JP6167803B2 - Laminated tube material for packaging, packaging tube body using the same, and laser printed body - Google Patents

Description

  The present invention has strength, waist and the like, is excellent in barrier properties against oxygen gas, water vapor, etc., content resistance, etc., and seasonings such as toothpaste, mayonnaise, kneaded wasabi, kneaded, ketchup, etc. Or a laminated tube material for packaging that can be printed by laser suitable for filling and packaging contents such as whipped cream and other foods such as creams, cosmetics, pharmaceuticals, etc. and packaging using the same The present invention relates to a tube and a tube body for laser printing packaging having a printed image by a laser on the tube.

  Conventionally, in addition to forming patterns such as letters, symbols, and drawings in advance on the surface of packaging containers such as cans, bottles, plastic bottles, packaging bags, and packaging materials for packaging these packages, for example, the year of manufacture A method of printing additional information such as date, manufacturer, product name, expiration date, etc. later with ink is widely known.

  Packaging bodies and packaging materials such as packaging containers and packaging bags are used for various purposes, and depending on the purpose and use situation, etc., selection of materials, laminating configuration or so as to meet a wide variety of demands and demands The structure is changed and used as a package. For this reason, the package has a variety of laminated structures depending on the form of the package, the change of the material according to the use situation, and the like.

  For such a wide variety of packaging materials, there is a need for a technique that can appropriately and accurately print additional information that requires a description for each packaging material.

  Packaging layers such as packaging containers and packaging bags and packaging materials have a printing layer formed in advance on most of the front and back sides, and there are fewer margins than containers such as boxes and cans. On the other hand, when the ink layer is displayed on the outer surface of the packaging bag over the existing printed layer, the appearance of the packaging bag is impaired, and the ink layer There is a disadvantage that reading of the display becomes difficult.

  In the case of a laminated tube for packaging suitable for filling and packaging contents such as foods, beverages, cosmetics, pharmaceuticals, etc., the laminated tube material for packaging is at least a surface polyolefin-based resin layer, an intermediate layer or a barrier film, and The backside polyolefin-based resin layer is sequentially laminated to form a laminated tube material for packaging. The surface of the surface polyolefin resin layer, which is the outermost layer at both ends of the laminated tube material for packaging, is overlapped with the surface of the back surface polyolefin resin layer, which is the innermost layer, and the opposite surface is heat sealed to form a cylindrical body Forming a head composed of a mouth portion, a shoulder portion, etc. in one opening of the cylindrical body, and further screwing a cap into the mouth to produce a tube container, The contents are filled from the other opening of the cylindrical body constituting the tube container, and the opening is hermetically sealed to form a bottom seal part to manufacture a packaged product made of the tube container.

  In such a wrapping laminated tube, a printing layer is formed on the outer peripheral surface of the body part, and displays a predetermined pattern such as a product name, manufacturer, seller, date of manufacture, etc., along with a desired pattern. ing. The printed layer is generally formed in advance by a gravure printing method or the like on the back surface of an intermediate layer on the back surface side of a raw film such as a resin film that forms a surface resin layer constituting a laminated tube container, and thereafter This is laminated with a material constituting the inner surface resin layer or the like to produce a laminated material, and then the laminated material is used to produce a laminated tube container.

  As described above, when printing additional information, necessary characters, symbols, etc. are displayed on the surface sealant layer of the packaging laminated tube material or packaging tube, and the binder of this ink layer is the same as that of the heat seal layer. The printing area is limited. Especially for packaging laminated tubes, which are packaging bodies with a narrow printing area and limited printing layers, for additional packaging of appropriate information accurately and accurately at any position and with improved visibility There is a need to provide a laminated tube material, a tube using the same, and a printed body. In addition, since the laminated tube for packaging is in direct contact with food or the like, when the ink layer is displayed on the outer surface of the tube or the back side of the raw film, pigments, vehicles, etc. contained in the ink layer In addition to touching, there was also a hygiene problem that fats and oils in foods dissolved the ink components.

