WO2008059705A1

WO2008059705A1 - Photogravure engraving roll and method for manufacturing the same

Info

Publication number: WO2008059705A1
Application number: PCT/JP2007/070918
Authority: WO
Inventors: Tatsuo Shigeta; Manabu Inoue; Tsutomu Sato; Hideki Nakamori
Original assignee: Think Laboratory Co., Ltd.; Nanotec Corporation
Priority date: 2006-11-13
Filing date: 2007-10-26
Publication date: 2008-05-22
Also published as: JPWO2008059705A1

Abstract

This invention provides a novel photogravure engraving roll, which is provided with a surface reinforcing covering layer free from toxicity and having no possibility of the occurrence of pollution and, at the same time, has excellent printing durability, and a method for manufacturing the same. The photogravure engraving roll comprises a plate base material, a copper plating layer provided on the surface of the plate base material and having on its surface a number of gravure cells, an adhesion layer provided on the surface of the copper plating layer, and a diamond-like carbon film covering the surface of the adhesion layer. The adhesion layer and the diamond-like carbon film are formed by CVD.

Description

Specification

Gravure plate making roll and method for producing the same

Technical field

TECHNICAL FIELD [0001] The present invention relates to a gravure plate roll and a method for producing the same, which can be provided with a surface-enhanced coating layer having sufficient strength without using chromium plating, and in particular, surface enhancement replacing a chrome layer. The present invention relates to a gravure printing roll provided with a diamond-like carbon (DLC) coating as a coating layer and a method for producing the same.

Background art

In gravure printing, on a gravure printing roll (gravure cylinder), a fine concave portion (gravure cell) corresponding to the plate making information is formed to produce a plate surface, and ink is filled in the gravure cell to be printed. Transcript. In a general gravure plate roll, a copper plating layer (plate material) for forming a plate surface is provided on the surface of a plate base material such as aluminum or iron, and a large number of microscopic plates are etched according to the plate making information by etching. A concave portion (gravure cell) is formed, and then a hard chromium layer is formed by chrome plating to increase the press life of the gravure plate making roll to form a surface-enhanced coating layer, and plate making (plate surface production) is completed. . However, because the highly toxic hexavalent chromium is used in the chromium plating process, there is an extra cost to maintain the safety of the work, and there is also a problem of pollution, and the surface that replaces the chromium layer At present, the emergence of a reinforced coating layer is awaited.

[0003] On the other hand, for the production of gravure printing rolls (gravure cylinders), a technique is known in which a diamond-like carbon (DLC) film is formed on a copper plating layer on which cells are formed and used as a surface reinforcing coating layer. (Patent Document 1) The DLC film has a problem that it is easily peeled off due to weak adhesion to copper. In addition, one of the applicants of the present application has a technology for forming a gravure printing plate by forming a rubber or resin layer on a plate base material, forming a diamond-like carbon (DLC) film thereon, and then forming cells. Proposed already! /, Ru (Patent Documents 2 to 4). Patent Document 1: JP-A-4 282296

Patent Document 2: Japanese Patent Laid-Open No. 11 309950

Patent Document 3: Japanese Patent Laid-Open No. 11 327124 Patent Document 4: Japanese Patent Laid-Open No. 2000-15770

Disclosure of the invention

Problems to be solved by the invention

[0004] In view of the above-mentioned problems of the prior art, the present inventors have conducted intensive research on a surface-enhanced covering layer that replaces the chromium layer. As a result, the adhesion layer formed by the CVD method and the CVD method are used. In combination with a specific diamond-like carbon (DLC) coating, or a specific base metal plating layer, an adhesion layer formed by a CVD method, and a diamond-like carbon (DLC) coating formed by a CVD method In combination, the present inventors have found that a surface-enhanced coating layer having a strength comparable to that of a chromium layer and having no toxicity and no concern about the occurrence of pollution can be obtained.

