JP2008254331A - Intaglio and method for manufacturing it - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an intaglio capable of easily obtaining a uniform shape of recessed part, a straightness of the edge of the recessed part, and an accuracy of the depth of the recessed part, and excellent in durability, and to provide a method for manufacturing it. <P>SOLUTION: The intaglio has a diamond-like carbon or an inorganic material on at least the surface, and on its surface, a recessed part for holding a transferred article is formed, and in addition, the recessed part is formed to be wider in the opening direction. The intaglio can be manufactured by a method comprising the process (A) wherein a removable projected pattern is formed on the surface of the substrate for the intaglio, the process (B) wherein on the surface of the substrate for the intaglio on which the removable projected pattern is formed, a film consisting of the diamond-like carbon or the inorganic material is formed, and the process (C) for removing the projected pattern. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to an intaglio such as an intaglio for gravure printing, an intaglio for application of an adhesive, an intaglio for transfer application of a resist material, an intaglio for forming a fine pattern such as a color filter used in a color liquid crystal display device, and a method for producing the same. .

  Conventional intaglios such as intaglios for gravure printing, intaglios for application of adhesives, intaglios for transfer application of resist materials, intaglios for forming fine patterns such as color filters used in color liquid crystal display devices, printing inks, adhesives A recess for holding the agent and the like is formed. Such an intaglio is usually formed by electroplating metal copper, which is easy to etch, on a roll or plate made of a metal such as iron, and after applying a photosensitive resin thereon, a direct latent image is obtained by laser exposure. Is formed by removing (developing) unnecessary portion of the resin to form an etching resist pattern, then performing etching, and further peeling the resin. The surface of the intaglio plate thus obtained is often subjected to, for example, electro nickel plating or electro chrome plating for the purpose of improving printing durability (see Patent Documents 1 and 2 above).

JP 2006-231668 A JP 2001-232747 A

Conventionally, the intaglio has a problem that the process is long as described above, and also has an etching process. Further, when electrochromic plating is performed, it is difficult to give a highly accurate shape. It was difficult to obtain a uniform shape of the recess, straightness of the recess edge, and accuracy of the recess depth.
Recently, as an alternative to electrochrome plating after etching, silicon oxide layers, titanium nitride layers, diamond-like carbon (DLC) layers, etc., which are inorganic materials, have been applied. It still does not change the need for metal etching.

  In view of such a problem, the present invention provides an intaglio which is easy to obtain the uniform shape of the recess, the straightness of the recess edge, and the accuracy of the recess depth, and is excellent in durability. A method of manufacturing such an intaglio plate, in particular, an etching method for producing an intaglio plate with high production efficiency, which eliminates the need for metal etching that is difficult to impart a shape with high accuracy and eliminates the need for electrochrome plating.

The present invention relates to the following.
1. An intaglio in which at least the surface has diamond-like carbon or an inorganic material, and a recess is formed on the surface for holding the transferred material, and the recess is formed wider toward the opening direction.
2. Item 2. The intaglio according to item 1, wherein the bottom surface of the recess is also made of diamond-like carbon or an inorganic material.
3. Item 3. The intaglio according to Item 1 or 2, wherein the diamond-like carbon or the inorganic material is a film or layer having a thickness of 0.1 to 100 µm.
4). Item 4. The intaglio according to any one of Items 1 to 3, which has diamond-like carbon at least on its surface.
5. Item 5. The intaglio according to item 4, wherein the diamond-like carbon has a hardness of 10 to 40 GPa.
6). Item 4 or wherein the diamond-like carbon film or layer is formed on the intaglio substrate via an intermediate layer containing at least one of Ti, Cr, W, Si, or a nitride or carbide thereof. The intaglio plate according to any one of 5 above.
7). The intaglio in any one of claim | item 1 -6 whose angle of a recessed part side surface is 30 degree | times or more and less than 90 degree | times.
8). Item 8. The intaglio according to item 7, wherein the angle of the side surface of the recess is 30 degrees or more and 60 degrees or less.
9. Item 8. The intaglio according to items 1 to 7, wherein the plate is a roll.
10. Item 8. The intaglio according to items 1 to 7, wherein the plate is generally a flat plate.
11. (A) forming a removable convex pattern on the surface of the intaglio substrate;
(B) including a step of forming a film made of diamond-like carbon or an inorganic material on the surface of the intaglio substrate on which a removable convex pattern is formed, and (C) a step of removing the convex pattern An intaglio manufacturing method characterized by the above.
12 Item 12. The method for producing an intaglio according to Item 11, wherein the intaglio substrate has diamond-like carbon or an inorganic material on the surface thereof.
13. Item 13. The method for producing an intaglio according to Item 11 or 12, wherein the removable convex pattern is formed by a photolithography method using a photosensitive resist.
14 Item 14. The method for producing an intaglio according to any one of Items 11 to 13, wherein the film made of diamond-like carbon or an inorganic material is formed so as to have different properties or characteristics on the side of the convex pattern on the intaglio substrate.
15. The width of the boundary surface between the film formed on the intaglio substrate and the film formed on the side surface of the removable convex pattern is not reduced in the standing direction of the convex pattern, Item 15. The method for producing an intaglio plate according to any one of Items 11 to 14, which is larger.
16. Item 17. The method for producing an intaglio according to any one of Items 11 to 16, wherein the film formed on the intaglio substrate is diamond-like carbon.
17. Item 17. The method for producing an intaglio according to Item 16, wherein the hardness of the diamond-like carbon film formed on the substrate for intaglio is larger than the hardness of the diamond-like carbon film formed on the side surface of the convex pattern.
18. Item 18. The intaglio plate according to item 17, wherein the diamond-like carbon film formed on the intaglio substrate has a hardness of 10 to 40 GPa, and the diamond-like carbon film formed on the side surface of the convex pattern has a hardness of 1 to 15 GPa. Production method.
19. Item 19. The method for producing an intaglio according to any one of Items 11 to 18, wherein the diamond-like carbon film is formed by a vacuum deposition method, a sputtering method, an ion plating method, an arc discharge method, an ionization deposition method or a plasma CVD method.
20. Before performing the step of forming a film on the surface of the intaglio substrate on which the removable convex pattern is formed, the intermediate layer is formed on the surface of the substrate on which the removable convex pattern is formed. Item 20. The method for producing an intaglio according to any one of Items 10 to 19, wherein the step of forming is performed.
21. Item 21. The method for producing an intaglio according to Item 20, wherein the intermediate layer contains one or more of Ti, Cr, W, Si, nitrides or carbides thereof.
22. Item 22. The method for producing an intaglio according to any one of Items 11 to 21, wherein the film made of diamond-like carbon or an inorganic material has a thickness of 0.1 to 100 μm.