  Packaging and packaging materials such as packaging containers and packaging bags can be printed on the surface of the packaging bag by a well-known printing method, inkjet printer, laser irradiation, etc. It is already known to print additional information between layers. When printing a predetermined pattern or fixed information on a packaging container or packaging material, a printing layer can be formed between layers by inkjet printing or general-purpose printing methods, but additional information that changes the information cannot be set in advance. In some cases, it may be printed on the surface of the package, the printing may dry out, the compatibility between the package and ink, the contact of the printed surface of the package moving at high speed, etc. The problem is that printing cannot be performed appropriately and accurately, such as in the state of.

  In order to solve the conventional problems, in particular, attention has been paid to printing of additional information by laser irradiation. In such laser printing, on the surface of a plastic molded article or the like formed with a resin composition containing a color former that develops color by laser light, or such a resin composition layer formed on the surface. The laser print image is directly formed, and there is a problem that the print is faded or erased by rubbing the surface of the laser print image.

As a technique for printing with a laser beam, printing on a film by irradiating a YAG laser, a YVO ₄ laser, or the like is known. As a multilayer laminated film for laser printing that can be printed by a laser, a film using a special ink that changes color by laser irradiation as an intermediate layer (coloring layer) is known (Patent Document 1).

  Since such special ink is very expensive, the special ink layer is preliminarily provided only on a portion to be printed on the substrate. However, even in that case, alignment is difficult and the print position cannot be easily changed. In addition, there is a drawback that the printed line is thin and difficult to read.

General inks also change color slightly when irradiated with YAG or YVO ₄ laser. Therefore, it is also known to use such normal ink as an intermediate layer (coloring layer) (Patent Document 2). However, in this method, it is necessary to form a printing portion in the intermediate layer by irradiating with powerful laser light. In other words, in order to obtain sufficient visibility, the laser power is output until the intermediate layer of the laser-irradiated part is completely evaporated over the entire thickness in the depth direction (direction from one surface of the film to the other surface). Need to increase.

  Accordingly, there is a problem that a hole is formed in the base film by irradiation with a powerful laser beam. In addition, there is a problem that the printing speed is slow because it is necessary to irradiate a powerful laser beam.

JP 2007-55110 A Japanese Patent Laid-Open No. 2007-217048

  The present invention provides a packaging material having a wide variety of laminated structures, particularly packaging laminated tube materials and packaging laminated tubes which are packaging bodies having a limited laminated structure imparted with barrier properties. In order to solve the conventional problems in printing, it is made of an inexpensive material, easy to manufacture, easy to change the printing position, and low output that does not damage the base film. Laminated tube material for packaging that can be printed with appropriate information accurately and accurately at any position and with improved visibility by irradiating a laser with an easily readable print line. And it aims at providing the laminated tube for packaging using the same, and those printed bodies.

  The present inventors, as a result of various researches, in the laminated tube material which is a packaged body having a limited laminated structure with a barrier property or a laminated tube using the same, prints additional information while packaging. In order to solve the conventional problems, white ink that is easy to obtain and highly versatile, and color ink that uses low-cost laser coloring material that develops color using low-power laser light are used. In this method, colored ink is utilized as a printing foundation layer for a printing layer generally applied to the printing layer, and an area of only the laser coloring ink foundation layer that can be printed by a low-power laser beam is formed on the printing layer, and the area is visually recognized. By irradiating low-power laser light from the side, the colored ink component spreads only on the surface of the print image area between the base film layer and the print layer on the viewing side. For packaging that can form a clear laser-printed image with a moderately thick line with an ink component formed by a laser color former at an appropriate position on the color ink base layer. A laminated tube material was found.