[0005] An object of the present invention is to provide a novel gravure printing roll having a surface-enhanced coating layer that is non-toxic and has no fear of causing pollution, and is excellent in printing durability, and a method for producing the same.

Means for solving the problem

[0006] In order to solve the above-mentioned problems, a first aspect of the gravure printing roll of the present invention is a copper base plate provided on the surface of the base plate and a number of gravure cells formed on the surface of the base plate. A adhesion layer provided on the surface of the copper plating layer; and a diamond-like carbon film covering the surface of the adhesion layer. The adhesion layer and the diamond-like carbon film are formed by a CVD method. It is characterized by creating by.

[0007] A second aspect of the gravure plate roll of the present invention includes a plate base material, a copper plating layer provided on the surface of the plate base material and having a number of gravure cells formed on the surface, and the gravure A base metal plating layer provided on the surface of the copper plating layer on which the cell is formed, an adhesion layer provided on the surface of the foundation metal plating layer, and a diamond-like carbon coating covering the surface of the adhesion layer And the base metal plating layer is a metal plating layer selected from the group consisting of nickel (Ni), cobalt (Co), and iron (Fe) forces, and the adhesion layer and the diamond-like force. It is characterized in that a Bonn film is formed by a CVD method.

[0008] A first aspect of the method for producing a gravure plate roll of the present invention includes a step of preparing a plate base material, a copper plating step of forming a copper plating layer on the surface of the plate base material, and the copper Surface of plating layer A gravure cell forming step for forming a large number of gravure cells, an adhesion layer forming step for forming an adhesion layer on the surface of the copper plating layer, and a diamond-like carbon coating for forming a diamond-like carbon film on the surface of the adhesion layer Forming the adhesion layer and the diamond-like carbon film by a CVD method.

[0009] A second aspect of the method for producing a gravure plate roll of the present invention includes a step of preparing a plate base material, a copper plating step of forming a copper plating layer on the surface of the plate base material, and the copper A gravure cell forming step of forming a number of gravure cells on the surface of the plating layer; a base metal plating layer forming step of forming a base metal plating layer on the surface of the copper plating layer on which the gravure cell is formed; An adhesion layer forming step of forming an adhesion layer on the surface of the underlayer metal plating layer; and a diamond-like carbon film formation step of forming a diamond-like carbon film on the surface of the adhesion layer, Is a plating layer of a metal selected from the group consisting of nickel (Ni), cobalt (Co), and iron (Fe) forces, characterized in that the adhesion layer and the diamond-like carbon film are formed by a CVD method.

[0010] The adhesion layer is preferably formed of one or more selected from the group consisting of aluminum (A1), phosphorus (P), titanium (Ti), and silicon (Si).

[0011] The copper plating layer has a thickness of 50 to 200 μm, the gravure cell has a depth of 5 to 150 μm, the adhesion layer has a thickness of 0.1 to 1111, and the diamond-like carbon coating The thickness is preferably 0.;! To 10 mm. Further, the thickness of the base metal plating layer is preferably 0.;! To 5 〜m.

[0012] In order to form the adhesion layer, one or more selected from the group consisting of trimethylaluminum, titanium tetraisopropoxide, titanium tetraethoxide, tetramethylsilane, trimethyl phosphite, and hexamethyldisiloxane. It is preferable to use these gas species.

The gravure cell may be formed by an etching method or an electronic engraving method, but an etching method is preferable. Here, the etching method is a method in which a gravure cell is formed by applying a photosensitive liquid to the plate cylinder surface of the gravure cylinder and baking it directly, followed by etching. The electronic engraving method is a method of engraving a gravure cell on a copper surface of a Daravia cylinder by mechanically operating a diamond engraving needle by a digital signal. The invention's effect

[0014] According to the first aspect of the gravure plate roll of the present invention, the adhesive layer formed by the CVD method and the diamond-like carbon (DLC) film formed by the CVD method are used in combination. As a surface-enhanced coating layer, it is possible to form a diamond-like force-bonded (DLC) film with high adhesion, and therefore, the chrome plating process can be omitted. This eliminates the need for extra costs for work safety, eliminates the risk of pollution, and the diamond-like carbon (DLC) coating has strength comparable to that of the chromium layer and has excellent printing durability. This is a great effect.