The intaglio in the present invention easily achieves a uniform shape of the recess, straightness of the recess edge, and accuracy of the recess depth, which eliminates the need for high precision and difficult etching of the base material in the manufacture of the intaglio. This is partly because electrochromic plating, which is difficult to be accurate, is unnecessary. Therefore, by using the intaglio according to the present invention, more uniform, more precise and more accurate transfer coating is possible.
Since the intaglio in the present invention can form a concave pattern by forming a convex pattern on the substrate and removing the convex pattern after forming the film, its manufacture is easy and productivity is improved. Rich.
The intaglio in the present invention is useful for gravure intaglio and pressure sensitive adhesive intaglio. The intaglio in the present invention is further useful as an intaglio for resist transfer coating, an intaglio for transfer coating on a substrate such as a glass substrate of color filter ink for forming a fine pattern of a color filter used in a color liquid crystal display device, and the like. These can be usefully used in the manufacturing process of fine structures such as precision electronic components.
Furthermore, the surface of the intaglio plate is made of diamond-like carbon or an inorganic material, resulting in excellent wear resistance. When a film made of diamond-like carbon or an inorganic material is formed on the surface of the intaglio plate, the adhesion to the substrate is excellent, and its peeling resistance is excellent. Excellent in properties. The adhesion between the substrate and the film can be improved by the intermediate layer, and thereby the life of the intaglio can be further increased for repeated use.

  According to the method for producing an intaglio according to the present invention, the number of steps is small, and in particular, since a wide concave portion can be easily produced in the opening direction, it can be produced with high production efficiency.

An example of the present invention will be described with reference to the drawings.
FIG. 1 is a partial perspective view showing an example of the intaglio of the present invention. FIG. 2 is a cross-sectional view taken along the line AA in FIG. FIG. 2A shows a case where the side surface of the recess is smooth and planar, while FIG. 2B shows a case where the side surface of the recess has gentle irregularities. The intaglio 1 has a diamond-like carbon (hereinafter abbreviated as “DLC”) film 3 (in the present invention, “film” includes the concept of “layer”) 3 on a base material 2 serving as a base. The concave portions 4 are formed in the DLC film 3, and the intaglio substrate 2 is exposed at the bottom of the concave portions 4.
In this example, the recess 4 is formed in a groove shape, but an appropriate shape is formed according to the purpose. The planar shape of the concave portion 4 is a triangle such as a regular triangle, an isosceles triangle, a right triangle, a square, a rectangle, a rhombus, a parallelogram, a trapezoid or other quadrangle, a (positive) hexagon, (positive) octagon, (positive) There are (positive) n-gons (n is an integer greater than or equal to 3) such as a dodecagon and (positive) icosahedron, a circle, an ellipse, and a star, and the shape is selected according to the purpose. Such shapes can be used in combination. Further, the distribution density of the recesses is appropriately determined according to the purpose.
An intermediate layer (not shown) may be laminated between the substrate 2 and the film 3 for the purpose of improving the adhesiveness of the film 3 or the like. Alternatively, the recess 4 is wide as a whole in the opening direction. It is not always necessary that the width is constant and wide at the gradient α as shown in the drawing. If there is no problem in printing ink transfer, the concave portion may have a portion whose width becomes narrower in the opening direction, but it is better not to have such a portion, and the concave portion narrows in the opening direction. It is preferable that it spreads as a whole.

