WO2008038716A1

WO2008038716A1 - Laminated flexible packaging material and method for manufacturing the same

Info

Publication number: WO2008038716A1
Application number: PCT/JP2007/068815
Authority: WO
Inventors: Shinichiro Sugiyama; Tatsuo Shigeta
Original assignee: Fuji Tokushu Shigyo Co., Ltd.; Think Laboratory Co., Ltd.
Priority date: 2006-09-29
Filing date: 2007-09-27
Publication date: 2008-04-03
Also published as: JPWO2008038716A1

Abstract

This invention provides a laminated flexible packaging material which has been gravure printed using an aqueous color ink, wherein the amount of a white ink used is limited, and, further, a VOC-containing anchor coating agent is not used to reduce the occurrence of VOC and to impart a high level of covering properties and, particularly in gravure printing, a gravure cylinder provided with a diamond-like carbon (DLC) layer as a surface strengthening covering layer instead of a chromium layer is used. There is also provided a method for manufacturing the same. The flexible packaging material comprises a base material film, an aqueous gravure color ink layer, an anchor coating agent layer, a white pigment-containing resin layer, and a sealant layer stacked in that order. The aqueous gravure color ink layer is formed by gravure printing using a gravure cylinder provided with a diamond-like carbon film.

Description

Specification

Laminated soft packaging material and method for producing the same

Technical field

[0001] The present invention is a laminated flexible packaging that has been subjected to gravure printing in consideration of environmental and health problems by reducing the amount of volatile organic compound (hereinafter referred to as "VOC") usage by up to about 92%. In particular, the present invention relates to a material and a method for producing the laminated soft packaging material, and uses a gravure cylinder provided with a diamond-like carbon (DLC) layer as a surface-enhanced coating layer replacing a chromium layer in gravure printing.

Background art

As shown in FIG. 10, a conventional soft packaging material subjected to gravure printing has an oil-based gravure color ink layer 12 formed on a base film 11 and an oil-based gravure white ink layer 13 formed on this surface. In general, an oil-based anchor coating agent layer 14 is formed on this surface, a melt-extruded laminating layer 15 is formed on this surface, and a heat-sealable thermoplastic resin film layer 16 is formed on this surface. is there. In the case of gravure inks used for printing, organic solvents are used for the adjustment, and environmental and health problems based on evaporation and diffusion of these organic solvents into the atmosphere have been pointed out!

[0003] Therefore, one of the applicants of the present application has proposed a gravure printing method using a water-based gravure ink that does not use an organic solvent (Patent Document 1). In addition, in the manufacturing method of soft packaging materials made of plastic film that has been subjected to gravure printing, the use of an anchor coating agent containing VOC is stopped, and a laminating method in which polarizing resin is used as a laminate material. This is also proposed (Patent Document 2).

[0004] In addition, in the case of soft packaging materials, there are those that have been imparted with the performance of concealing the contents, and as this concealment method, in addition to so-called solid printing using printing ink, lamination of aluminum foil or There are methods for laminating aluminum-deposited aluminum films. However, if concealment is imparted using these methods, there is a disadvantage that the product cost increases in addition to the VOC problem.

[0005] In more detail, the VOC problem will be explained. It is common to improve the design of packaging materials by gravure printing with ink. At this time, printing with only color inks is limited in printing expression, so white press printing is generally applied to the entire surface. For this reason, the amount of white ink used normally accounts for more than 60% of the total ink usage including color ink, and when oil-based ink is used, a large amount of VOC is generated. The composition of oil-based inks in use is usually 20% for pigments and resins, and 80% for solvents (ethyl acetate, MEK, IPA, etc.). In other words, about 80% of the ink used is VOC and is evaporated and emitted into the air.

[0006] In order to reduce this released VOC, the oil-based ink using an organic solvent can be changed to a water-based ink, which can be greatly reduced. However, even with water-based inks, 100% water-based printing has not been achieved at present due to technical problems, and almost 20% alcohol-based solvents are used.

[0007] On the other hand, in gravure printing, a gravure cylinder (gravure plate making roll) is formed with a minute recess (gravure cell) corresponding to the plate making information to produce a plate surface, and the gravure cell is filled with ink and covered. It is transferred to printed matter. In general gravure plate-making rolls, a copper plating layer (plate material) for forming a plate surface is provided on the surface of a metal hollow roll such as aluminum or iron, and a large number of plate-forming rolls are etched to form a large number of plates according to the plate-making information. Forming a small concave part (gravure cell) and forming a hard chrome layer by chrome plating to increase the press life of the gravure printing roll in the next! Is completed. The chrome plating process uses highly toxic hexavalent chromium, which incurs extra costs to maintain work safety, and there are also problems of pollution. At present, the emergence of a reinforced coating layer is awaited.

[0008] On the other hand, regarding the manufacture of gravure cylinders, a technique is known in which diamond-like carbon (DLC) is formed on a copper plating layer in which cells are formed and used as a surface reinforcing coating layer. Patent Document 3), DLC layer Had a problem that the adhesiveness with copper was weak and easy to peel off. In addition, the other of the applicants of the present application forms a rubber or resin layer on a metal hollow roll, forms a diamond-like carbon (DLC) film thereon, forms cells, and produces a gravure printing plate. We have already proposed the technology to do! /, Ru (Patent Documents 4 to 6).