[0015] According to the second aspect of the gravure plate roll of the present invention, the specific underlayer metal plating layer, the adhesion layer formed by the CVD method, and the diamond-like carbon (DLC) formed by the CVD method When used in combination with a coating, a diamond-like carbon (DLC) coating with high adhesion can be formed as a surface-enhanced coating layer, and therefore the chrome plating step can be omitted. This eliminates the need to use valence chromium, eliminates the need for extra costs for work safety, eliminates the risk of pollution, and the diamond-like carbon (DLC) coating has a strength comparable to that of the chromium layer. It has a great effect of having excellent printing durability.

Brief Description of Drawings

FIG. 1 is an explanatory view schematically showing a production process of a first embodiment of a gravure printing roll of the present invention, wherein (a) is an overall sectional view of the plate base material, and (b) is a view of the plate base material. Partial enlarged sectional view showing a state in which a copper plating layer is formed on the surface, (c) is a partial enlarged sectional view showing a state in which a gravure cell is formed in the copper plating layer of the plate base material, and (d) is a plate base material. (E) is a partially enlarged sectional view showing a state in which a diamond-like carbon (DLC) film is coated on the surface of the adhesive layer of the plate base material. It is.

FIG. 2 is a flowchart showing a production method of the first embodiment of the gravure plate making roll of the present invention.

FIG. 3 is an enlarged cross-sectional view of the main part of the first aspect of the gravure printing roll of the present invention.

FIG. 4 is an explanatory view schematically showing the production process of the second embodiment of the gravure plate making roll of the present invention. (A) is an overall cross-sectional view of the plate base material, (b) is a partially enlarged cross-sectional view showing a state in which a copper plating layer is formed on the surface of the plate base material, and (c) is a copper plating of the plate base material. (D) is a partially enlarged sectional view showing a state in which a base metal plating layer is formed on the surface of the copper plating layer of the plate base material, and (e) is a partial enlarged sectional view showing a state in which the gravure cell is formed in the layer. Partial enlarged cross-sectional view showing a state where an adhesion layer is formed on the surface of the base metal plating layer of the plate base material, (f) shows a state where the surface of the adhesion layer of the plate base material is coated with a diamond-like carbon (DLC) film It is a partial expanded sectional view.

FIG. 5 is a flowchart showing a production method of the second embodiment of the gravure printing roll of the present invention.

FIG. 6 is an enlarged cross-sectional view of the main part of the second aspect of the gravure printing roll of the present invention.

FIG. 7 is a schematic explanatory view showing a scratch testing machine.

Explanation of symbols

[0017] 10: Plate base material (hollow roll), 10a, 10b: Gravure plate roll, 12: Copper plating layer, 14:

Gravure cell, 15: base metal plating layer, 16: adhesion layer, 18: diamond-like carbon (DLC) coating.

BEST MODE FOR CARRYING OUT THE INVENTION

[0018] Embodiments of the present invention will be described below, but these embodiments are exemplarily shown, and it goes without saying that various modifications are possible without departing from the technical idea of the present invention. .

[0019] A first embodiment of the method of the present invention will be described with reference to Figs. In FIGS. 1 (a) and 3, reference numeral 10 denotes a plate base material, and a hollow roll made of aluminum, iron, carbon fiber reinforced resin (CFRP) or the like is used (step 100 in FIG. 2). A copper plating layer 12 is formed on the surface of the hollow roll 10 by copper plating (step 102 in FIG. 2).

[0020] A large number of minute recesses (gravure cells) 14 are formed on the surface of the copper plating layer 12 (see FIG.