によってαを決定する。
αは、角度で３０度以上９０度未満が好ましく、３０度以上６０度以下が特に好ましい。これにより、印刷インク、粘着剤、レジスト用材料、カラーフィルタ用インク等の転写物が、容易に転写される。 The side surface of the recess is not necessarily smooth and flat. In this case, as shown in FIG. 2 (b), the gradient α obtains the height h of the recess and the width s of the side surface of the recess (measured in the width direction of the side surface of the recess in the horizontal direction)

Determines α.
α is preferably 30 ° or more and less than 90 °, and particularly preferably 30 ° or more and 60 ° or less. Thereby, transfer materials, such as printing ink, an adhesive, a resist material, and color filter ink, are easily transferred.

  The thickness of the film is preferably in the range of 0.1 μm to 100 μm. If the film is too thick, it takes a long time to form the film and the working efficiency tends to decrease. On the other hand, if the film is too thin, the amount of ink, pressure-sensitive adhesive or other transferred material is reduced, resulting in uneven printing, uneven coating, and uneven transfer. The thickness of the film is particularly preferably 5 to 30 μm.

Here, the size of the recess is appropriately determined depending on the use, but as a planar shape, the length of a square piece is preferably 5 to 1000 μm, and particularly preferably 50 to 300 μm in width. Other shaped objects are preferably sized so as to have the same area as such a square.
The interval between the recesses is also appropriately used according to the purpose. However, when the transfer product is uniformly applied to a transfer substrate such as paper (paper) or the like, or the transfer substrate such as adhesive (plastic film or the like) is applied. When the coating is uniformly applied, the interval between the concave portions in the corresponding intaglio at the location is preferably 1 to 30 μm, particularly preferably 5 to 20 μm in width.
The moving direction of the blade or squeegee used for uniformly filling the concave portion with the transferred material is appropriately selected such that it is relatively difficult to catch the convex portion separating the concave portion. If it is a simple figure, it is preferable that the moving direction of the blade or squeegee is 45 to 60 degrees with respect to the side.

  Examples of the shape of the intaglio substrate include a sheet shape, a plate shape, and a roll shape. In the case of a roll, the roll itself, a sheet, or a plate may be attached to a rotating body (roll).

  The material used for the intaglio substrate in the present invention is particularly preferably made of iron, aluminum, stainless steel, chromium or nickel plated iron, titanium, titanium-lined material, nickel or the like.

  As a film used in the present invention, a DLC film is particularly preferable because it is excellent in chemical resistance.

As a method for forming a DLC thin film, dry deposition such as a vacuum deposition method, a sputtering method, an ion plating method, an arc discharge method, a physical vapor deposition method such as an ionization deposition method, a chemical vapor deposition method such as a plasma CVD method, etc. Although a method can be adopted, a plasma CVD method using a high frequency or pulse discharge in which the film formation temperature can be controlled from room temperature is particularly preferable.
In order to form the DLC thin film by the plasma CVD method, a hydrocarbon-based gas is preferably used as a carbon source as a raw material. For example, alkane gases such as methane, ethane, propane, butane, pentane, hexane, alkene gases such as ethylene, propylene, butene, pentene, alkadiene gases such as pentadiene, butadiene, acetylene, methylacetylene, etc. Alkyne gases, aromatic hydrocarbon gases such as benzene, toluene, xylene, indene, naphthalene and phenanthrene, cycloalkane gases such as cyclopropane and cyclohexane, cycloalkene gases such as cyclopentene and cyclohexene, methanol And alcohol gases such as ethanol, ketone gases such as acetone and methyl ethyl ketone, and aldehyde gases such as methanal and ethanal. The said gas may be used independently and may use 2 or more types together. Further, a mixture of the above-described carbon source and hydrogen gas as a raw material gas containing carbon and hydrogen as elements, and the above-described carbon source and a gas of a compound composed only of carbon and oxygen such as carbon monoxide gas and carbon dioxide gas. A mixture of a compound gas composed of only carbon and oxygen, such as a mixture, carbon monoxide gas, carbon dioxide gas, and hydrogen gas; a compound gas composed of only carbon and oxygen, such as carbon monoxide gas, carbon dioxide gas; Examples thereof include a mixture with oxygen gas or water vapor. Further, these source gases may contain a rare gas. The rare gas is a gas composed of an element belonging to Group 0 of the periodic table, and examples thereof include helium, argon, neon, and xenon. These rare gases may be used alone or in combination of two or more.

The film may be entirely formed of the insulating DLC thin film described above, but the adhesion of the DLC thin film to an intaglio substrate such as a metal plate is improved to further improve the durability of the film. In order to achieve this, it is preferable to insert an intermediate layer composed of at least one component selected from Ti, Cr, W, Si, nitrides or carbides thereof, or the like, between the two.
The Si or SiC thin film has excellent adhesion to, for example, a metal such as stainless steel, and forms SiC at the interface with the insulating DLC thin film laminated thereon, thereby improving the adhesion of the DLC film. Has the effect of improving.
The intermediate layer can be formed by the dry coating method as described above.
The thickness of the intermediate layer is preferably 1 μm or less, and more preferably 0.5 μm or less in consideration of productivity. A coating of 1 μm or more is not suitable because the coating time becomes long and the internal stress of the coating film increases.

