by writing once, it is possible to print a plurality of sheets without rewriting by continuously transferring the ink film by the transfer means. .. Further, the pattern formed on the surface layer is erased by an erasing step described later, and an external stimulus is further applied on the same surface layer to form a second writing step of forming a pattern composed of a hydrophilic part and a hydrophobic part. By doing so, it can be easily rewritten. By repeating the erasing process and the writing process in this way, a plurality of printing patterns can be formed on one original plate surface. The original plate of the present invention is excellent in durability that small characters and fine images can be printed clearly and with good reproducibility even if such repetition is performed.

The pattern composed of the hydrophilic portion and the hydrophobic portion formed on the surface layer of the original plate 1 moves with the rotation of the plate cylinder 2 and is used for forming the ink film.

[Ink film forming means (process)]
In the pattern film forming apparatus according to the embodiment of the present invention, the ink film forming means is, for example, an ink roller 5 as shown in FIG.

The ink film forming means applies ink to the pattern formed in the writing step to form an ink film. In addition, in this specification, "ink film formation" means that the ink is held at a predetermined position (hydrophilic part or hydrophobic part) of a pattern in a state where it can be transferred to an object 8 to be printed.

The ink is not particularly limited as long as it can be transferred to the object to be printed 8, and known inks such as water-based inks, oil-based inks, and emulsion inks can be used. When water-based ink is used, an ink film is formed on the hydrophilic portion of the pattern. When oil-based ink or emulsion ink is used, an ink film is formed on the hydrophobic portion of the pattern.

The formed ink film moves with the rotation of the plate cylinder 2 provided with the original plate 1 and is sent so as to come into contact with the blanket 3.

[First transfer means (process)]
In the pattern film forming apparatus according to the embodiment of the present invention, the first transfer means is, for example, a blanket 3 as shown in FIG.

In the first transfer step, the ink formed on the pattern is formed by relatively pressing and pulling the ink film surface of the blanket 3 against the original plate 1 having the ink film formed in the ink film forming step. Transfer the membrane.

As described above, the position where the ink film is formed may be a hydrophilic part or a hydrophobic part depending on the type of ink, but the hydrophobic ink has a relatively high viscosity and is less likely to cause image collapse during transfer. From the viewpoint, the form in which only the ink film on the hydrophobic part is transferred to the blanket is preferable.

The material of the blanket 3 is not particularly limited as long as the ink film is transferred, and known materials can be used.

The ink film remaining on the blanket 3 is removed by, for example, a cleaning blade (not shown).

[Second transfer means (process)]
In the pattern film forming apparatus according to the embodiment of the present invention, the second transfer means is, for example, an impression cylinder 4 as shown in FIG.

In the second transfer step, the ink film is transferred to the surface of the printed matter 8 by relatively pressing and pulling the printed matter 8 against the blanket 3 having the transferred ink film by the impression cylinder 4. NS.

The material of the impression cylinder 4 is not particularly limited, and known materials can be used.

The object to be printed 8 is not particularly limited as long as the ink film is transferred, and for example, paper, resin film, resin or metal plate-like material (sheet or the like), cloth, or the like can be used.

[Erasing means (process)]
It is preferable that the pattern film forming apparatus of the present invention further has an erasing means for erasing the pattern by applying an external stimulus to the surface layer of the original plate 1.

When the surface layer of the original plate contains a photoresponsive compound, the erasing means is a monochromatic laser that emits visible light (preferably visible light in the wavelength region of 400 nm or more and 600 nm or less) from the viewpoint of the rate of change in affinity with water. It can be a light source or a light emitting diode.

When the surface layer of the original plate contains a temperature-responsive compound, the erasing means is, for example, a cold air generator capable of generating cold air in the range of 5 ° C. or higher and 20 ° C. or lower, and a range of 5 ° C. or higher and 20 ° C. or lower. A constant temperature bath and the like can be mentioned.

The pattern is erased by such an erasing means, and the surface layer of the original plate has the same properties as before the external stimulus is applied. After that, by performing the above writing step again, a new pattern can be formed on the surface layer. That is, the original version of the present invention can easily rewrite the pattern digitally.

Therefore, it is preferable that the pattern film forming method according to the present invention further includes an erasing step of erasing the pattern by applying an external stimulus to the surface layer of the original plate after the transfer step. Further, the external stimulus used in this erasing step is preferably light or a temperature change. Further, the external stimulus used in this erasing step is preferably visible light.

The erasing means may be activated at least when printing different printed matter by changing the image pattern, and may not be used when printing a plurality of the same printed matter. As described above, the pattern formed on the surface layer by the first writing step is erased by the erasing step, an external stimulus is applied on the same surface layer, and a pattern consisting of a hydrophilic part and a hydrophobic part is formed. Rewriting can be easily performed by further performing the second writing step. By repeating the erasing process and the writing process in this way, a plurality of printing patterns can be formed on one original plate surface. The original plate of the present invention is excellent in durability that small characters and fine images can be printed clearly and with good reproducibility even if such repetition is performed.