Step 104 of 2). The gravure cell 14 can be formed by an etching method (a photosensitive liquid is applied to the plate cylinder surface and directly baked and then etched to form the gravure cell 14). A force etching method that can use a known method such as engraving the Daravia cell 14 on the copper surface by mechanically operating the copper plate is suitable. Next, the adhesion layer 16 is formed on the surface of the copper plating layer 12 (including the gravure cell 14) on which the gravure cell 14 is formed (step 106 in FIG. 2). As a method for forming the adhesion layer 16, a CVD method, preferably a plasma CVD method is applied.

[0022] The CVD method includes APCVD (Atmospheric Pressure Chemical Vapor Deposition), which is formed at normal pressure, LPCVD (Low Pressure Chemical Vapor Deposition), which is formed at a reduced pressure of 0.05 Torr, and 600 Torr, which is slightly lower than normal pressure. SACVD (Subatmospheric Pressure Chemical Vapor Deposition), ultra-high-vacuum chemical vapor deposition (UHVCVD), 600-1000. C high-temperature thermal CVD, plasma CVD (plasma-enhanced chemical vapor deposition) using 200 to 450 ° C using high-frequency plasma energy, photo-CVD using ultraviolet excitation, and organic metal as the source Power plasma CVD, which is known for MOCVD (Metal Organic Chemical Vapor Deposition) for compound crystal growth, is suitable.

[0023] The plasma CVD method is a method in which a source gas is decomposed using plasma excitation and reactively deposited on a substrate for the purpose of forming a thin film at a lower temperature when performing the CVD method under reduced pressure.

[0024] The adhesion layer 16 is preferably formed of one or more selected from the group consisting of aluminum (A1), phosphorus (P), titanium (Ti), and silicon (Si) force.

[0025] In order to form the adhesion layer 16, one or two selected from the group consisting of trimethylaluminum, titanium tetraisopropoxide, titanium tetraethoxide, tetramethylsilane, trimethyl phosphite, and hexamethyldisiloxane. It is preferable to use the above gas species.

[0026] Since the aluminum (A1), phosphorus (P), titanium (Ti), and silicon (Si) contained in the gas species used as the adhesion layer 16 are covalently bonded to the copper plating layer 12, the copper plating layer Adhesion is improved by a method in which a diamond-like carbon (DLC) film 18 is directly formed on 12. The bond between the diamond-like carbon (DLC) coating 18 and the adhesion layer 16 is good! / The reason is that the gas is a hydrocarbon gas, so the adhesion with the diamond-like carbon (DLC) coating 18 is high. . Further, since the gas is introduced into the chamber and formed by the plasma CVD method, there is an advantage that the adhesion layer 16 is uniformly formed on the entire surface. Subsequently, a diamond-like carbon (DLC) film 18 is formed on the surface of the adhesion layer 16 (step 108 in FIG. 2). As a method for forming the diamond-like carbon (DLC) film 18, a CVD method, preferably a plasma CVD method, is applied as in the formation of the adhesion layer 16.

[0028] The thickness of the copper plating layer 12 is 50 to 200 μm, and the depth of the gravure cell 14 is 5 to 150.

It is preferable that the thickness of the adhesion layer 16 is 0.1 to 1 m, and the thickness of the diamond-like carbon film 18 is 0.1;! to 10 mm.

[0029] By coating with the above-mentioned diamond-like carbon (DLC) coating 18 and making this diamond-like carbon (DLC) coating 18 act as a surface-enhanced coating layer, there is no toxicity and no concern about the occurrence of pollution. Capable of obtaining gravure plate roll 10a with excellent printing durability.

[0030] A second embodiment of the method of the present invention will be described with reference to Figs. 4 (a) and 6, reference numeral 10 denotes a plate base material, and a hollow roll made of aluminum, iron, carbon fiber reinforced resin (CFRP) or the like is used (step 200 in FIG. 5). A copper plating layer 12 is formed on the surface of the hollow roll 10 by a copper plating process (step 202 in FIG. 5).