Even when the film is formed of an inorganic material such as Al ₂ O ₃ or SiO ₂ , a physical vapor deposition method such as a sputtering method or an ion plating method or a chemical vapor deposition method such as plasma CVD can be used. For example, in the case of forming by sputtering, an oxide or nitride such as SiO ₂ or Si ₃ N ₄ can be formed by introducing Si or Al as a target and introducing oxygen, nitrogen or the like as a reactive gas. it can. In the case of using the ion plating method, Si or Al can be used as a raw material, and an electron beam can be irradiated to evaporate to form a film on the substrate. At that time, an oxide, nitride, or carbide film can be formed by introducing a reactive gas such as oxygen, nitrogen, or acetylene.
In the case of forming a film by the CVD method, the film can be formed by using a chemical gas such as a metal chloride, a metal hydride, an organometallic compound, etc. as a raw material. The CVD of silicon oxide can be performed by plasma CVD using, for example, TEOS or ozone. The CVD of silicon nitride can be performed by plasma CVD using ammonia and silane, for example.

The method for producing an intaglio plate in the present invention includes a step of forming a film on the surface of the intaglio substrate so that a recess is formed.
This step is a step (A) of forming a removable convex pattern on the surface of the intaglio substrate,
(B) including a step of forming a film on the surface of the intaglio substrate on which a removable convex pattern is formed, and (C) a step of removing the convex pattern.
The above-mentioned concave portions have a large number of concave portions so that a latent image is drawn on the transfer base material when the transferred material stored in the concave portions is transferred. It is preferable that it consists of.

The step of forming a removable convex pattern on the surface of the (A) intaglio substrate can utilize a method of forming a resist pattern using a photolithographic method.
This method
(A-1) a step of forming a photosensitive resist layer on the intaglio substrate,
(A-2) exposing the photosensitive resist layer to a desired latent image (latent image pattern) composed of a concave portion for holding ink with laser light or ultraviolet rays through a mask; and (a-3) photosensitivity after exposure. A step of developing the resist layer.

In addition, the step of forming a removable convex pattern on the surface of the (A) intaglio substrate,
(B-1) forming a resin layer on the intaglio substrate,
(B-2) including a step of sublimating the resin layer with a laser beam to form a desired latent image (latent image pattern) including a concave portion for holding ink.

  As the photosensitive resist, a well-known negative resist (a portion irradiated with light is cured) can be used. Further, a positive resist can be used as the photosensitive resist.

  As a specific method, a convex film pattern is formed by laminating a dry film resist (photosensitive resin layer) on a base for intaglio, or applying a liquid resist, and then exposing to laser light or wearing a mask and exposing to ultraviolet rays. The remaining portion can be cured, the unnecessary portion can be developed, and the unnecessary portion can be developed and removed. In addition, the convex pattern is left as a convex pattern by applying a liquid resist to the intaglio substrate and then drying or pre-curing the solvent, followed by laser light exposure or wearing a mask and exposing. It can also be formed by setting the part in a cured state, making the unnecessary part developable, and developing and removing the unnecessary part. The liquid resist can be applied by spraying, dispenser, dipping, roll, spin coating or the like.

In the above, as long as patterning can be performed by irradiating the photocurable resin with active energy rays with or without a mask, the mode is not limited.
When the size of the conductive substrate is large, a method using a dry film resist is preferable from the viewpoint of productivity, and when the intaglio substrate is a roll or the like, laser light is applied without applying a mask after applying the liquid resist. For example, a direct exposure method is preferable.
Here, a layer of DLC or an inorganic material is formed in advance on the entire surface of the intaglio substrate, and this can be used again as the intaglio substrate. Thereby, the bottom part of a recessed part will also be covered with DLC or an inorganic material, and especially a chemical-resistant improvement can be aimed at.

An example of a method for producing an intaglio plate according to the present invention will be described with reference to the drawings.
FIG. 3 is a sectional view showing an example of a process showing a method for manufacturing an intaglio.

  A photosensitive resist layer (photosensitive resin layer) 5 is formed on the intaglio substrate 2 (FIG. 3A). The photosensitive resist layer 5 is patterned by applying a photolithographic method to the photosensitive resist layer (photosensitive resin layer) 5 of the laminate (FIG. 3B). For patterning, a photomask on which a pattern is formed is placed on the photosensitive resist layer 5, exposed, and then developed to remove unnecessary portions of the photosensitive resist layer 5 to leave the convex pattern 6. Is done. The convex pattern is considered to correspond to the concave portion 4 on the intaglio substrate 2.

At this time, in the cross-sectional shape of the convex pattern 6, the maximum value d ₁ of the convex pattern width must be equal to or larger than the width d ₀ in contact with the convex pattern and the intaglio substrate 2. This is because the recess width of the film having good adhesion is determined by d ₁ . Here, as a method for increasing the width d ₀ of the convex pattern width in contact with the convex pattern and the intaglio substrate 2 in the sectional shape of the convex pattern 6, the convex pattern width maximum value d ₁ is as follows. It is sufficient to use a resist having a characteristic of over-development during development or having an undercut shape. d ₁ is preferably is realized at the top of the convex portion.
The pattern shape of the removable convex portion is associated with the shape of the concave portion. As the planar shape, the length of a square piece is preferably 3 to 1000 μm, and particularly preferably 50 to 300 μm in width. Other shaped objects are preferably sized so as to have the same area as such a square. The interval between the convex portions is also appropriately used according to the purpose. However, when the transfer product is uniformly applied to a transfer substrate such as a printing target or an adhesive application target, the interval between the corresponding convex portions is 1 A width of ˜30 μm, particularly a width of 5 to 20 μm is desirable.