The writing means and the erasing means may be provided in the same housing as the housing in which the plate cylinder 2, the blanket 3, and the impression cylinder 4 are provided, or the plate cylinder 2, the blanket 3, and the impression cylinder 4 may be provided. It may be provided outside the housing in which 4 is provided. If the writing means and the erasing means are provided in the same housing as the housing in which the plate cylinder 2, the blanket 3, and the impression cylinder 4 are provided, the first with respect to the surface layer of the original plate 1 installed in the plate cylinder 2. The writing step, the erasing step, and the second writing step after that can be continuously repeated. When it is desired to print the same image pattern continuously, it is possible to print without performing the erasing step and the subsequent second writing step. It is also possible to print the same image pattern continuously by transferring the image to the printing object 8 once, performing an erasing step, and writing the same image on the surface layer of the original plate 1 again.

The pattern film forming apparatus (method) of the present invention may have means (steps) other than the above means (steps). For example, in the pattern film forming method, before the first writing step, an external stimulus is applied to the entire surface layer of the original plate to change the affinity of the stimulus-responsive compound contained in the entire surface layer with water ( A method may be adopted in which the steps after the first writing step are performed after performing hydrophobicity → hydrophilicity or hydrophilicity → hydrophobicity).

Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. In the examples, the indication of "parts" or "%" is used, but unless otherwise specified, it indicates "parts by mass" or "% by mass".

<Synthesis of a compound having an azobenzene structure represented by the above chemical formula (1a)>
After adding 75 mL of 2.4N hydrochloric acid to 4-amino-2-chlorophenol (8.61 g, 60 mmol), dissolve sodium nitrite (4.98 g, 72 mmol) in 6 mL of distilled water while cooling and stirring at 0 ° C. The solution was added, and stirring was continued at 0 ° C. for 60 minutes. A mixed solution of 2-chlorophenol (7.71 g, 60 mmol) and 24 mL of a 20% aqueous sodium hydroxide solution was added to this solution, and the mixture was stirred for 20 hours. The precipitated precipitate was filtered and the solid was washed with water. The obtained solid was purified by silica gel column chromatography using a mixed solution of ethyl acetate and hexane as a developing solvent to obtain Intermediate A (see Reaction Scheme A for the structure). To this intermediate A (2.83 g, 10 mmol), 100 mL of DMF, 1-bromohexane (9.90 g, 60 mmol), and potassium carbonate (6.91 g, 50 mmol) were added, and the mixture was stirred at 80 ° C. for 2 hours and then at room temperature. Stirring was continued at (25 ° C.) for 20 hours. The solvent was evaporated under reduced pressure, extracted with ethyl acetate, the organic layer was washed with saturated brine, and dried over anhydrous magnesium sulfate. After filtering this, the solvent was distilled off under reduced pressure, and the obtained solid was purified by silica gel column chromatography using a mixed solution of ethyl acetate and hexane as a developing solvent, whereby intermediate B (the structure was the above reaction). (See Equation A) was obtained. To this intermediate B (2.58 g, 5 mmol), 12 mL of a 20% aqueous sodium hydroxide solution was added, and the mixture was stirred at 340 ° C. and 150 atm for 2 hours, then 10 mL of 1.2N hydrochloric acid was added, and the mixture was stirred at room temperature (25 ° C.) for 1 hour. bottom. The mixture was extracted with ethyl acetate, the organic layer was washed with saturated brine, and dried over anhydrous magnesium sulfate. After filtering this, the solvent is distilled off under reduced pressure, and the obtained solid is purified by silica gel column chromatography using a mixed solution of ethyl acetate and hexane as a developing solvent to obtain a compound having an azobenzene structure (the above chemical formula). (See (1a)) was obtained.

<Compound having a stilbene structure represented by the above chemical formula (2a)>
The compound having a stilbene structure represented by the above chemical formula (2a) (isorabontigenin; Japanese name: 3,4', 5-trihydroxy-3'-methoxy-trans-stilbene) is manufactured by Tokyo Chemical Industry Co., Ltd. "Product code: I0804" was purchased and used.