[0031] A large number of minute recesses (gravure cells) 14 are formed on the surface of the copper plating layer 12 (see FIG.

Step 204 of 5). As a method for forming the gravure cell 14, the method described above in Step 104 can be used in the same manner.

Next, the base metal plating layer 15 is formed on the surface of the copper plating layer 12 (including the gravure cell 14) on which the gravure cell 14 is formed (step 206 in FIG. 5). The underlying metal plating layer 15 is a metal plating layer selected from the group consisting of nickel (Ni), cobalt (Co), and iron (Fe) forces. The thickness of the base metal plating layer 15 is preferably 0.1 to 5111.

Further, the adhesion layer 16 is formed on the surface of the base metal plating layer 15 (step 208 in FIG. 5). As a method for forming the adhesion layer 16, the method S described above in Step 106 can be applied in the same manner.

Subsequently, a diamond-like carbon (DLC) film 18 is formed on the surface of the adhesion layer 16 (step 210 in FIG. 5). As a method for forming the diamond-like carbon (DLC) film 18, the method described above in Step 108 can be similarly used. [0035] The surface of the adhesion layer 16 is covered with the diamond-like carbon (DLC) coating 18 described above, and this diamond-like carbon (DLC) coating 18 acts as a surface-enhanced coating layer, thereby causing no toxicity and causing pollution. The gravure printing roll 10b with excellent printing durability can be obtained.

Example

[0036] The ability of the present invention to be described more specifically with reference to the following examples. Needless to say, these examples are given by way of illustration and should not be construed as limiting.

[0037] (Example;! To 3)

A gravure cylinder (aluminum hollow roll) with a circumference of 600mm and a surface length of 1100mm is installed in the measuring tank, and the anode chamber is brought close to the air roll up to 20mm by an automatic slide device using a computer system, overflowing the measuring liquid, A copper plating layer of 80 μm was formed at 18 A / dm ² , 6.0 V by immersing it all. The plating time was 20 minutes, and there was no pit formation on the plating surface, and a uniform copper plating layer was obtained.

[0038] The copper plating layer formed above is coated with a photosensitive film, and the image is laser-exposed, developed, and burned to form a resist image, followed by dry etching, such as plasma etching, with a gravure cell. A printing plate was formed by engraving an image consisting of and then removing the resist image. At this time, three hollow rolls having a gravure cell depth of 10 m (Example 1), 18 111 (Example 2), and 30 m (Example 3) were produced.

[0039] An aluminum (A1) layer having a thickness of 0.1 m was formed by plasma CVD using trimethylaluminum as a gas species on the upper surface of the copper plating layer on which the gravure cell was formed.

Next, a diamond like carbon (DLC) film having a thickness of ππι was formed on the upper surface of aluminum (A1) by plasma CVD. In this way, a gravure printing roll (gravure cylinder) was completed.

[0041] Using the above three gravure cylinders, water-based ink for the gravure cylinder of Example 1 (gravure cell depth: 10 mm), Example 2 (depth of gravure cell: 18 mm) For example, an oil-based ink was used, and for Example 3 (gravure cell depth: 30 mm), a silver paste ink was applied, and an OPP film (Oriented Polypropylene Film) was used for a printing test. (Printing speed: 200m / min, OPP film Length: 4000m). All of the obtained printed materials had good transferability that the plate capri had. As a result, it was confirmed that the diamond-like carbon (DLC) film has performance comparable to that of the conventional chromium layer and can be used as a substitute for the chromium layer.