Next, a film 7 is formed on the surface of the intaglio substrate 2 having the convex pattern 6 (FIG. 3C). The method for forming the film is as described above.
Further, the convex pattern is removed with the film 7 attached (FIG. 3D).
A commercially available resist stripping solution, inorganic, organic alkali, organic solvent, or the like can be used to remove the resist to which the film is attached. In addition, if there is a dedicated stripping solution corresponding to the resist used to form the pattern, it can be used.
As a peeling method, for example, it is possible to remove the resist after it has been swelled, broken or dissolved by immersion in a chemical solution. In order to sufficiently impregnate the resist with the solution, techniques such as ultrasonic waves, heating, and stirring may be used in combination. In addition, the liquid can be applied with a shower, a jet or the like in order to promote peeling, and can be rubbed with a soft cloth or cotton swab.
In addition, when the heat resistance of the film is sufficiently high, a method of baking at a high temperature to carbonize the resist and removing it, or irradiating with a laser to burn off can be used.
As the stripping solution, for example, a 3% NaOH solution is used, and showering or dipping can be applied as the stripping method.

The film formed on the intaglio substrate 2 and the film formed on the side surface of the convex pattern 6 have different properties. That is, the hardness of the former is greater than the latter. For this reason, when the convex pattern is removed, the film is separated at this boundary. As a result, the inclination angle α of the side surface of the concave is preferably 30 degrees or more and less than 90 degrees, and preferably 30 degrees or more and 60 degrees or less. It is particularly preferable that when the DLC film is formed by plasma CVD, it becomes easy to control at approximately 45 to 60 degrees. That is, the concave portion 4 is formed so as to become wider toward the opening direction.
The film formed on the intaglio substrate 2 and the film formed on the side surface of the convex pattern 6 have different properties. This is because in the formation of the film, the intaglio substrate does not become a shadow of the resist, so the film on the intaglio substrate is uniform in nature. On the other hand, the film is formed on the side surface of the convex pattern because the side surface of the convex pattern has an angle with respect to the film thickness direction on the intaglio substrate. Cannot obtain a film having the same characteristics (for example, the same hardness) as the film on the intaglio substrate. In such a heterogeneous film contact surface, a film boundary surface is formed as the film grows, and since the boundary surface is a film growth surface, it is smooth. For this reason, when removing the convex pattern, the film (particularly the DLC film) is easily separated at this boundary. Further, the inclination angle α which becomes the boundary surface, that is, the side surface of the concave portion is that the growth of the film is delayed on the side surface of the convex portion pattern with respect to the film thickness direction on the intaglio substrate. , Controlled as described above.

In the present invention, the hardness of the film formed on the intaglio substrate is preferably 10 to 40 GPa. A film having a hardness of less than 10 GPa is soft and has a low durability in repeated use of the intaglio. When the hardness is 40 GPa or more, it is not preferable because when the intaglio is processed such as bending, it cannot follow the deformation of the base material, and the film is cracked or cracked. More preferably, it is 12-30 GPa.
On the other hand, the hardness of the film formed on the side surface of the convex pattern is preferably 1 to 15 GPa. The film formed on the side surface of the convex pattern is preferably formed so as to be at least lower in hardness than the film formed on the intaglio substrate. By doing so, a boundary surface is formed between the two, and a wide concave portion is formed after a process of peeling the convex pattern to which the film is attached later. The hardness of the film formed on the side surface of the convex pattern is more preferably 1 to 10 GPa.
The hardness of the film can be measured using a nanoindentation method. In the nanoindentation method, a regular triangular pyramid (Berkovic type) indenter with a diamond tip is pressed into the surface of a thin film or material, and the hardness is obtained from the load applied to the indenter and the projected area under the indenter. As a measurement by the nanoindentation method, a device called a nanoindenter is commercially available. The hardness of the film formed on the intaglio substrate can be measured by pushing the indenter directly onto the intaglio substrate. In addition, in order to measure the hardness of the film formed on the side surface of the convex pattern, after forming the film, a part of the intaglio substrate having the convex pattern is cut out and cast with a resin, and the convex part is projected from the cross section. Measurement can be performed by pressing an indenter into the film formed on the side surface of the part pattern. Normally, in the nanoindentation method, the hardness is measured by applying a minute load of 1 to 100 mN to the indenter, but in the present invention, the value measured by applying a load of 3 mN for 10 seconds is described as the hardness value.
In this way, the intaglio 1 can be produced.

FIG. 4 shows a sectional view of an intaglio having an intermediate layer and its precursor.
Before forming the film 7 on the surface of the intaglio substrate 2 on which the convex pattern 6 is formed, it is preferable to form the intermediate layer 8 (FIG. 4 (c ′)). As the intermediate layer, those described above can be used, and the formation method is also as described above. In this example, the intaglio plate obtained is such that the intaglio substrate 2 is exposed at the bottom of the recess 4, and a film 7 is formed on the intermediate layer 8 in other cases (FIG. 4D). ).