<Synthesis of a compound having an azomethine structure represented by the above chemical formula (3b)>
2-Methyl-4-nitrophenol (3.1 g, 20 mmol), 1-iodohexane (12.9 g, 60.7 mmol), carbonate in a 100 ml 4-headed flask equipped with a cooling tube, nitrogen introduction tube, and thermometer. Potassium (7.0 g, 50.6 mmol) and 30 ml of dimethylformamide were added, and the mixture was heated under reflux. The reaction mixture was washed with water, concentrated, and purified by column chromatography (ethyl acetate: heptane = 1: 9 (volume ratio)) to obtain Intermediate C. Subsequently, 40 ml each of Intermediate C (3.3 g, 14 mmol), palladium carbon (0.07 g, 150 mmol), ethanol and tetrahydrofuran were placed in a 500 ml Erlenmeyer flask, and the mixture was stirred while enclosing _{hydrogen (H 2).} Palladium on carbon was removed from the reaction solution, the obtained solution was concentrated, and then recrystallized from ethanol to obtain Intermediate D. Subsequently, in a 100 ml 4-headed flask equipped with a cooling tube, a nitrogen introduction tube, and a thermometer, intermediate D (1.0 g, 5.0 mmol) and 5-bromo-2-flualdehyde (0.9 g, 5. 0 mmol) and 20 ml of ethanol were added, and the mixture was heated and stirred at 50 ° C. The reaction solution was suction filtered, and the obtained powder was washed with cooling ethanol. Further, recrystallization was carried out in a mixed solvent of methanol / ethanol to obtain Intermediate E. Finally, 12 mL of a 20% aqueous sodium hydroxide solution was added to Intermediate E (1.5 g, 4.0 mmol), and the mixture was stirred at 340 ° C. and 150 atm for 2 hours, then 10 mL of 1.2N hydrochloric acid was added, and the room temperature (25 ° C.) Was stirred for 1 hour. The mixture was extracted with ethyl acetate, the organic layer was washed with saturated brine, and dried over anhydrous magnesium sulfate. After filtering this, the solvent is distilled off under reduced pressure, and the obtained solid is purified by silica gel column chromatography using a mixed solution of ethyl acetate and hexane as a developing solvent to obtain a compound having an azomethine structure (the above chemical formula). (See (3b)) was obtained.

<Synthesis of a compound having a heterocyclic structure represented by the above chemical formula (4)>
After adding 75 mL of 2.4N hydrochloric acid to 5-amino-o-cresol (7.39 g, 60 mmol), sodium nitrite (4.98 g, 72 mmol) was dissolved in 6 mL of distilled water while cooling and stirring at 0 ° C. The solution was added and stirring was continued at 0 ° C. for 60 minutes. To this solution was added a mixed solution of 5-hydroxy-1-methyl-1H-pyrazole (5.89 g, 60 mmol) and 24 mL of a 20% aqueous sodium hydroxide solution, and the mixture was stirred for 20 hours. The precipitated precipitate was filtered and the solid was washed with water. The obtained solid was purified by silica gel column chromatography using a mixed solution of ethyl acetate and hexane as a developing solvent to obtain a compound having a heterocyclic structure (see the above chemical formula (4)).

<Synthesis of crosslinked polymer represented by the above chemical formula (5)>
After adding 75 mL of 2.4N hydrochloric acid to 3-chloro-4- (hexyloxy) aniline (13.66 g, 60 mmol), distilled water of sodium nitrite (4.98 g, 72 mmol) while cooling and stirring at 0 ° C. The solution dissolved in 6 mL was added, and stirring was continued at 0 ° C. for 60 minutes. A mixed solution of 2-chlorophenol (7.71 g, 60 mmol) and 24 mL of a 20% aqueous sodium hydroxide solution was added to this solution, and the mixture was stirred for 20 hours. The precipitated precipitate was filtered and the solid was washed with water. The obtained solid was purified by silica gel column chromatography using a mixed solution of ethyl acetate and hexane as a developing solvent to obtain Intermediate C (see Reaction Scheme C for the structure). To this intermediate C (7.35 g, 20 mmol), 100 mL of DMF, 3-bromo-1-hexanol (10.9 g, 60 mmol), and potassium carbonate (6.91 g, 50 mmol) were added, and the mixture was stirred at 80 ° C. for 2 hours. , Stirring was continued for 20 hours at room temperature (25 ° C.). The solvent was evaporated under reduced pressure, extracted with ethyl acetate, the organic layer was washed with saturated brine, and dried over anhydrous magnesium sulfate. After filtering this, the solvent was distilled off under reduced pressure, and the obtained solid was purified by silica gel column chromatography using a mixed solution of ethyl acetate and hexane as a developing solvent, whereby intermediate D (the structure was the above reaction). (See Equation C) was obtained. To this intermediate D (4.67 g, 10 mmol) was added 100 mL of tetrahydrofuran to prepare a tetrahydrofuran solution of intermediate D. Separately, to add acryloyl chloride (1.09 g, 12 mmol) and triethylamine (2.43 g, 24 mmol), a tetrahydrofuran solution of intermediate D was added dropwise at 0 ° C., followed by stirring at 0 ° C. for 30 minutes. The temperature was raised to room temperature (25 ° C.), and the mixture was further stirred at room temperature (25 ° C.) for 2 hours. The obtained reaction solution was washed with water and saturated brine, the solvent was evaporated under reduced pressure, and the mixture was recrystallized from methanol to obtain intermediate E. To this intermediate E (2.61 g, 5 mmol), 12 mL of a 20% aqueous sodium hydroxide solution was added, and the mixture was stirred at 340 ° C. and 150 atm for 2 hours, then 10 mL of 1.2N hydrochloric acid was added, and the mixture was stirred at room temperature (25 ° C.) for 1 hour. bottom. The mixture was extracted with ethyl acetate, the organic layer was washed with saturated brine, and dried over anhydrous magnesium sulfate. After filtering this, the solvent was distilled off under reduced pressure, and the obtained solid was purified by silica gel column chromatography using a mixed solution of ethyl acetate and hexane as a developing solvent to obtain Intermediate F. To this intermediate F (1.45 g, 3 mmol), 40 mL of a benzene / tetrahydrofuran mixed solvent (mass ratio 1: 1) was added, and further, 2,2-azobisisobutyronitrile (AIBN) was added as a polymerization initiator. 20% by mass was added to the body F, and the mixture was stirred at 70 ° C. for 20 hours. Then, it was reprecipitated with ethanol to obtain an azobenzene derivative (polymer 2) (crosslinked polymer represented by the above chemical formula (5)). The obtained polymer 2 had a repeating unit x in the above chemical formula (5) of about 500.