[0042] (Examples 4 to 6)

In the same manner as in Examples 1 to 3, three hollow rolls having a gravure cell depth of 10 m (Example 4), 18 m (Example 5), and 30 m (Example 6) were produced. The above three hollow rolls were treated in the same manner as in Examples 1 to 3, except that titanium tetraisopropoxide was used as the gas species and a 0.1 am thick titanium (Ti) layer was formed by plasma CVD. When a gravure platemaking roll was completed and a printing test was conducted in the same manner, it was possible to obtain a printed material having the same transferability as the plate capri. Also in these examples, it was confirmed that the diamond-like carbon (DLC) coating had a performance comparable to that of the conventional chromium layer and could be sufficiently used as a substitute for the chromium layer.

[0043] Titanium tetraethoxide, tetramethylsilane, trimethylol phosphite, and hexamethyldisiloxane were used as gas species, and a titanium (Ti) layer having a thickness of 0 · I nm by a plasma CVD method, A silicon (Si) layer, a phosphorus (P) layer, and a silicon (Si) layer were formed, and the same experiment was conducted to confirm that the same result was obtained.

[0044] (Example 7)

A gravure cylinder (aluminum hollow roll) with a circumference of 600mm and a surface length of 1100mm is installed in the mating tank, and the anode chamber is brought close to the air roll up to 20mm by an automatic slide device using a computer system. Was completely submerged to form an 80 m copper plating layer at 18 A / dm ² , 6.0 V. The plating time was 20 minutes, and a uniform copper plating layer with no pits on the plating surface was obtained.

[0045] The above-described copper plating layer is coated with a photosensitive film, and the image is laser-exposed, developed, and burned to form a resist image, followed by dry etching such as plasma etching at! /, And gravure. A printing plate was formed by engraving the cell image and then removing the resist image. At this time, a hollow roll with a gravure cell depth of 10 m was produced.

[0046] Cobalt plating is performed on the hollow roll by the cobalt plating tank under the following conditions. To form a cobalt plating layer having a thickness of 1 μm.

Cobalt plating solution composition (solvent: water)

Cobalt sulfate 250g / L

Cobalt chloride 40g / L

Boric acid 30g / L

pH 4.5

Liquid temperature 50 ° C

Current density 2A / dm ²

Plating time 3 minutes

[0047] A silicon (Si) layer having a thickness of 0.1 m was formed on the upper surface of the cobalt plating layer by plasma CVD using hexamethyldisiloxane as a gas species.

[0048] Next, a diamond-like carbon (DLC) film having a thickness of 2 m was formed on the upper surface of the silicon (Si) layer by plasma CVD. In this way, a gravure printing roll (gravure cylinder) was completed. The Vickers hardness of the diamond-like carbon (DLC) coating on this gravure cylinder was measured and found to be 1280, indicating that it had sufficient hardness. Further, when the scratch test was conducted, the scratch test value was 8.34 N, and it was found that the adhesion was further improved as compared with Example 8.

[0049] The scratch test will be described with reference to FIG. FIG. 7 is a schematic explanatory diagram showing a scratch testing machine. In FIG. 7, a substrate 52 having a thin film 50 formed thereon is placed on a table (not shown), a diamond indenter 54 is brought into close contact with the substrate 52, and a load 56 is gradually applied. Is moved at a constant speed and the adhesion is measured. At this time, the AE (acoustic emission) sensor 58 detects ultrasonic noise as a result of peeling or cracking of the thin film 50 formed on the substrate 52, and at the same time detects the friction force. S can. From the observation of scratch mark 60 with an optical microscope, the sudden rise in the waveform of friction force and the sudden change in the waveform of AE, each point and critical peeling load are read and the mechanical strength and adhesion are considered. In particular, the critical peeling load is often compared industrially as the adhesion of thin films. In addition, attention must be paid to the radius of curvature of the indenter tip used for the film thickness. In FIG. 7, 62 is a depth sensor and 64 is a friction force sensor. . ISO20502: 2005 (E) shows an example of a scratch peeling mode. A commonly used indenter 54 is a 200 m diamond indenter. In the figure, PD is a depth sensor and FT is a friction force sensor.