  The present invention relates to a laminated tube material for packaging having a sealant layer on both outermost surfaces of a laminated structure which is laminated in the order of a substrate, a pattern printing layer, and a base layer for printing, and has a gas barrier layer, the pattern printing layer In the laminated tube material for packaging having a printed layer in which a region where only the printing base layer is formed and a region where only the printing base layer is formed, the printing base layer is irradiated with laser light. A coloring ink layer that can be printed by a laser beam containing a coloring material that develops color, in particular, a bismuth-based compound, a metal oxide or a complex oxide, or a copper-based compound or a molybdenum-based compound It is a layer made of an ink composition containing two or more kinds of compounds, and includes a base material on the viewing side of the laminated tube material for packaging and a base layer for color ink printing that can color and print. This is a laminated tube material for packaging which forms a laser-printing region that forms a color-developing region colored by laser light only on the surface of the underlying layer for color ink printing in the meantime, and can achieve the above object.

And this invention enables the laser printing by the following points in the laminated tube material for packaging and the laminated tube for packaging which have the specific layer structure which provides barrier property. 1. A laminated tube material for packaging having a sealant layer on both outermost surfaces of a laminated structure having a gas barrier layer and laminated in the order of a substrate, a pattern printing layer, and a printing base layer, the pattern printing layer and the laser printing layer In the laminated tube material for packaging having a gas barrier layer by forming a printing layer having a region where only the printing foundation layer overlaps with a region where only the printing foundation layer is formed, the printing foundation layer is irradiated with laser light. This is a coloring ink layer that can be printed by a laser beam containing a coloring material that develops color by the above, and is a laminated tube material for packaging in which the region of only the printing base layer is a laser printing region.
2. It is preferable to use a laminated tube material for packaging using a bismuth-based compound as a coloring material because it can be colored and printed by a low-power laser beam.
3. A bismuth-based compound that uses one or two or more compounds selected from bismuth hydroxide, bismuth oxide, bismuth carbonate, and bismuth nitrate to produce a laminated tube material for packaging that develops color with low-power laser light and is clear Therefore, it is preferable that laser printing is possible.
4). Colored ink that contains one or more compounds selected from the group consisting of metal oxides, complex oxides, or their groups, and made into a laminated tube material for packaging, is colored by low-power laser light. Clear printing is possible and preferable.
5. Colored ink is made of laminated tube material for packaging using one or two or more compounds selected from copper-based compounds, molybdenum-based compounds or their groups. A clear laser printing is possible and preferable.
6). The gas barrier layer is a gas barrier transparent vapor deposition layer, and the laminated tube material for packaging used as a transparent vapor deposition film provided with a gas barrier transparent vapor deposition layer on the substrate can be laser printed with low output laser light. It is preferable.
7). The gas barrier layer is an aluminum metal layer, and the laminated tube material for packaging located on the opposite side of the base material of the white ink layer that is the base layer for printing is capable of laser printing with low-power laser light. It is preferable.
8). What formed the packaging tube using the said laminated tube material for packaging is a thing which can perform laser printing with a low output laser beam, and is preferable.
9. By irradiating the laminated tube material for packaging or the laminated tube for packaging with YAG or YVO ₄ laser light from the substrate side, the color development area of the colored ink spreads to the boundary between the substrate and the printing base layer. A laser-printed image formed by a low-power laser beam and laser-printed with additional information is preferred as a laminated tube printed body for packaging.

  The laminated tube material for packaging of the present invention does not need to use an expensive special ink for laser printing, for example, using a white ink that is generally used as a base for printing a packaging film. In addition, a printing base layer formed as a white ink layer that can be printed by a low-power laser beam is formed on the entire area of the laminated tube material for packaging, and the necessary pattern printing layer is formed on the substrate side of the printing base layer. By using a laminated tube material for packaging in which a laser printing layer is formed with a laminated structure in which layers are stacked, an area of only the printing base layer can be provided at an arbitrary position, and a low-power laser is irradiated to the area. The color can be developed by the laser printing area.

  The present invention uses a coloring material, particularly a coloring ink layer containing a bismuth compound, as a white pigment used in a commonly used white ink as a base for printing a package, or further a metal oxide, a composite oxidation As a base layer that can be colored with a low-power laser and can be used as a print printing layer for laser printing of additional information. The laminated tube for packaging can function efficiently as an underlayer of the printed layer and can be efficiently produced from an inexpensive material.