(Preparation of original plate for forming ink film)
First, the support portion was formed on the substrate by the nanoimprint method according to the arrangement of the support portion as viewed in a plane corresponding to each embodiment shown in Table 1, the structure of the cross section, and the requirements of a, b, and c. The above-mentioned a is the length of the support portion in the structure (A), the above-mentioned b is the length of the functional material portion in the structure (A), and the above-mentioned c is the length of the functional material portion in the structure (B). .. As the substrate, a polycarbonate plate (Examples 1 to 3 and 6 to 18), a copper foil (Example 4), and an anodized aluminum substrate (Example 5) were used, respectively. Next, a functional material portion was formed on the produced support portion using a blade coater to obtain an ink film forming original plate having a surface layer. Hereinafter, each embodiment will be described in detail.

(Examples 1 to 3 and 6 to 15: Preparation of original plates 1 to 3 and 6 to 15 for forming an ink film)
360 parts by mass of dichloromethane, 360 parts by mass of toluene, and 570 parts by mass of the compound represented by the chemical formula (1a) synthesized above, which is a photoresponsive compound, were stirred and mixed at 50 ° C. for 1 hour to obtain a solution for forming a surface layer. .. The solution was well dispersed at room temperature (25 ° C.) for 30 minutes using a paint shaker. Then, the above solution was applied to the recesses of the support portion using a blade coater on a substrate (length 360 mm × width 180 mm × thickness 30 mm) in which the support portion corresponding to each embodiment was formed by the nanoimprint method. After coating, it is air-dried for 30 minutes, and then dried at 30 ° C. for 2 hours using a vacuum dryer to form a functional material portion in the recess between the support portions, and has a surface layer having a thickness of 10 μm on the substrate. Original plates 1 to 3 and 6 to 15 for forming an ink film were obtained, respectively. The substrate and the support portion are integrally molded using a polycarbonate plate by the nanoimprint method, and since there is no boundary line (boundary surface) between the substrate and the support portion, the thickness h of the surface layer (Fig.) 2 to FIG. 4) are the depths of the recesses between the supports, and this depth h is measured.

The nanoimprint method by the thermocompression bonding method was used to form the support portion corresponding to each embodiment by the nanoimprint method. The nanoimprint method by this thermocompression bonding method was performed using a small thermal imprint apparatus manufactured by Toray Engineering Co., Ltd. The polycarbonate plate was heated to 150 ° C., the fine concavo-convex pattern surfaces of the mold were brought into contact with each other, and thermocompression bonding was performed at 5 MPa for 30 seconds. After cooling to 40 ° C., the polycarbonate plate was taken out from the mold to obtain a polycarbonate plate to which the fine concavo-convex structure was transferred by microfabrication. The mold is uneven so that the polycarbonate plate has the arrangement, structure, a, b, c, and d of the support portion corresponding to each of the examples (Examples 1 to 3 and 6 to 15) shown in Table 1. The one having a part was used (see FIGS. 2 to 4).

(Example 16: Preparation of original plate 16 for forming an ink film)
In Example 3, the compound represented by the chemical formula (2a) synthesized above was used in place of the compound represented by the chemical formula (1a) synthesized above, which is a photoresponsive compound, except that the compound represented by the chemical formula (2a) synthesized above was used in Example 3. In the same manner as above, the original plate 16 for forming an ink film was obtained.