When applying gravure printing or pressure-sensitive adhesive using the intaglio plate of the present invention, apply printing ink or pressure-sensitive adhesive on the surface of the gravure roll, rub the surface of the gravure roll with a doctor blade, and ink on the convex portions other than the concave portions. Or the adhesive is scraped off, a transfer substrate such as paper is pressure-bonded to the gravure roll, and the ink or adhesive stored in the recesses is transferred to the transfer substrate. Such a method is suitable for a flexible transfer substrate. The transferred material may be a resist.
When performing transfer coating of color filter ink or colored resist onto a substrate such as a glass substrate or transfer of resist onto a substrate such as a copper-clad laminate, the color filter ink or colored resist is formed in the concave portion of the intaglio plate. Alternatively, an appropriate amount of resist can be stored, transferred to a transfer device such as a stamp or a roll, and further transferred to a substrate such as a glass substrate or a copper clad laminate. Such a method is particularly suitable for a rigid transfer substrate. Such a method can also be used for transfer coating of a printing ink containing a light-emitting substance such as organic EL or inorganic EL onto a substrate.

(Formation of convex pattern)
A resist film (Photech RY3315, 10 μm thickness, manufactured by Hitachi Chemical Co., Ltd.) was bonded to both sides of a 150 mm square stainless steel plate (SUS316L, mirror polished, thickness 300 μm, manufactured by Nisshin Steel Co., Ltd.) (FIG. 3). Corresponding to (a)). The bonding conditions were a roll temperature of 105 ° C., a pressure of 0.5 MPa, and a line speed of 1 m / min. Next, the width of one side of the rectangular light transmitting portion is 140 μm, the rectangular pitch is 200 μm, and the bias angle is 60 ° (in the regular square, the rectangle is arranged at an angle of 60 degrees with respect to the regular square side. The negative film in which the pattern was formed with a size of 120 m square was left still on one side of the stainless steel plate. Using an ultraviolet irradiation device, ultraviolet rays were irradiated at 120 mJ / cm ² from above and below the stainless plate on which the negative film was placed under a vacuum of 600 mmHg or less. further. By developing with a 1% sodium carbonate aqueous solution, a pattern (printing pattern) made of a resist film having a width of 140 to 145 μm on one side, a rectangular pitch of 200 μm, and a bias angle of 60 degrees was formed on a SUS plate. Note that the entire surface opposite to the surface on which the pattern is formed is exposed and is not developed, and a resist film is formed on the entire surface (corresponding to FIG. 3B).

(Formation of film)
A DLC film is formed by a PBII / D apparatus (Type III, manufactured by Kurita Manufacturing Co., Ltd.). A stainless steel substrate with a resist film attached thereto was placed in the chamber, the inside of the chamber was evacuated, and the substrate surface was cleaned with argon gas. Next, hexamethyldisiloxane was introduced into the chamber, and an intermediate layer was formed to a thickness of 0.1 μm. Next, toluene, methane, and acetylene gas were introduced, and a DLC layer was formed on the intermediate layer so as to have a film thickness of 20 μm (corresponding to FIG. 3C). At that time, the thickness of the DLC film on both sides of the convex portion formed by the resist film was 15 to 17 μm. The angle of the boundary surface was 45 to 50 degrees. The thickness of the DLC film and the angle of the boundary surface were measured by cutting a part of the conductive substrate and casting it with a resin, and observing the cross section with SEM at a magnification of 3000 times. Since the measurement points were 5 points and both sides of the resist film were measured, a maximum value and a minimum value of 10 points in total were adopted.

(Concavity formation; removal of convex pattern with film attached)
The stainless steel substrate with the film attached was immersed in an aqueous sodium hydroxide solution (10%, 50 ° C.) and left for 8 hours with occasional shaking. The resist film forming the convex pattern and the DLC film adhering thereto have been peeled off. Since there was a part that was difficult to peel off, the entire surface was peeled off by lightly rubbing with a cloth to obtain an intaglio (corresponding to FIG. 3D).
The shape of the recess was wider toward the opening direction, and the inclination angle of the side surface of the recess was the same as the angle of the boundary surface. The depth of the recess was 19 to 20 μm. Moreover, the width | variety in the bottom part of a recessed part was 140-143 micrometers, and the width | variety (maximum width) in an opening part was 180-185 micrometers. The pitch of the recesses was 200 μm, and an intaglio plate having a uniform shape of the recesses, straightness of the recess edges, and uniformity of the recess depths was obtained.

  Using the above intaglio, gravure printing can be repeated 1000 times or more without peeling off the film.