Patent Document 1: Japanese Patent Laid-Open No. 2002-178622 Patent Document 2: JP 2002-326335 A

Patent Document 3: Japanese Patent Laid-Open No. 4 282296

Patent Document 4: JP-A-11 309950

Patent Document 5: Japanese Patent Laid-Open No. 11 327124

Patent Document 6: Japanese Unexamined Patent Publication No. 2000-15770

Non-patent document 1: “New edition dye manual” (edited by the Society of Synthetic Organic Chemistry, Maruzen Co., Ltd., issued on July 20, 1945)

Disclosure of the invention

Problems to be solved by the invention

[0009] The present invention is intended to solve the above-described problems of the prior art, and is gravure printing using water-based color ink, further restricting the amount of white ink used, and reducing the amount of VOC contained. The use of an anchor coating agent can be stopped to reduce the generation of VOCs and provide high concealing properties.In particular, a gravure cylinder with a diamond-like carbon (DLC) layer is provided as a surface-enhanced coating layer that replaces the chromium layer during gravure printing. It is an object to provide a gravure-printed laminated soft packaging material and a method for producing the same.

Means for solving the problem

[0010] In order to achieve the above object, the first aspect of the flexible packaging material of the present invention includes a base film, a water gravure color ink layer, an anchor coating agent layer, a white pigment-containing resin layer, and a sealant layer sequentially laminated. A soft wrapping material, wherein the water-based gravure color ink layer is formed by forming a hollow roll, a copper plating layer provided on the surface of the hollow roll and having a plurality of gravure cells formed on the surface, and the copper It is characterized in that it is carried out by gravure printing using a gravure cylinder including a diamond-like carbon film covering the surface of the plating layer.

[0011] A second aspect of the flexible packaging material of the present invention is a flexible packaging material in which a base film, an aqueous gravure color ink layer, an anchor coating agent layer, and a white pigment-containing resin layer are sequentially laminated. A gravure color ink layer is formed by forming a hollow roll, a copper plating layer provided on the surface of the hollow roll and having a number of gravure cells formed on the surface, and a diamond-like carbon coating covering the surface of the copper plating layer. Gravure mark using a gravure cylinder containing It is characterized by being performed by printing.

[0012] A third aspect of the soft packaging material of the present invention is a soft packaging material in which a base film, a water-based gravure color ink layer, a white pigment-containing resin layer, and a sealant layer are sequentially laminated, and the white pigment The white pigment-containing resin of the containing resin layer is an adhesive polarity imparting resin, and the formation of the aqueous gravure color ink layer is performed on the surface of the hollow roll and the hollow roll, and a number of gravure cells are formed on the surface. The present invention is characterized in that it is performed by gravure printing using a gravure cylinder including the copper plating layer thus formed and a diamond-like carbon coating film covering the surface of the copper plating layer.

[0013] In the first and second embodiments of the flexible packaging material of the present invention, it is preferable that the anchor coating agent is water-based.

[0014] In the first to third embodiments of the flexible packaging material of the present invention, it is preferable that white pressing is performed with a water-based gravure color ink while limiting an area necessary for ensuring a printing state during a printing operation. Good.

[0015] In the first to third embodiments of the soft packaging material of the present invention, the white pigment of the white pigment-containing resin layer is titanium oxide, and the content of titanium oxide in the white pigment-containing resin layer is 2 to 50 wt. % Is preferred.

[0016] In the first aspect of the method for producing a gravure-printed laminated flexible packaging material of the present invention, a water-based gravure color ink layer and an anchor coating agent layer are formed on a base film, and a heat-sealable thermoplastic resin film is formed thereon. Is a method for producing a gravure-printed laminated soft packaging material in which a molten white pigment-containing resin is extruded in a layered manner between the substrate side and the base material side and the heat-sealable thermoplastic resin film side. Ink layer formation includes a hollow roll, a copper plating layer provided on the surface of the hollow roll and having a number of gravure cells formed thereon, and a diamond-like carbon coating covering the surface of the copper plating layer It is characterized by being performed by gravure printing using a gravure cylinder.

[0017] In a second aspect of the method for producing a gravure-printed laminated flexible packaging material of the present invention, a water-based gravure color ink layer is formed on a base film, and a heat-sealable thermoplastic resin film is opposed to the film, The molten white pigment-containing resin is extruded in layers to heat the substrate and heat A method for producing a gravure-printed laminated flexible packaging material for pressure-bonding to a thermoplastic resin film side, wherein the white pigment-containing resin of the white pigment-containing resin layer is an adhesive polarity-imparting resin, and the water-based gravure color Ink layer formation includes a hollow roll, a copper plating layer provided on the surface of the hollow roll and having a number of gravure cells formed on the surface, and a diamond-like carbon coating covering the surface of the copper plating layer It is characterized by performing gravure printing using a gravure cylinder.

In the present invention, a metal layer is provided on the surface of the copper plating layer, a metal carbide layer of the metal is provided on the surface of the metal layer, and a diamond-like carbon film is formed on the surface of the metal carbide layer. preferable.

[0019] In the present invention, the metal carbide layer is a metal carbide inclined layer, and the carbon composition ratio in the metal carbide inclined layer is such that the carbon ratio from the metal layer side to the diamond-like carbon coating direction. A configuration that is set to gradually increase is preferable.

[0020] In the present invention, the thickness of the copper plating layer is 50 to 200 µm, the depth force of the gravure cell is 5 to 1; and the thickness force of the metal layer is 0.001 to 1111, preferably Is 0.001—0.1 〃m, more preferably 0.001—0. Ο δ μ ΐΐΐ ^ the carbon-metal layer thickness force is 0. l—l ^ m, and the diamond-like carbon coating The thickness is preferably 0.;! To 10 m.