[0050] Using the gravure cylinder described above, applying water-based ink and printing test using OPP film (Oriented Polypropylene Film) (printing speed: 200 m / min, length of OPP film) : 4000m). All of the obtained printed materials had good transferability that the plate capri had. As a result, we confirmed that the diamond-like carbon (DLC) coating has performance comparable to that of the conventional chromium layer and can be used as a substitute for the chromium layer.

[0051] (Example 8)

A gravure platemaking roll was completed in the same manner as in Example 7 except that the hollow roll was not subjected to cobalt plating. The Vickers hardness of the diamond-like carbon (DLC) coating on this gravure cylinder was measured and found to be 1280. When the scratch test was conducted, the scratch test value was 7.05N.

[Example 9]

The same treatment as in Example 7 was performed except that tetramethylsilane was used as the gas species for the hollow roll instead of hexamethyldisiloxane and a 0.1 m thick silicon (Si) layer was formed by plasma CVD. The gravure platemaking roll was completed. The Vickers hardness of the diamond-like carbon (DLC) coating on this gravure cylinder was measured and found to be 1380, indicating that it had sufficient hardness. Further, when the scratch test was conducted, the scratch test value was 10.58 N, and it was found that the adhesion was further improved as compared with Example 10. When a printing test was conducted in the same manner using this gravure cylinder, a printed matter having a good transferability as well as the plate capri was obtained. In these examples, it was confirmed that V, even diamond-like carbon (DLC) coating, had a performance comparable to that of the conventional chromium layer and could be used as a substitute for the chromium layer.

[Example 10]

A gravure printing roll was completed in the same manner as in Example 9 except that the hollow roll was not subjected to cobalt plating. This gravure cylinder diamond-like carbon The Vickers hardness of the coating (DLC) film was 1380. When the scratch test was conducted, the scratch test value was 9.21N.

[Example 11]

A gravure printing roll was completed by treating in the same manner as in Example 7 except that a nickel plating layer having a thickness of 1 _μm was formed on the hollow roll instead of cobalt plating under the following conditions.

Nikkenore Meat Solution Composition (Solvent: Water)

Nickenole sulfate 250g / L

Nickel chloride 40g / L

Boric acid 30g / L

pH 4.5

Liquid temperature 50 ° C

Current density 2A / dm ²

Plating time 3 minutes

[0055] The Vickers hardness of the diamond-like carbon (DLC) film of this gravure cylinder was measured and found to be 1280, which was sufficient. Further, when the scratch test was conducted, the scratch test value was 7.19 N, and it was found that the adhesion was further improved as compared with Example 8. When a printing test was conducted in the same manner using this gravure cylinder, it was possible to obtain a printed material having the same transferability as the plate capri. Also in these examples, it was confirmed that the diamond-like carbon (DLC) coating had a performance comparable to that of the conventional chromium layer and could be sufficiently used as a substitute for the chromium layer.

[Example 12]

A gravure printing roll was completed in the same manner as in Example 9 except that a nickel plating layer having a thickness of 1 _μm was formed on the hollow roll instead of cobalt plating. The Vickers hardness of this gravure cylinder diamond-like carbon (DLC) film was measured and found to be 1380, which was sufficient. Further, when the scratch test was conducted, the scratch test value was 10.27 N, and it was found that the adhesion was further improved as compared with Example 10. When a printing test was conducted in the same manner using this gravure cylinder, a printed matter having good transferability as well as the plate capri was obtained. These fruits Also in the examples, it was confirmed that the diamond-like carbon (DLC) coating had performance comparable to that of the conventional chromium layer and could be used as a substitute for the chromium layer.

In addition, titanium tetraethoxide, titanium tetraisopropoxide, trimethyl phosphite, and trimethylaluminum are used as the gas species, and a titanium (1) layer and a phosphorus (P) layer having a thickness of 0.1 111 by plasma CVD, respectively. Then, an aluminum (A1) layer was formed and the same experiment was conducted, and it was confirmed that the same result was obtained.