By irradiating the laminated tube material for packaging of the present invention with a YAG or YVO ₄ laser from the substrate side, the ink component containing the coloring material forming the printing layer is colored by the low-power laser irradiation and partially carbonized. However, since the color development area is widened at the boundary between the base material and the printing underlayer, the output is weak, that is, there is no need to increase the laser output until the entire printing layer is evaporated, and the white ink base as the base With this contrast, a laser-printed image having excellent visibility from the substrate side can be clearly formed.

  Further, in the printed body of the present invention, the laser-printed image is applied not inside the film surface but inside, that is, between the substrate and the printing layer. Therefore, since this image has excellent wear resistance, it is possible to effectively prevent disappearance due to rubbing or the like, and to prevent change of the additional information.

  From these advantages, according to the laminated tube material for packaging of the present invention and the packaging tube using the same, additional information can be formed in an area other than the heat-sealed portion of the tube. Variable information such as date, manufacturer, product name, expiration date, and production location can be read more easily than a conventional inkjet printer, and a large amount of information can be printed as a laser-printed image.

Without the ink contacting the surface of the laminated tube material for packaging, the printing underlayer of the color ink at least the inner layer other than the layer in contact with the contents of the laminated tube tube becomes a printable layer that can be printed by laser beam irradiation. Printing can be performed, and it is possible to obtain a product having excellent hygiene without dissolving ink printed by the oil and fat derived from the contents of the laminated tube material for packaging.
Moreover, in the manufacturing process of the laminated tube material for packaging, only the same printing process as the normal printing process is performed, and it is not necessary to provide an additional layer for laser printing, and the manufacturing process can be simplified.

It is a schematic sectional drawing which shows the example about the laminated constitution of the laminated tube material for packaging of this invention. It is a schematic sectional drawing which shows another example about the laminated constitution of the laminated tube material for packaging of this invention. FIG. 2 is a schematic cross-sectional view showing an example of the layer structure of a printed body that uses the laminated tube material for packaging according to the present invention shown in FIG. .

  The laminated tube material for packaging according to the present invention, the laminated tube for packaging using the same, and the layer structure of those printed bodies will be exemplified and described in detail below with reference to the drawings.

FIG. 1 is a schematic cross-sectional view showing an example of the layer structure of the laminated tube material for packaging of the present invention.
As shown in FIG. 1, the laminated tube material for packaging of the present invention is laminated in the order of a base material, a pattern printing layer, and a printing base layer, and has a sealant layer on both outermost surfaces of a laminated structure having a gas barrier layer. A laminated tube material for packaging having a printed layer in which an area where a pattern printing layer and a printing underlayer serving as a laser printing layer overlap each other and a region of only the printing underlayer are formed In the material, the base layer for printing is basically composed of a laminated tube material for packaging which is a white ink layer that can be printed by laser light.

  In another aspect, as shown in FIG. 2, the pattern printing layer is composed of two or more layers, each of which is made of the same or different ink and has excellent adhesion to the substrate. A stacked structure may be used.

As shown in FIG. 3, the printed body of the present invention is produced by irradiating the laminated tube material for packaging of the present invention with a YAG or YVO ₄ laser from the substrate side. On the surface of the ink cartridge has a print portion in which the carbonized ink component spreads.

(Base material)
In the present invention, the substrate is a resin film according to the purpose of use, application, etc., and when the printing layer is laminated, the lamination strength with the printing base layer is higher than the lamination strength with the pattern printing layer. Any resin film that is somewhat smaller can be used.

  Specifically, it becomes a basic material, and further, after printing, it constitutes a surface protective layer and can be seen through a laser-printed image, etc., so it is excellent in mechanical, physical, chemical, etc. A resin film having strength, excellent puncture resistance, and the like, and excellent heat resistance, moisture resistance, transparency, and the like can be used.

  In the present invention, examples of such resin films include various resin films such as polyolefin resins such as polyethylene resins and polypropylene resins, cyclic polyolefin resins, fluororesins, polystyrene resins, polyester resins, polyamide resins, and cellulose resins. You can choose.