[0021] The metal is preferably a metal that can be carbonized and has a high affinity for copper. The metal may be one or more metals selected from the group consisting of tungsten (W), silicon (Si), titanium (Ti), chromium (Cr), tantalum (Ta), and zirconium (Zr) force. Is preferably used.

[0022] It is preferable that the metal layer, the metal carbide layer, preferably the metal carbide inclined layer, and the diamond-like carbon film are respectively formed by a sputtering method.

In the present invention, a CVD method can also be applied to form a diamond-like carbon film. In this case, it is preferable to form an adhesion layer on the surface of the copper plating layer, and to form a diamond-like carbon film that covers the surface of the adhesion layer. Is formed. [0024] 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).

[0025] In this case, the copper plating layer has a thickness of 50 to 200 μm, and the gravure cell has a depth of 5 to

It is preferable that the thickness of the adhesive layer is 150 m, the thickness of the adhesion layer is 0.! To 1 μm, and the thickness of the diamond-like carbon film is 0.

[0026] In order to form the adhesion layer, one or more gas species selected from trimethylaluminum, titanium tetraisopropoxide, titanium tetraethoxide, tetramethylsilane, trimethyl phosphite, and hexamethyldisiloxane. Is preferably used.

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 of forming a gravure cell by applying a photosensitive solution to the copper plating layer of the gravure cylinder and baking it directly. The electronic engraving method is a method of engraving a gravure cell on the surface of a copper plating layer of a gravure cylinder by mechanically operating a diamond engraving needle by a digital signal.

The invention's effect

[0028] According to the present invention, the following effects are achieved.

1. In soft packaging materials, by laminating with a white pigment-containing resin, the white ink is not pressed, or the area and coating amount required to confirm the printing state during the printing operation are limited. By using white press, the use of white press ink is eliminated or becomes weak when using water-based color ink, so it is possible to reduce this VOC. This makes it possible to prevent global warming by reducing environmental issues, health issues, resource saving, energy saving, and carbon dioxide generation.

2. VOC can be further reduced by using water-based ink as gravure ink.

3. By using the white pigment-containing adhesive polarity-imparting resin as the laminate resin, the use of an anchor coating agent can be eliminated, thus further reducing VOC.

4. In the case of food packaging materials, use water-based color ink, and do not perform white pressing that accounts for 60% or more of the total ink usage, or limit the area required to check the printing work status To reduce the amount of ink used and use organic solvents. Therefore, a safer packaging material with less residual solvent in the packaging material can be provided.

5. Since white ink is used only for the area required for checking the printing state during printing operations without white pressing, the ink drying property is greatly improved and the printing speed is increased. Is possible.

6. Since white ink is used only for the area required for checking the printing state during printing operations without white pressing, the amount of ink used can be reduced and it is economical.

7. Compared with white ink, white pigment-containing resin containing titanium oxide pigment has better dispersibility of the pigment in the resin, and the white pigment after lamination is smooth and smooth, improving the printing expression effect.

8. By using a diamond-like carbon (DLC) coating as a surface-enhanced coating layer, the chrome plating process can be omitted, so that highly toxic hexavalent chromium is not used and the work safety is improved. No extra cost is required, there is no concern about pollution, and the diamond-like carbon (DLC) coating has strength comparable to that of the chromium layer and has excellent printing durability.

Brief Description of Drawings

FIG. 1 is a cross-sectional explanatory view showing a first example of the flexible packaging material of the present invention.

FIG. 2 is a cross-sectional explanatory view showing a second example of the flexible packaging material of the present invention.

FIG. 3 is an explanatory sectional view showing a third example of the flexible packaging material of the present invention.

FIG. 4 is an explanatory view schematically showing an example of the production process of a gravure cylinder used in the present invention, where (a) is an overall cross-sectional view of the hollow roll, and (b) is a copper plating layer on the surface of the hollow roll. (C) is a partially enlarged cross-sectional view showing a state in which a gravure cell is formed on a copper plating layer of a hollow roll, and (d) is a carbonized tungsten carbide on the surface of the copper plating layer of the hollow roll. (E) is a partially enlarged cross-sectional view showing a state in which a metal carbide layer is formed on the surface of the metal layer of the hollow roll, and (f) is a surface of the metal carbide layer in the hollow roll. FIG. 3 is a partially enlarged cross-sectional view showing a state in which a diamond-like carbon (DLC) film is coated.

[FIG. 5] A flow chart showing an example of a method for producing a gravure cylinder used in the present invention is shown. FIG. 6 is an enlarged cross-sectional view of a main part of an example of a gravure cylinder used in the present invention.

FIG. 7 is an explanatory view schematically showing another example of the production process of the gravure cylinder used in the present invention, in which (a) is an overall sectional view of the hollow roll, and (b) is a copper plating on the surface of the hollow roll. (C) is a partially enlarged cross-sectional view showing a state in which a gravure cell is formed on a copper plating layer of a hollow roll, and (d) is a close contact with the copper plating layer surface of the hollow roll. FIG. 4E is a partially enlarged sectional view showing a state in which a layer is formed, and FIG. 5E is a partially enlarged sectional view showing a state in which a diamond-like carbon (DLC) coating is coated on the surface of the adhesion layer of the hollow roll.

FIG. 8 is a flow chart showing another example of a method for producing a gravure cylinder used in the present invention.