(Example 17: Preparation of original plate 17 for forming an ink film)
In Example 3, the compound represented by the chemical formula (3b) synthesized above was used in place of the compound represented by the chemical formula (1a) synthesized above, which is a photoresponsive compound, except that the compound represented by the chemical formula (3b) synthesized above was used in Example 3. In the same manner as above, the original plate 17 for forming an ink film was obtained.

(Example 18: Preparation of original plate 18 for forming an ink film)
Example 3 except that the compound represented by the chemical formula (4) synthesized above was used in place of the compound represented by the chemical formula (1a) synthesized above, which is a photoresponsive compound. In the same manner as above, the original plate 18 for forming an ink film was obtained.

(Example 19: Preparation of original plate 19 for forming an ink film)
In Example 3, a crosslinked polymer of the polymer represented by the chemical formula (5) synthesized above was used instead of the compound represented by the chemical formula (1a) synthesized above, which is a photoresponsive compound. , An original plate 19 for forming an ink film was obtained in the same manner as in Example 3.

(Example 20: Preparation of original plate 20 for forming an ink film)
In Example 3, dichloromethane, toluene, and a photoresponsive compound, which are compounds represented by the chemical formula (1a) synthesized above, are used as raw materials for the surface layer forming solution, and a styrene acrylic resin (Starlight PMC) is further used as the resin. A prototype 20 for forming an ink film was obtained in the same manner as in Example 3 except that 5 parts by mass of US-1071) manufactured by Co., Ltd. was used.

(Example 4: Preparation of original plate 4 for forming an ink film)
360 parts by mass of dichloromethane, 360 parts by mass of toluene, and 570 parts by mass of the compound represented by the chemical formula (1a) synthesized above, which is a photoresponsive compound, were stirred and mixed at 50 ° C. for 1 hour to obtain a solution for forming a surface layer. .. The solution was well dispersed at room temperature (25 ° C.) for 30 minutes using a paint shaker. Then, the above solution was applied to the recesses of the support portion using a blade coater on a substrate (length 360 mm × width 180 mm × thickness 30 mm) in which the support portion corresponding to Example 4 was formed by a photolithography method. After coating, it is air-dried for 30 minutes, and then dried at 30 ° C. for 2 hours using a vacuum dryer to form a functional material portion in the recess between the support portions, and has a surface layer having a thickness of 10 μm on the substrate. An original plate 4 for forming an ink film was obtained.

In order to form the support portion corresponding to Example 4 by the above photolithography method, a photosensitive resin composition (manufactured by Tokyo Ohka Kogyo Co., Ltd.) as a raw material for the support portion is used as a substrate copper foil (JX Nippon Mining & Metals Co., Ltd.). A photosensitive resin composition coating film was obtained by applying a spin coating method on the surface of a shine surface or a matte surface manufactured by a company, model number: "JTCS 35 μm"). Next, a photomask was placed on a photosensitive resin composition coating film dried at 90 ° C. for 5 minutes in an infrared hot air dryer, and a 2 kW ultra-high pressure mercury lamp irradiator (JP-2000-EXC manufactured by ORC Manufacturing Co., Ltd.) was used. Then, the image (each support portion; and the desired depth between the support portions = the thickness h of the surface layer) was irradiated with an exposure amount obtained. Irradiate the developer consisting of 10 mass% tetramethylammonium hydroxyammonium aqueous solution (manufactured by Tokyo Oka Kogyo Co., Ltd.) / 1,4-dioxane (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) = 2/1 (mass ratio). After the subsequent coating film was immersed or ultrasonically treated, it was washed with pure water and dried with an infrared lamp to obtain a copper foil on which a coating film (support portion) in which the exposed portion remained was formed. In the above photomask, the exposed portion (= recessed portion between the support portions) so that the photosensitive resin composition coating film has the arrangement and structure of the support portion corresponding to Example 4 shown in Table 1, a and b. ) Was used (see FIGS. 2D (a), (b), and (c)). The thickness h of the surface layer (depth of the recess between the supports) was adjusted by the amount of exposure.

(Example 5: Preparation of original plate 5 for forming an ink film)
360 parts by mass of dichloromethane, 360 parts by mass of toluene, and 570 parts by mass of the compound represented by the chemical formula (1a) synthesized above, which is a photoresponsive compound, were stirred and mixed at 50 ° C. for 1 hour to obtain a solution for forming a surface layer. .. The solution was well dispersed at room temperature (25 ° C.) for 30 minutes using a paint shaker. Then, the above solution was applied to the recesses of the support portion using a blade coater on a substrate (length 360 mm × width 180 mm × thickness 30 mm) in which the support portion corresponding to Example 5 was formed by a dry etching method. After coating, it is air-dried for 30 minutes, and then dried at 30 ° C. for 2 hours using a vacuum dryer to form a functional material portion in the recess between the support portions, and has a surface layer having a thickness of 10 μm on the substrate. An original plate 5 for forming an ink film was obtained. The substrate and the support portion are integrally microfabricated using an anodized aluminum substrate by a dry etching method, and there is no boundary line (boundary surface) between the substrate and the support portion, so that the surface layer The thickness h (see FIG. 2D (c)) was taken as the depth of the recess between the support portions, and this depth h was measured.