(Formation of convex pattern)
A liquid resist (ZPN-2000, manufactured by Nippon Zeon Co., Ltd.) was applied on both sides to a 150 mm square titanium plate (pure titanium, mirror polished, thickness 400 μm, manufactured by Nippon Metal Co., Ltd.). By applying three times, a resist film having a thickness of 6 μm was obtained. After pre-baking at 110 ° C. for 1 minute, the width of one side of the rectangular light transmitting portion is 120 μm, the rectangular pitch is 150 μm, and the bias angle is 60 ° (in the regular square, the angle is 60 degrees with respect to the regular square side. The negative chrome mask in which the pattern was formed with a size of 110 mm square was allowed to stand on one side of the titanium plate. Using an ultraviolet irradiation device, the substrate was adsorbed under a vacuum of 600 mmHg or less, and ultraviolet rays were irradiated at 200 mJ / cm ² from the top of the titanium plate on which the chromium mask was placed. The back surface was irradiated with 200 mJ / cm ² without a mask. After heating at 115 ° C. for 1 minute and developing with 2.38% tetramethylammonium hydroxide (TMAH), one side width 120-122 μm, rectangular pitch 150 μm, bias angle 60 ° on a titanium plate A pattern made of a resist film was formed.

(Formation of film)
After coating to the intermediate layer in the same manner as in Example 1, DLC was coated to a thickness of 10 μm. At that time, the thickness of the DLC film on both sides of the convex portion formed by the resist film was 7 to 8 μm. The angle of the boundary surface was 45 to 51 degrees. The film thickness and the interface angle were measured in the same manner as in Example 1.
(Concavity formation; removal of convex pattern with film attached)
The titanium substrate to which the film was adhered was immersed in an aqueous sodium hydroxide solution (10%, 50 ° C.) and left for 2 hours while applying ultrasonic waves at 50 kHz. The resist film forming the convex pattern and the DLC film adhering thereto have been peeled off. Since there was a part that was difficult to peel off, the entire surface was peeled off by rubbing lightly with a cloth to obtain an intaglio.
The shape of the recess was wider toward the opening direction, and the inclination angle of the side surface of the recess was the same as the angle of the boundary surface. The depth of the recess was 9 to 10 μm. The width at the bottom of the recess was 120 to 122 μm, and the width at the opening (maximum width) was 140 to 142 μm. The pitch of the recesses was 150 μm, and an intaglio plate having a uniform shape of the recesses, straightness of the recess edges, and uniformity of the recess depths was obtained.

  Using the above intaglio, gravure printing can be repeated 1000 times or more without peeling off the film.

A liquid resist (KMPR-1050, manufactured by Nippon Kayaku Co., Ltd.) was applied to both surfaces of a stainless steel substrate (SUS304, 314 × 150 mm, manufactured by Nisshin Steel Co., Ltd.) with a thickness of 15 μm. After pre-baking at 90 ° C. for 10 minutes, the width of one side of the rectangular light transmitting portion is 120 μm, the rectangular pitch is 150 μm, and the bias angle is 60 ° (in the regular square, an angle of 60 degrees with respect to the regular square side Thus, two negative chrome masks having a pattern of 110 mm square size were placed side by side on one side of a stainless steel plate and allowed to stand. The substrate was adsorbed under a vacuum of 600 mmHg or less using an ultraviolet irradiation device, and ultraviolet rays were irradiated at 200 mJ / cm ² from the top of the stainless steel plate on which the chromium mask was placed. The back surface was irradiated with 200 mJ / cm ² without a mask. After heating at 95 ° C. for 7 minutes and developing with 2.38% tetramethylammonium hydroxide (TMAH), one side has a width of 120 to 125 μm, a rectangular pitch of 150 μm, and a bias angle of 60 ° on a stainless steel plate. A pattern made of a resist film was formed.

(Formation of film)
As in Example 2, DLC was coated to a thickness of 10 μm. At this time, the thickness of the DLC film on both sides of the convex portion formed by the resist film was 6 to 7 μm. The angle of the boundary surface was 45 to 48 degrees.

(Concavity formation; removal of convex pattern with film attached)
The stainless steel substrate to which the film was attached was immersed in a resist stripping solution (RemoverPG, Nippon Kayaku Co., Ltd., 70 ° C.) and left for 8 hours with occasional rocking. The resist film forming the convex pattern and the DLC film adhering thereto have been peeled off. Since there was a part that was difficult to peel off, the entire surface was peeled off by rubbing lightly with a cloth to obtain an intaglio.
The shape of the recess was wider toward the opening direction, and the inclination angle of the side surface of the recess was the same as the angle of the boundary surface. The shape of the recess was wider toward the opening direction, and the inclination angle of the side surface of the recess was the same as the angle of the boundary surface. The depth of the recess was 9 to 10 μm. The width at the bottom of the recess was 120 to 123 μm, and the width at the opening (maximum width) was 140 to 143 μm. The pitch of the recesses was 150 μm, and an intaglio plate having a uniform shape of the recesses, straightness of the recess edges, and uniformity of the recess depths was obtained.

  Using the above intaglio, gravure printing can be repeated 1000 times or more without peeling off the film.

(Formation of convex pattern) to (Removal of convex pattern with film attached)
In the same manner as in Example 2, a liquid resist was applied, a convex pattern was formed by laser exposure, a DLC film was formed to be 10 μm, the convex pattern to which the film was attached was removed, and a gravure printing roll was formed. As a result, an intaglio plate having a uniform shape of the recess, straightness of the recess edge, and uniformity of the recess depth was obtained.

(Repeated use)
As a result of gravure printing using the above intaglio, gravure printing could be repeated 1000 times or more without peeling of the film.