FIG. 9 is an enlarged cross-sectional view of the main part of another example of a gravure cylinder used in the present invention.

FIG. 10 is an explanatory view showing a laminated structure of a conventional soft packaging material using oil-based gravure color ink.

[0030] 11: Base film, 12: Oil-based gravure color ink layer, 13: Oil-based gravure white ink layer, 14: Oil-based anchor coating layer, 15: Melt extrusion laminate layer, 16: Sealant layer, Heat-sealable thermoplastic Resin film layer, 17: aqueous gravure color ink layer, 18: aqueous gravure white ink layer, 19: anchor coating agent layer, 20: white pigment containing resin layer, white pigment containing extruded laminate resin layer, 21: white pigment containing resin Layer, white pigment-containing adhesive polarity-imparting resin layer, 30: plate base material (hollow roll), 30a: gravure plate roll, 32: copper plating layer, 34: gravure senore, 36: metal layer, 37: adhesion layer, 38: Metal carbide layer, preferably metal carbide gradient layer, 40: Diamond-like carbon (DLC) coating.

BEST MODE FOR CARRYING OUT THE INVENTION

[0031] The present inventor performs gravure printing using water-based color ink instead of oil-based ink in order to reduce alcohol solvent, and does not print white ink in order to reduce the amount of white ink used. Alternatively, use only white pigment-containing resin instead of the minimum use (reduction of area and coating amount concentration) necessary for checking the printing status during the printing operation. As a result, we have found that it is possible to achieve securing and VOC reduction, and as a result, it is possible to maintain high concealment. That is, the present inventor can achieve VOC reduction and high concealability by sequentially laminating a base film, a water-based gravure color ink layer, an anchor coating agent layer, a white pigment-containing resin layer, and a sealant layer. I found. By using an aqueous anchor coating agent as the anchor coating agent, VOC reduction can be further achieved.

Regarding the relationship between the pigment size and the hiding power, the hiding power increases as the particles become smaller, and the limit value determined by the color, i.e., titanium white, reaches a maximum value of 0.7 to 0.4 111-. It is known that when it becomes smaller, light scattering occurs, and when it is less than half the wavelength of light, it becomes abruptly transparent (Non-Patent Document 1).

[0033] The composition of the water-based ink in use is usually 27% as pigment and resin, 53% water, and 20% by weight alcohol. In other words, in the case of water-based ink, 20% of the ink used is VOC, which is a low percentage compared to oil-based ink.

In addition, water-based inks are shallower than oil-based inks due to their characteristics, and the coating amount is about 60% compared with oil-based inks. As described above, water-based ink has a low VOC solvent ratio and its coating amount is small, so the amount of VOC generated can be reduced by 85% compared to oil-based ink. In addition, according to the present invention, if water-based ink is used and white ink is not printed, the amount of VOC generated can be reduced by 90% compared to water-based ink.

[0034] Furthermore, the present inventors have found that VOC can be further reduced by using an adhesive polarity imparting resin that does not require the application of an anchor coating agent when laminating a flexible packaging material. That is, the present inventor omits the anchor coating agent and uses the white pigment-containing adhesive polarity-imparting resin as the white pigment-containing resin, and uses the base film, the aqueous gravure color ink layer, the white pigment-containing resin layer, and the sealant. It was found that further VOC reduction can be achieved by laminating layers one after another.

[0035] The coating amount of the oil-based anchor coating agent as an adhesive for laminating is about 3 kg / 500 mm ² , and the composition is such that the solid content is 8% as a resin component and ethyl acetate is 92% as a solvent. It is normal. By using a water-based anchor coating agent and the ability to replace the oil-based anchor coating agent with an adhesive polarity imparting resin, it is possible to reduce VOC by 88% when using water-based ink. Further, according to the present invention, a white pigment-containing adhesive polarity-imparting resin is used without using a water-based color ink and printing a white ink, and further using a water-based anchor coating agent, or without using an anchor coating agent. By using it, it is possible to reduce VOC by 93% compared to oil-based color inks and oil-based anchor coating agents.

[0036] Then, the present inventor opposes a heat-sealable thermoplastic resin film serving as a sealant layer to a base film subjected to gravure printing using a water-based gravure color ink and an anchor coating agent, While extruding the molten white pigment-containing resin in layers, the base film side and the heat-sealable thermoplastic resin film mold are pressed with the white pigment-containing resin sandwiched between them, thereby reducing the VOC. I came up with a manufacturing method.

[0037] Further, the present inventor makes a base film on which gravure printing using a water-based gravure color ink is applied and a heat-sealable thermoplastic resin film as a sealant layer facing each other, and the water-based gravure color ink is interposed therebetween. VOC was reduced by pressing the base film side and the heat-sealable thermoplastic resin film side while extruding the white pigment-containing resin polarized so that it can be bonded without an anchor coating agent in layers. We have come up with a method for manufacturing flexible packaging materials.

[0038] Furthermore, the present inventor uses a diamond-like carbon (DLC) layer to provide 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. Found that you can get.

[0039] Embodiments of the present invention will be described below in detail with reference to the accompanying drawings. However, these embodiments are exemplarily shown, and various modifications can be made without departing from the technical idea of the present invention. It ’s possible to do that.