  In addition, at the time of film formation using one or more of the above-mentioned various resins, for example, film processability, heat resistance, weather resistance, mechanical properties, dimensional stability, antioxidant properties, slipperiness, release properties, etc. Various plastic compounding agents and additives can be added for the purpose of improving and modifying moldability, flame retardancy, antibacterial properties, electrical properties, strength, laminate strength, etc. Can be arbitrarily added from a very small amount to several tens of percent depending on the purpose.

  In the above, as a general additive, for example, a lubricant, a crosslinking agent, an antioxidant, an ultraviolet absorber, a light stabilizer, a filler, a reinforcing agent, an antistatic agent, a pigment, and the like can be used. Furthermore, a modifying resin or the like can also be used.

  In order to adjust the laminate strength and adhesion between the laser color ink layer and the substrate, any surface can be subjected to a desired surface treatment before lamination as required. As the surface treatment, for example, pretreatment such as corona discharge treatment, ozone treatment, low temperature plasma treatment using oxygen gas or nitrogen gas, glow discharge treatment, oxidation treatment using chemicals or the like can be performed. .

Moreover, you may provide a primer coating agent layer, an undercoat agent layer, an anchor coating agent layer etc. between a printing foundation layer and a base material, for example.
As the resin film, any of an unstretched film or a stretched film stretched in a uniaxial direction or a biaxial direction can be used.

  In the present invention, as the various resin films, for example, one or more of the various resins described above are used, and film forming methods such as an extrusion method, a cast molding method, a T-die method, a cutting method, and an inflation method are used. Using various methods, the above-mentioned various resins can be formed into a single film, or two or more types of resins can be used and mixed before forming into a film to form a film of various resins. Further, for example, any of a stretched film stretched in a uniaxial direction or a biaxial direction using a tenter method, a tubular method, or the like can be used.

In the present invention, the thickness of the resin film may be a thickness that can be kept to the minimum necessary for strength, puncture resistance, and the like. On the other hand, if it is too thin, the strength, puncture resistance and the like are reduced, which is not preferable.
In the present invention, for the reasons described above, 10 to 100 μm, preferably 10 to 50 μm is desirable.

  In the present invention, as the resin film for forming the substrate, polyethylene terephthalate (PET) and a PET substrate on which a transparent vapor deposition layer is formed can be particularly preferably used. The polyethylene terephthalate film is excellent in terms of stability, processability, cost, heat resistance, chemical resistance, etc., particularly in applications as packaging materials, and is a printing ink suitably used as a printing layer described later. When laminating, a preferable laminate strength with the printed layer can be obtained. When using PET having a transparent vapor deposition layer as a substrate, it is not necessary to provide a gas barrier layer separately, but a barrier layer may be laminated as necessary.

(Print layer)
In the present invention, the printing layer includes at least a printing foundation layer composed of a pattern printing layer and a laser-colored white ink layer, and is laminated with a commonly used color ink and laser-colored ink on a substrate by printing or coating. It is a layer provided in this way.
In the present invention, the pattern print layer is formed by printing a desired print pattern such as a character, a figure, a symbol, a pattern, and a pattern on a base material using a normal printing method.

  On the other hand, the laser coloring ink layer, which is the printing underlayer of the present invention, functions as a laser printing portion that can be colored and printed by laser light, and the laser coloring ink layer is colored by low-power laser light. A coloring ink containing a pigment component containing at least a coloring material is preferably used, and an inorganic compound is used for the pigment component. Preferably, the constituent pigment component includes an inorganic compound such as a white pigment. The printing underlayer can also obtain a clear printed image by further providing a printing underlayer on the laser coloring ink layer and multilayering the printing underlayer.