Claims

The scope of the claims

[1] A plate base material, a copper plating layer provided on the surface of the plate base material and having a number of gravure cells formed on the surface, an adhesion layer provided on the surface of the copper plating layer, and the adhesion A gravure plate making roll, comprising: a diamond-like carbon film covering a surface of the layer, and forming the adhesion layer and the diamond-like carbon film by a CVD method.

[2] A plate base material, a copper plating layer provided on the surface of the plate base material and having a number of gravure cells formed on the surface, and a copper plating layer provided with the gravure cell. An underlayer metal plating layer, an adhesion layer provided on the surface of the underlayer metal plating layer, and a diamond-like carbon film covering the surface of the adhesion layer. A gravure plate making roll characterized by being a metal plating layer selected from the group consisting of (Ni), cobalt (Co), and iron (Fe) forces, wherein the adhesion layer and the diamond-like carbon film are formed by a CVD method.

[3] The copper plating layer has a thickness of 50 to 200 μm, the gravure cell has a depth of 5 to 150 μm, the adhesion layer has a thickness of 0.1 to 1111, and the diamond-like carbon coating The gravure printing roll according to claim 1, wherein the thickness of the gravure is 0 .;

[4] The thickness of the copper plating layer is 50 to 200 μm, the depth of the gravure cell is 5 to 150 μm, the thickness of the base metal plating layer is 0.1 to 5 111, and the adhesion layer The gravure plate-making roll according to claim 2, wherein the thickness of the film is 0.1 l-l ^ m, and the thickness of the diamond-like carbon coating is 0 ·! -10 m.

[5] The adhesion layer is composed of one or more selected from the group force consisting of aluminum (A1), phosphorus (P), titanium (Ti), and silicon (Si). The gravure plate-making roll of any one of 1-4.

[6] To form the adhesion layer, one or more selected from the group consisting of trimethylaluminum, titanium tetraisopropoxide, titanium tetraethoxide, tetramethylsilane, trimethyl phosphite, and hexamethyldisiloxane. The gravure printing roll according to any one of claims 1 to 5, wherein the gas type is used.

[7] A step of preparing a plate base material, a copper plating step of forming a copper plating layer on the surface of the plate base material, and a gravure cell formation step of forming a number of gravure cells on the surface of the copper plating layer When, An adhesion layer forming step for forming an adhesion layer on the surface of the copper plating layer; and a diamond-like carbon film formation step for forming a diamond-like carbon film on the surface of the adhesion layer. A method for producing a gravure plate making roll, characterized in that a carbon film is formed by a CVD method.

[8] A step of preparing a plate base material, a copper plating step of forming a copper plating layer on the surface of the plate base material, and a gravure cell formation step of forming a number of gravure cells on the surface of the copper plating layer Forming a base metal plating layer on the surface of the copper plating layer on which the gravure cell is formed; and forming an adhesion layer on the surface of the base metal plating layer. And a diamond-like carbon film forming step for forming a diamond-like carbon film on the surface of the adhesion layer, wherein the base metal plating layer has a nickel (Ni), cobalt (Co), and iron (Fe) force. A method for producing a gravure printing roll, which is a plating layer of a metal selected from the group consisting of forming the adhesion layer and the diamond-like carbon film by a CVD method.

[9] The adhesive layer is composed of one or more selected from the group force consisting of aluminum (A1), phosphorus (P), titanium (Ti), and silicon (Si). A method for producing a Daravia plate roll according to 7 or 8.

[10] To form the adhesion layer, one or more selected from the group consisting of trimethylaluminum, titanium tetraisopropoxide, titanium tetraethoxide, tetramethylsilane, trimethyl phosphite, and hexamethyldisiloxane. The method of producing a gravure plate-making roll according to any one of claims 7 to 9, wherein the gas type is used.