[0040] FIG. 1 is a cross-sectional explanatory view showing a first example of the VOC-reduced soft packaging material of the present invention, which includes a base film 11, an aqueous gravure ink layer 17, an anchor coating agent layer 19, and a white pigment-containing resin. It is composed of a layer 20 and a sealant layer 16. FIG. 2 is a cross-sectional explanatory view showing a second example of the laminated soft packaging material of the present invention, which is a base film 11, an aqueous gravure color ink layer 17, an aqueous gravure white ink layer 18, an anchor coating agent layer 19, It is composed of a white pigment-containing resin layer 20 and a sealant layer 16.

[0041] The base film 11 is a film capable of gravure printing using water-based ink. Any material can be used. For example, OPP, 0-NYLON, polyester film, etc. can be used as a base material. The thickness of the base film 11 is not particularly limited, and can be appropriately selected according to the purpose of use.

[0042] The water-based gravure color ink layer 17 is based on a resin such as a water-based urethane resin, and a force S, each resin and white pigment material is typically composed of water + alcohol as a solvent. Gravure printing can be performed without being specified, and water or water + alcohol ink may be used. In addition, when performing gravure printing using this water-based gravure color ink, white press printing is not necessary and can be eliminated if the printing state during the printing operation can be confirmed. However, if the minimum area is printed as required, the plate depth is decreased to make it shallower than the normal white printing plate, and the maximum is 10%.

[0043] Further, as the aqueous gravure color ink layer, a plurality of aqueous ink layers, for example, an aqueous gravure color ink layer 17 and an aqueous gravure white ink layer 18 as shown in FIG.

[0044] As the anchor coating agent used for the anchor coating agent layer 19, a force and water-based anchor coating agent that can use a known anchor coating agent are suitable.

[0045] The white pigment-containing resin layer 20 is gravure-printed with water-based gravure color ink! /, At which time white printing is not performed, or white printed on a printed matter that is performed with a minimum area and application concentration. This is done in place of ink, and gives the appearance of printing and concealment to packaging materials. As a result, VOC can be reduced. The white pigment-containing resin layer 20 is preferably a laminate resin layer formed by an extrusion lamination method or the like.

[0046] As the white pigment-containing resin, a resin in which a white pigment is dispersed in a thermoplastic resin is preferably used. As the white pigment, it is necessary to use a pigment that does not affect contents such as food, has high hiding properties, and can sufficiently block ultraviolet rays and visible light. Such a white pigment is not limited to the force S that can increase titanium oxide.

As the thermoplastic resin, a thermoplastic resin conventionally used in such a packaging material can be used. For example, polyethylene, polypropylene, and acid copolymer can be used favorably.

[0047] The mixing ratio of the white pigment varies depending on the type of pigment used and the type of thermoplastic resin. If the amount is too small, the concealability is sufficient, and if it is too much, it becomes brittle. Therefore, generally 2-50% by weight is desirable.

[0048] The sealant layer 16 is a layer for heat-sealing when the packaging material of the present invention is formed into a bag, and may be any heat-sealable thermoplastic resin that does not affect the contents. Examples of the heat-sealable thermoplastic resin include polyethylene and polypropylene. The thickness of the sealant layer can be selected according to the purpose of use and is not particularly limited.

[0049] The same effect can be obtained by using the white pigment-containing resin layer also as the sealant layer. Furthermore, a packaging material having a similar purpose can be obtained by separately preparing a white pigment-containing film and bonding it by a bonding method such as a dry lamination method or an extrusion sand resin method.

FIG. 3 is a cross-sectional explanatory view showing a third example of the soft packaging material of the present invention, which is a base film 11, an aqueous gravure color ink layer 17, a white pigment-containing adhesive polarity-imparting resin layer 21, It consists of a sealant layer 16.

[0051] As a white pigment-containing resin as shown in FIG. 3, an anchor coat agent is not required for adhesion with water-based gravure ink! /, White pigment-containing adhesive polarity imparting resin (for example, acid copolymer) is used. Therefore, it is possible to omit the anchor coat layer, and to reduce the VOC by IJ.

In addition to the copolymer, the adhesive polarity-imparting resin may be a copolymer resin of ethylene (meth) acrylic acid or a polyolefin resin such as low-degree polyethylene or linear low-density polyethylene, or a polar-giving agent such as unsaturated carboxylic acid. However, it is not limited to these.

[0052] Next, an example of a gravure cylinder used in the present invention will be described with reference to Figs. Fig. 4 is an explanatory view schematically showing an example of the manufacturing process of a gravure cylinder (gravure plate making roll). (A) is an overall cross-sectional view of the hollow roll, and (b) is a copper plating layer formed on the surface of the hollow roll. (C) is a partially enlarged sectional view showing a state where a gravure cell is formed on a copper plating layer of a hollow roll, and (d) is a metal layer formed on the surface of the copper plating layer of the hollow roll. The partial expanded sectional view which shows a state, (e) is the partial expanded sectional view which shows the state which formed the metal carbide layer in the metal layer surface of a hollow roll, (f) is charcoal of a hollow roll FIG. 3 is a partial enlarged cross-sectional view showing a state in which a surface of a metallized metal layer is coated with a diamond-like carbon (DLC) coating. Fig. 5 is a flowchart showing an example of a gravure cylinder manufacturing method. FIG. 6 is an enlarged cross-sectional view of the main part of an example of the gravure cylinder.

[0053] A method of manufacturing the gravure cylinder will be described with reference to FIGS. Figure 4 (a) and Figure

In FIG. 6, reference numeral 30 denotes a plate base material, and a hollow roll made of a metal such as aluminum or iron or a reinforced resin such as carbon fiber reinforced resin (CFRP) is used (step 100 in FIG. 5). A copper plating layer 32 is formed on the surface of the hollow roll 30 by a copper plating process (step 102 in FIG. 5).