In order to form the support portion corresponding to Example 5 by the above dry etching method, a photosensitive resin composition coating film produced in the same manner as in Example 4 is coated on an anodic oxide substrate by a spin coating method. A resist pattern was formed using a light exposure apparatus. Next, using a dry etching apparatus (Prinnacle 8000) manufactured by PMT Co., Ltd., the etching gas is CF _4, and dry etching is performed under the conditions of a gas flow rate of 75 sccm, a pressure of 2.5 mTorr, and an output of 2500 W to obtain a desired pattern. Processed into. After that, the resist pattern is ashed by oxygen plasma ashing, then immersed in an organic resist stripping agent (manufactured by Tokyo Ohka Kogyo Co., Ltd.) and washed with pure water to completely remove the resist pattern and dry etching. An anodized aluminum substrate on which a fine concavo-convex structure (support portion) was formed by microfabrication was obtained. The resist pattern is applied to the exposed portion (= recessed portion between the support portions) so that the surface of the anodized aluminum substrate has the arrangement, structure, and a and b of the support portion corresponding to the fifth embodiment shown in Table 1. A mask with an open corresponding portion was used (see FIGS. 2D (a), (b), (c)).

(Comparative Example 1: Preparation of Original Plate 21 for Ink Film Formation)
360 parts by mass of dichloromethane, 360 parts by mass of toluene, and 570 parts by mass of the compound represented by the above chemical formula (1a), which is a photoresponsive compound, are stirred and mixed at 50 ° C. for 1 hour to obtain a solution for forming a surface layer. rice field. This solution was well dispersed at room temperature (25 ° C.) for 30 minutes using a paint shaker, and then a blade coater was placed on an electropolished flat aluminum substrate (length 360 mm × 180 mm × thickness 30 mm). It was applied so that the thickness after drying was 6 μm. After coating, it was air-dried for 30 minutes and then dried at 30 ° C. for 2 hours using a vacuum dryer to obtain an ink film forming master plate 21 having a surface layer made of a photoresponsive compound on the substrate.

(Comparative Example 2: Preparation of Original Plate 22 for Ink Film Formation)
600 parts by mass of dichloromethane, 600 parts by mass of toluene, 570 parts by mass of the compound represented by the chemical formula (1a) synthesized above, which is a photoresponsive compound, and a styrene acrylic resin (manufactured by Seikou PMC Co., Ltd., US) which is a thermoplastic resin. −1071) 380 parts by mass was stirred and mixed at 50 ° C. for 1 hour to obtain a surface layer forming solution. This solution was well dispersed at room temperature (25 ° C.) for 30 minutes using a paint shaker, and then placed on an electropolished flat aluminum substrate (length 360 mm x width 180 mm x thickness 30 mm) with a blade coater. Was applied so that the thickness after drying was 6 μm. After coating, it was air-dried for 30 minutes and then dried at 30 ° C. for 2 hours using a vacuum dryer to obtain an ink film forming master plate 22 having a surface layer composed of a photoresponsive compound and a thermoplastic resin on the substrate. ..

The configurations of the original plates 1 to 22 for forming an ink film are shown in Table 1 below. The "resin content" in Table 1 indicates the content of the resin with respect to the total mass of the stimulus-responsive compound and the resin in the functional material portion.

(Continued from Example 1; Fabrication of a pattern film forming apparatus using the ink film forming original plate 1 and a pattern film forming method using this apparatus)
An adhesive layer is provided on the surface of the plate cylinder of the pattern film forming apparatus having the configuration as shown in FIG. 5, and the original plate 1 for forming an ink film is further attached and installed on the adhesive layer, and a monochromatic laser beam having a wavelength of 365 nm is emitted. The non-image portion of the image pattern (thin line width: 0.1 mm) shown in 6 was irradiated with an ^{irradiation amount of 2 J / cm 2.} As a result, the ink film forming surface 1 having a pattern in which the light irradiation portion, that is, the non-image portion becomes a hydrophilic portion and the image portion becomes a hydrophobic portion is formed.