(Preparation of intaglio substrate)
First, a roll having a diameter of 200 mm and a length of 300 mm (SUS304, mirror polished, manufactured by Nisshin Steel Co., Ltd.) was prepared, and a PBII / D apparatus (Type III, manufactured by Kurita Manufacturing Co., Ltd.) was used on the entire cylindrical surface. 1, a DLC film (thickness of 1 μm) was formed, and this was again used as an intaglio substrate.

(Formation of convex pattern) to (Removal of convex pattern with film attached)
Using the above intaglio substrate instead of the 150 mm square titanium plate in Example 2, application of liquid resist (however, peripheral surface), formation of convex pattern, formation of DLC film in the same manner as in Example 2. As a result of removing the convex part pattern (including the formation of the intermediate layer) and the convex pattern to which the film is adhered and producing the roll for gravure printing, it has a uniform shape of the concave part, straightness of the concave part edge, and uniformity of the concave part depth. An intaglio was obtained. In this gravure printing roll, the bottom of the recess is also covered with a DLC film, and in particular, chemical resistance can be improved.

  Using the above intaglio (gravure printing roll), gravure printing can be repeated 1000 times or more without film peeling.

The perspective view which shows an example of the intaglio of this invention. AA sectional drawing of FIG. Sectional drawing which shows an example of the process which shows the manufacturing method of an intaglio. Sectional drawing of an example of the intaglio which has an intermediate | middle layer, and its precursor.

Explanation of symbols

1: Intaglio 2: Intaglio substrate 3: Film 4: Recess 5: Photosensitive resist layer (photosensitive resin layer)
6: Convex pattern 7: DLC film 8: Intermediate layer

Claims (22)

  An intaglio in which at least the surface has diamond-like carbon or an inorganic material, and a recess is formed on the surface for holding the transferred material, and the recess is formed wider toward the opening direction.   The intaglio according to claim 1, wherein the bottom surface of the recess is also made of diamond-like carbon or an inorganic material.   The intaglio according to claim 1 or 2, wherein the diamond-like carbon or the inorganic material is a film or layer having a thickness of 0.1 to 100 µm.   The intaglio according to any one of claims 1 to 3, which has diamond-like carbon at least on its surface.   The intaglio according to claim 4, wherein the hardness of diamond-like carbon is 10 to 40 GPa.   5. A diamond-like carbon film or layer is formed on an intaglio substrate via an intermediate layer containing at least one of Ti, Cr, W, Si, or a nitride or carbide thereof. Or the intaglio according to any one of 5;   The intaglio according to any one of claims 1 to 6, wherein the angle of the side surface of the recess is 30 degrees or more and less than 90 degrees.   The intaglio according to claim 7, wherein the angle of the side surface of the recess is 30 degrees or more and 60 degrees or less.   The intaglio according to claim 1, wherein the plate is a roll.   The intaglio according to claim 1, wherein the plate is generally a flat plate. (A) forming a removable convex pattern on the surface of the intaglio substrate;
(B) including a step of forming a film made of diamond-like carbon or an inorganic material on the surface of the intaglio substrate on which a removable convex pattern is formed, and (C) a step of removing the convex pattern An intaglio manufacturing method characterized by the above.   12. The method for producing an intaglio according to claim 11, wherein the intaglio substrate has diamond-like carbon or an inorganic material on the surface thereof.   The method for producing an intaglio according to claim 11 or 12, wherein the removable convex pattern is formed by a photolithography method using a photosensitive resist.   The method for producing an intaglio according to any one of claims 11 to 13, wherein the film made of diamond-like carbon or an inorganic material is formed so that the property or characteristic is different between the intaglio substrate and the side surface of the convex pattern.   The width of the boundary surface between the film formed on the intaglio substrate and the film formed on the side surface of the removable convex pattern is not reduced in the standing direction of the convex pattern, The manufacturing method of the intaglio in any one of Claims 11-14 which is large as.   The method for producing an intaglio according to any one of claims 11 to 16, wherein the film formed on the intaglio substrate is diamond-like carbon.   The method for producing an intaglio according to claim 16, wherein the hardness of the diamond-like carbon film formed on the intaglio substrate is greater than the hardness of the diamond-like carbon film formed on the side surface of the convex pattern.   The intaglio plate according to claim 17, wherein the hardness of the diamond-like carbon film formed on the intaglio substrate is 10 to 40 GPa, and the hardness of the diamond-like carbon film formed on the side surface of the convex pattern is 1 to 15 GPa. Manufacturing method.   The method for producing an intaglio according to any one of claims 11 to 18, wherein the diamond-like carbon film is formed by a vacuum deposition method, a sputtering method, an ion plating method, an arc discharge method, an ionization deposition method or a plasma CVD method.   Before performing the step of forming a film on the surface of the intaglio substrate on which the removable convex pattern is formed, the intermediate layer is formed on the surface of the substrate on which the removable convex pattern is formed. The method for producing an intaglio according to any one of claims 10 to 19, wherein a step of forming a film is performed.   21. The method for producing an intaglio according to claim 20, wherein the intermediate layer contains at least one of Ti, Cr, W, Si, nitrides or carbides thereof.   Item 22. The method for producing an intaglio according to any one of Items 11 to 21, wherein the film made of diamond-like carbon or an inorganic material has a thickness of 0.1 to 100 μm.

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