A large number of minute recesses (gravure cells) 34 are formed on the surface of the copper plating layer 32 (see FIG.

Step 104 of 5). The gravure cell 34 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 34). A force etching method that can use a known method such as engraving the Daravia cell 34 on the copper surface by mechanically operating the copper plate is preferable.

Next, the metal layer 36 is formed on the surface of the copper plating layer 32 (including the gravure cell 34) on which the gravure cell 34 is formed (step 106 in FIG. 5). Further, the metal metal carbide layer, preferably the metal carbide inclined layer 38, is formed on the surface of the metal layer 36 (step 108 in FIG. 5). The metal layer 36 and the metal carbide layer, preferably the metal carbide inclined layer 38, can be formed by a vacuum deposition method (electron beam method), ion plating method, MBE in addition to the sputtering method shown in FIGS. Known methods such as (molecular beam epitaxy method), laser ablation method, ion-assisted film formation method, CVD method (including plasma CVD method) can be applied.

[0056] The metal is carbonizable and has a high affinity with copper! /, Preferably a metal! /. As this metal, tungsten (W), silicon (Si), titanium (Ti), chromium (Cr), tantalum (Ta), zirconium (Zr), and the like can be used.

[0057] As the metal in the metal carbide layer, preferably the metal carbide inclined layer 38, the same metal as the metal layer 36 is used. The composition ratio of carbon in the metal carbide inclined layer 38 is set so that the ratio of carbon gradually increases from the metal layer 36 side to the diamond-like carbon (DLC) coating 40 described later. In other words, the composition ratio of carbon is 0% to gradually (step or The film is formed so that the ratio is increased (in a stepless manner), and finally, the ratio is almost 100%.

In this case, a known method may be used as a method for adjusting the composition ratio of carbon in the metal carbide layer, preferably the metal carbide inclined layer 38. For example, a sputtering method (using a solid metal target and an argon gas atmosphere) The injection rate of hydrocarbon gas such as methane gas, ethane gas, propan gas, butane gas, and acetylene gas is gradually increased stepwise or steplessly), so that the carbon ratio in the metal carbide layer 38 is a copper plating layer. Diamond-like carbon (DLC) coating from the 32 side Metal carbide layer in which the composition ratio of both carbon and metal is changed so as to gradually increase stepwise or steplessly in the 40 direction, that is, metal carbide The graded layer 38 can be formed.

[0059] By adjusting the carbon ratio of the metal carbide layer 38 in this manner, the adhesion of the metal carbide layer 38 to both the copper plating layer 32 and the diamond like carbon (DLC) coating 40 can be improved. it can. Further, if the injection amount of the hydrocarbon gas is constant, a metal carbide layer having a constant composition ratio of carbon and metal can be obtained, and the same action as that of the metal carbide inclined layer can be performed.

Subsequently, a diamond-like carbon (DLC) film 40 is formed on the surface of the metal carbide layer, preferably the metal carbide inclined layer 38 (step 110 in FIG. 5). As a method for forming the diamond-like carbon (DLC) film 40, a sputtering method may be used as in the formation of the metal layer 36 and the metal carbide layer, preferably the metal carbide inclined layer 38, but a vacuum deposition method (electron beam). Method), ion plating method, MBE (molecular beam epitaxy method), laser ablation method, ion-assisted film formation method, plasma CVD method and the like can be applied.

[0061] By coating with the diamond-like carbon (DLC) coating 40 described above and making this diamond-like carbon (DLC) coating 40 act as a surface-enhanced coating layer, there is no toxicity and no concern about the occurrence of pollution. Capable of obtaining gravure printing roll 30a with excellent printing durability.

In this case, the thickness of the copper plating layer 32 is 50 to 200 μm, the depth force of the gravure cell 34 is 5 to 1; and the thickness force of the metal layer 36 is 0.001 to 1 mm. m, preferably 0. 001—0.1 〃m, more preferably 0. 001—0. Ο δ μ ΐΐΐ ^ Thickness force of the charcoal metal layer 38 0.1-1 μ m, and the diamond-like carbon coating 40 preferably has a thickness of 0.;! to 10 m.

[0063] Here, the sputtering method is a method for producing a thin film by depositing the splashed material on a substrate when ions are struck against a material (target material) to be formed into a thin film. Another feature is that a thin film with few restrictions on the target material can be produced in a large area with good reproducibility.

[0064] In the vacuum evaporation method (electron beam method), a thin film is formed! / The material is irradiated with an electron beam to heat and evaporate, and the evaporated material is deposited (deposited) on the substrate to produce a thin film. This method is characterized by high film formation speed and low damage to the substrate.

[0065] The ion plating method is a thin film! / After the material is evaporated, the substrate is ionized by radio frequency (RF) (RF ion plating method) or arc (arc ion plating method). This is a method of depositing a thin film, and has features such as high film formation speed and high adhesion strength.

[0066] The molecular beam epitaxy method is a method of forming a thin film by evaporating a source material in an ultra-high vacuum and supplying it to a heated substrate.

[0067] The laser ablation method is a method in which ions are emitted by making a high-density laser pulse incident on a target to form a thin film on an opposing substrate.

[0068] The ion-assisted film formation method is a method in which an evaporation source and an ion source are installed in a vacuum vessel, and the film is formed using ions in an auxiliary manner.

[0069] 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.