Hydrophobic ink was applied to the image portion (hydrophobic portion) of the ink film forming surface 1 using an ink roller to form an ink film. The ink film was transferred to the blanket by relatively pressing and pulling the ink film surface 1 of the blanket against the ink film forming original plate 1 having the ink film. The ink film was transferred to the surface of the paper by relatively pressing and pulling the J paper A3 as the object to be printed against the blanket having the ink film, and a printed image was obtained (this printed image is "initial"). The same shall apply hereinafter). Further, 1000 print images were continuously output (the 1000th print image is referred to as "after 1000 printouts"; the same applies hereinafter). Then, as an erasing step, the entire surface of the ink film forming surface 1 was irradiated with a monochromatic laser beam having a wavelength of 365 nm. After light irradiation, when water was applied to the entire surface of the ink film forming surface 1 using a water roller, water was repelled, so that a hydrophobic surface similar to that of the original plate 1 before the writing operation was obtained. It was confirmed.

Further, by writing by irradiating the non-image portion of the output image with a monochromatic laser beam having a wavelength of 365 nm at an irradiation amount of ² J / cm 2, the photoresponsive compound is structurally changed (photoisomerized), and the light irradiation portion, that is, the light irradiation portion, that is, A pattern was formed in which the non-imaging part became a hydrophilic part and the image part became a hydrophobic part.

Ink was applied to the hydrophobic portion of this pattern using an ink roller to form an ink film. The ink film was transferred to the blanket by relatively pressing and pulling the ink film surface 1 of the blanket against the original plate 1 having the ink film. Further, the ink film is transferred to the surface of the paper by relatively pressing and pulling the paper as the object to be printed against the blanket having the ink film to obtain a printed image, and 1000 sheets of this printed image are continuously printed. Output (this 1000th printed image is referred to as "writing process and after 1000 printing". The same shall apply hereinafter).

(Continued from Examples 2 to 20 and Comparative Examples 1 and 2; Fabrication of a pattern film forming apparatus using the ink film forming original plates 2 to 22 and a pattern film forming method using this apparatus)
Continuation of Example 1 (Preparation of a pattern film forming apparatus using the ink film forming original plate 1) except that the ink film forming original plate 1 was changed to the ink film forming original plates 2 to 22 as shown in Table 1 below. And the pattern film forming method using this apparatus), the printed image was output.

[Evaluation method]
<Thin line reproducibility>
The printed images of the image patterns obtained above "initial", "after 1000 sheets are printed", and "writing process and after 1000 sheets are printed" are printed with a digital microscope "VHX-600" (KEYENCE Co., Ltd.). Made by). From the obtained monitor image, the line width of the thin line and the line width of the thin line at the intersection were observed by the indicator and ranked according to the following criteria. A to D pass. Further, FIG. 7 is a diagram showing the intersections of the thin lines used for the evaluation, in which the thick solid line circles are the intersections of the four straight lines, the fine solid line circles are the intersections of the three straight lines, and the broken line circles are the intersections of the two straight lines.

-Evaluation criteria for fine line reproducibility-
A: There are no thin lines or intersections where the line width is thick. B: The line is thick at the intersection of 4 straight lines. C: The line is thick at the intersection of 3 straight lines. D: The intersection of 2 straight lines. The line is thicker with E: The thin line itself is thicker.

The evaluation results are shown in Table 1 below.

As is clear from Table 1 above, it was found that when the original plates 1 to 18 of Examples 1 to 18 were used, the pattern could be easily rewritten digitally and the durability was excellent.

On the other hand, when the original plate 19 of Comparative Example 1 is used, the printed images of "after 1000 sheets are printed" and "after the writing process and 1000 sheets are printed" are unacceptable, and it is difficult to rewrite the pattern digitally. It was found that the durability before and after rewriting was insufficient.

Further, when the original plate 20 of Comparative Example 2 is used, the printed image of "the writing process and after 1000 sheets are printed" is unacceptable, it is difficult to rewrite the pattern digitally, and the durability after rewriting is also high. It turned out to be inadequate.

1,11 Original plate for forming ink film,
2nd edition body,
3 blanket,
4 impression cylinder,
5 ink roller,
6 water roller,
7 Monochromatic laser light source,
8 Printed material,
10 Pattern film forming device,
12 boards,
13 Support part,
14 Functional Materials Department,
15 Surface layer.

Claims (19)

With the board
It has a surface layer provided on the substrate and
The surface layer includes a functional material portion containing a stimulus-responsive compound whose affinity with water changes reversibly in response to an external stimulus, a convex support portion that supports the functional material portion, and a convex support portion. Original plate for forming an ink film, including. The cross section in the vertical direction along the line connecting the center points of the upper surface of the adjacent support portion, the center points of the top ridgeline, or the vertices with respect to the original plane is
(A) A structure in which a quadrangular support portion is arranged on a substrate with a gap, and a concave functional material portion is arranged in a gap between the quadrangular shapes (A).
(B) A structure (B) in which a triangular support portion is arranged without gaps on a substrate and a concave functional material portion is arranged in a gap between each triangular shape, or (c) a triangular support portion. Has a structure (C) in which a concave functional material portion is arranged in a gap between each triangular shape and is arranged with a gap on the substrate.
In the structure (A), the length a of each support portion and the length b of each functional material portion on the uppermost surface portion of the cross section satisfy the following equation.
In the structure (B), the length c of each functional material portion on the uppermost surface portion of the cross section satisfies the following formula.
The original plate for forming an ink film according to claim 1, wherein in the structure (C), the length d of each functional material portion on the uppermost surface portion of the cross section satisfies the following formula.

The ink film forming original plate according to claim 1 or 2, wherein the functional material portion and the support portion are arranged in a line when viewed from above the surface layer on the side opposite to the substrate. Original plate for forming an ink film. In the ink film forming original plate, the functional material portion and the support portion are arranged in a grid pattern when the pattern on the substrate surface is viewed through from above the surface layer on the opposite side of the substrate. The original plate for forming an ink film according to claim 1 or 2. In the ink film forming original plate, the functional material portion and the support portion are arranged in a checkered pattern when the pattern on the substrate surface is viewed through from above the surface layer on the opposite side of the substrate. The original plate for forming an ink film according to claim 1 or 2. The original plate for forming an ink film according to any one of claims 1 to 5, wherein the stimulus-responsive compound is a photoresponsive compound. The original plate for forming an ink film according to claim 6, wherein the photoresponsive compound is a compound represented by the following chemical formula (I).

In the above chemical formula (I),
R _{1 to} R ₅ are groups independently selected from the group consisting of a hydrogen atom, an alkyl group, an alkoxy group, a halogen group, a hydroxy group and a carboxyl group.
R ₆ is a substituent having at least one cyclic structure. A first writing step of applying an external stimulus to the surface layer of the ink film forming original plate according to any one of claims 1 to 7 to form a pattern composed of a hydrophilic portion and a hydrophobic portion. A pattern forming method having. The pattern forming method according to claim 8, wherein the external stimulus is light. The pattern forming method according to claim 8 or 9, wherein the external stimulus is light in a wavelength region of 280 to 400 nm. The pattern consisting of the hydrophilic part and the hydrophobic part is
An erasing step of applying an external stimulus to the pattern to erase the pattern, and
After the erasing step, a second writing step of applying an external stimulus to form a pattern consisting of a hydrophilic part and a hydrophobic part, and
The pattern forming method according to any one of claims 8 to 10, which can be rewritten by further performing. The first writing step of applying an external stimulus to the surface layer of the original plate for forming an ink film to form a pattern consisting of hydrophilic parts and hydrophobic parts, and
The process of forming an ink film on the pattern and
By relatively pressing and pulling the ink film surface of the blanket against the original plate on which the ink film is formed, only the ink film formed on the hydrophobic portion of the pattern on the ink film surface of the blanket. The first transfer step of transferring
A second transfer step of transferring the ink film to the surface of the object to be printed by relatively pressing and pulling the object to be printed against the blanket having the transferred ink film.
It is a pattern film forming method having
A method for forming a pattern film, wherein the original plate for forming an ink film is used as the original plate for forming an ink film according to any one of claims 1 to 7. The pattern film forming method according to claim 12, further comprising an erasing step of applying an external stimulus to the pattern to erase the pattern after the step of transferring the ink film to the surface of the object to be printed. The pattern film forming method according to claim 13, wherein the external stimulus used in the erasing step is light. The pattern film forming method according to claim 13 or 14, wherein the external stimulus used in the erasing step is visible light. The pattern can be rewritten by applying an external stimulus after the erasing step and further performing a second writing step of forming a pattern composed of a hydrophilic portion and a hydrophobic portion, according to claims 13 to 15. The pattern film forming method according to any one item. Original plate for forming ink film and
A writing means that applies an external stimulus to the surface layer of the original plate to form a pattern consisting of hydrophilic and hydrophobic sites.
An ink film forming means for forming an ink film on the pattern,
By relatively pressing and pulling the ink film surface of the blanket against the original plate on which the ink film is formed, the ink film formed on the hydrophobic portion of the pattern on the ink film surface of the blanket. The first transfer means to transfer only the ink
A second transfer means for transferring the ink film to the surface of the object to be printed by relatively pressing and pulling the object to be printed against the blanket having the transferred ink film.
It is a pattern film forming apparatus having
The pattern film forming apparatus, wherein the ink film forming original plate is the ink film forming original plate according to any one of claims 1 to 7. The pattern film forming apparatus according to claim 17, further comprising an erasing means for erasing the pattern by applying an external stimulus to the pattern. The pattern consisting of the hydrophilic part and the hydrophobic part is
An erasing step of applying an external stimulus to the pattern to erase the pattern, and
After the erasing step, a writing step of applying an external stimulus to form a pattern consisting of a hydrophilic part and a hydrophobic part,
The pattern film forming apparatus according to claim 17 or 18, which can be rewritten by further performing the above.

Images