Further, another example of the gravure cylinder used in the present invention will be described with reference to FIGS. FIG. 7 is an explanatory view schematically showing another example of the production process of the gravure cylinder used in the present invention, where (a) is an overall cross-sectional view of the hollow roll, and (b) is a copper plating layer on the surface of the hollow roll. (C) is a partially enlarged sectional view showing a state in which a gravure cell is formed on a copper plating layer of a hollow roll, and (d) is an adhesive layer formed on the surface of the copper plating layer of the hollow roll. (A) is a close-up cross-sectional view showing a state in which the hollow roll is in close contact FIG. 3 is a partially enlarged cross-sectional view showing a state where a diamond-like carbon (DLC) coating is coated on the surface of a layer. FIG. 8 is a flowchart showing another example of a method for producing a gravure cylinder used in the present invention. FIG. 9 is an enlarged cross-sectional view of the main part of another example of the gravure cylinder used in the present invention.

[0071] Another example of the manufacturing method of the gravure cylinder will be described with reference to FIGS.

7 to 9, the metal layer 36 and the metal carbide layer 38 in FIGS. 4 to 6 are replaced with the adhesion layer 37 (the formation of the metal layer 106 and the formation of the metal carbide layer 108 in FIG. The only difference is that the adhesion layer and the diamond-like carbon film were formed by CVD, preferably plasma CVD, instead of sputtering. Since it is the same as above, the detailed description will be omitted.

[0072] The adhesion layer 37 is preferably formed of one or more selected from the group consisting of aluminum (A1), phosphorus (P), titanium (Ti), and diametral (Si).

In this case, the thickness of the copper plating layer 32 is 50 to 200 μm, the depth force of the gravure cell 34 is 150 μm, and the thickness of the adhesion layer 37 is 0 ·! To 1 μm. The diamond-like force is preferably 0.1 l-m.

[0074] In order to form the adhesion layer 37, one or more gases selected from trimethylaluminum, titanium tetraisopropoxide, titanium tetraethoxide, tetramethylsilane, trimethyl phosphite, and hexamethyldisiloxane are used. Use of seeds is preferred

[[00007755]] The power to explain the present invention more concretely and concretely by giving examples of actual working examples below. Examples of actual implementations of the present invention should be interpreted in a limited and definite way, as they are shown illustratively. I can't just leave it. .

[[00007766]] ((Example 11 of actual implementation))

Based on a 22300 axially stretched and stretched polypropylene polypropylene film having a thickness of 3300 (manufactured by Toyo Toyobo Co., Ltd., trade name: pp22116611) It is assumed that the base material material is film 1111, and water-based gugla raviavia color (Intoukiki, manufactured by Toinyo Toyoyo Inkinki Co., Ltd., trade name: JJWW225500) is used. A stamp printing was performed. . It should be noted that the above-mentioned printing of Gugla La Biabia prints described above will be described later.

Separately, a 30-thick unstretched polypropylene film (trade name P-11128, manufactured by Toyobo Co., Ltd.) was prepared as the sealant layer 16.

[0077] Further, as a white pigment-containing resin, 10% of a master batch containing a thermoplastic polyethylene resin M-I IP (manufactured by Prime Polymer Co., Ltd.) and 70% titanium oxide as a white pigment is added to obtain a final titanium oxide content. 6. 25% white pigment containing resin for extrusion lamination was made

Yes

[0078] The white pigment-containing resin was melt extruded and the gravure-printed base film 11 and the sealant layer 16 were pressure-bonded to produce a VOC-reduced flexible packaging material.

At this time, it is necessary to coat the water-based gravure color ink surface with an anchor coating agent so as to have adhesion. As an anchor coating agent to be used, an aqueous anchor coating agent (trade name EL—667, manufactured by Toyo Moton Co., Ltd.) )It was used.

The VOC-reduced soft packaging material obtained in this example had the performance of achieving the effects of the present invention as described above!

[0079] (Example 2)

Add 10% masterbatch with white pigment in the thermoplastic adhesive polarity-added acid copolymer resin (Mitsui DuPont) and titanium oxide 70% as the white pigment-containing resin without using the anchor coating agent. A flexible packaging material was produced in the same manner as in Example 1 except that 6.25% of white pigment-containing adhesive polarity imparting resin was used as the final titanium oxide content. The resulting soft packaging material had a white pigment-containing resin surface and a water-based ink surface joined together, greatly reducing VOC.

[0080] (Example 3)

A VOC-reduced flexible packaging material was produced in the same manner as in Example 1 except that gravure printing was performed using the gravure cylinder of Experimental Example 2 described later, and similar results were obtained.

[0081] (Experiment 1)

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 is 20 minutes and the plating surface is There was no occurrence of pits and a uniform copper plating layer was obtained.

[0082] 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, a hollow roll with a gravure cell depth of 10 m was produced.

A tandastain (W) layer was formed by sputtering on the upper surface of the copper plating layer on which the gravure cell was formed. The sputtering conditions are as follows. Tungsten (W) sample: solid tungsten target, atmosphere: argon gas atmosphere, film formation temperature: 200 to 300 ° C., film formation time: 60 minutes, film formation thickness: 0.03 m.

Next, a tungsten carbide layer was formed on the upper surface of the tungsten layer (W). The sputtering conditions are as follows. Tungsten (W) sample: solid tungsten target, atmosphere: gradually increase hydrocarbon gas in argon gas atmosphere, deposition temperature: 200-300 ° C, deposition time: 60 minutes, deposition thickness: 0.1 m .

[0085] Further, a diamond-like force single bond (DLC) coating was formed on the upper surface of the tungsten carbide layer by sputtering. The sputtering conditions are as follows. DLC sample: solid carbon target, atmosphere: argon gas atmosphere, deposition temperature: 200 to 300 ° C., deposition time: 150 minutes, deposition thickness: 1 m. In this way, a gravure cylinder was completed.

Yes

[0086] (Experiment 2)

In the same manner as in Experimental Example 1, a hollow roll with a gravure cell depth of 10 am was produced. A gravure cylinder was completed in the same manner as in Experiment 1 except that the tungsten (W) sample was changed to a silicon (Si) sample for the hollow roll.

[0087] (Example 4)

A VOC-reduced packaging material was produced in the same manner as in Example 1 except that gravure printing was performed using the gravure cylinder of Experimental Example 3 described later, and similar results were obtained.

[0088] (Experiment 3)

A hollow roll with a gravure cell depth of 10 m was prepared in the same manner as in Experimental Example 1. This An aluminum (A1) layer having a thickness of 0.1 m was formed on the upper surface of the copper plating layer of the hollow roll by plasma CVD using trimethylaluminum as a gas species.

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

[0090] (Example 5)

A VOC-reduced packaging material was produced in the same manner as in Example 1 except that gravure printing was performed using the gravure cylinder of Experimental Example 4 described later, and similar results were obtained.

[0091] (Experiment 4)

A hollow roll with a gravure cell depth of 10 m was prepared in the same manner as in Experimental Example 1. Gravure in the same manner as in Experimental Example 3, except that titanium tetraisopropoxide was used as the gas species on the upper surface of the copper plating layer of this hollow roll and a 0.1 am-thick titanium (Ti) layer was formed by plasma CVD. Completed the cylinder.

[0092] 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.

Claims

The scope of the claims

[1] A soft packaging material in which a base film, an aqueous gravure color ink layer, an anchor coating agent layer, a white pigment-containing resin layer, and a sealant layer are sequentially laminated, and the formation of the aqueous gravure color ink layer is hollow. By gravure printing using a gravure cylinder comprising a roll, a copper plating layer provided on the surface of the hollow roll and having a number of gravure cells formed on the surface, and a diamond-like carbon coating covering the surface of the copper plating layer A flexible packaging material characterized by what it does.

[2] A soft packaging material in which a base film, an aqueous gravure color ink layer, an anchor coating agent layer, and a white pigment-containing resin layer are sequentially laminated, and the formation of the aqueous gravure color ink layer includes a hollow roll, It is performed by gravure printing using a gravure cylinder provided on a surface of a hollow roll and including a copper plating layer having a number of gravure cells formed on the surface and a diamond-like carbon film covering the surface of the copper plating layer. A flexible packaging material characterized by the above.

[3] A soft packaging material in which a base film, an aqueous gravure color ink layer, a white pigment-containing resin layer, and a sealant layer are sequentially laminated, and the white pigment-containing resin of the white pigment-containing resin layer has an adhesive polarity The formation of the water-based gravure color ink layer, a hollow roll, a copper plating layer provided on the surface of the hollow roll and having a number of gravure cells formed on the surface, and a surface of the copper plating layer A soft packaging material characterized in that it is formed by gravure printing using a Daravia cylinder including a diamond-like carbon film for coating the material.

[4] The soft packaging material according to [1] or [2], wherein the anchor coating agent layer is aqueous.

[5] The force according to any one of claims 1 to 4, wherein a white presser is applied to the water-based gravure ink layer while limiting an area necessary for confirming a printing state during a printing operation. Flexible packaging material

Yes

[6] The white pigment in the white pigment-containing resin layer is titanium oxide, and the titanium oxide content in the white pigment-containing resin layer is 2 to 50% by weight; Any one of the flexible packaging materials.

7. The flexible packaging material according to any one of claims 1 to 6, wherein the diamond-like carbon film is formed by a sputtering method or a CVD method.

[8] A water-based gravure color ink layer and an anchor coating agent layer are formed on a base film, and a heat-sealable thermoplastic resin film is opposed to the base film, and the molten white pigment-containing resin is extruded in layers between the layers. A method for producing a gravure-printed laminated soft packaging material in which a film side and a heat-sealable thermoplastic resin film side are pressure-bonded, wherein the formation of the water-based gravure color ink layer is provided on the surface of the hollow roll and the hollow roll A gravure printing is performed by gravure printing using a gravure cylinder including a copper plating layer having a large number of gravure cells formed on the surface and a diamond-like carbon coating covering the surface of the copper plating layer. Manufacturing method of printed laminated soft packaging material.

[9] A water-based gravure color ink layer is formed on the base film, and a heat-sealable thermoplastic resin film is opposed to the base film, and the molten white pigment-containing resin is extruded in layers to heat-seal the base film side. A method for producing a gravure printing layer soft packaging material for pressure bonding with a thermoplastic resin film side, wherein the white pigment-containing resin is an adhesive polarity-imparting resin, and the formation of the water-based gravure color ink layer is performed with a hollow roll. And a gravure printing using a gravure cylinder including a copper plating layer provided on the surface of the hollow roll and having a number of gravure cells formed on the surface, and a diamond-like carbon coating covering the surface of the copper plating layer. A process for producing a gravure-printed laminated soft packaging material, characterized by being made.

10. The method for producing a flexible packaging material according to claim 8, wherein the diamond-like carbon film is formed by a sputtering method or a CVD method.