  As the coloring material that develops color by laser light used in the present invention, a conventionally known coloring material can be used as the coloring material. Specifically, colorants such as dyes and pigments, clays, and the like can be used. Specifically, yellow iron oxide, inorganic lead compounds, manganese violet, cobalt violet, mercury, cobalt, copper, nickel, etc. Metallic compounds, nacreous pigments, silicon compounds, mica, kaolins, silica sand, diatomaceous earth, talc, titanium oxide coated mica, tin dioxide coated mica, antimony coated mica, tin + antimony coated mica, tin One type or two or more types such as + antimony + titanium oxide-coated mica can be used.

  In the present invention, at least a bismuth compound is particularly used as a coloring material that develops color with a low-power laser. Specific examples of the bismuth compound include, but are not limited to, bismuth nitrates such as bismuth oxide, bismuth nitrate, and bismuth oxynitrate, bismuth halides such as bismuth chloride, bismuth oxychloride, bismuth sulfate, and bismuth acetate. Bismuth citrate, bismuth hydroxide, bismuth titanate and the like are mentioned. Among them, bismuth nitrate and bismuth hydroxide are preferable from the viewpoint of easy availability and low cost. As a bismuth-type compound, 1 type, or 2 or more types of compounds can be included. In the present invention, a coloring material containing at least a bismuth compound is used, and other coloring materials than bismuth compounds can be used in combination as long as the coloring material is colored by laser light.

In the present invention, a coloring material containing at least a bismuth-based compound is used, and a coloring material that develops color with laser light and / or an inorganic compound can be used to increase coloring efficiency. It is possible to use a metal oxide, a composite oxide, a metal salt, or one or more compounds thereof as the inorganic compound, and even if there is an inorganic compound even when irradiated with low-power laser light, Add inorganic compounds to function and / or to increase the whiteness of the white ink containing the coloring material and white pigment by helping the coloring of the coloring material by functioning and increasing the heat generation efficiency of the inorganic compound It is preferable.

  In the present invention, it is possible to use a pigment used in white ink that is generally used as a general-purpose printing foundation layer in printing. Preferably, the metal oxide can contain one or more of titanium oxide, magnesium oxide, zinc oxide, aluminum oxide, silicon oxide, nickel oxide, tin oxide, neodymium oxide, mica, zeolite, kaolinite and the like. .

  In the present invention, not limited to metal oxides, copper compounds, molybdenum compounds, copper / molybdenum composite oxides, copper / tungsten compounds, metal salts, and the like can also be suitably used because they also function as coloring materials. .

  As the copper-based compound, for example, copper, copper oxide, copper halide, formic acid, citric acid, salicylic acid, lauric acid, oxalic acid, maleic acid and other organic acid copper, copper phosphate, hydroxyphosphate copper and the like are suitable. Can be used.

  As the molybdenum-based compound, molybdenum, molybdenum dioxide, molybdenum trioxide, molybdenum chloride, and metal molybdate (metals: K, Zn, Ca, Ni, bismuth, Mg, and the like) can be preferably used.

  As the metal salt, a salt of an acid such as sulfuric acid, nitric acid, oxalic acid, or carbonic acid with a metal such as barium, cobalt, magnesium, nickel, or iron can be used.

  In the present invention, in particular, a laser coloring ink that contains at least a bismuth-based compound as a coloring material and that contains titanium oxide as a white pigment is preferably used.

  The bismuth compound color-developing material that develops color with a low-power laser beam is contained in the range of 0.1 to 95.0% by weight in terms of solid content with respect to the ink composition. In the present invention, the content of the coloring material is preferably 1 to 30% by weight. If it is less than 1% by weight, it is not preferable because the color development, printing is insufficient, and the image becomes unclear, and as the content increases, the color development of the print becomes deeper. The difference in the visibility due to the color is not recognizable, but rather the cost increases, the printing underlayer becomes hard, cracks and strength decreases, and the pigment color of the coloring material itself that develops color when irradiated with laser light is the printing underlayer It is not preferable because of coloring it.

  The content of the inorganic compound including the color developing material that develops color with a low-power laser beam is 1 to 99% by weight in terms of solid content of the inorganic compound. As the content increases, the color of the print becomes darker, but the content is preferably 5 to 65% by weight. If it is less than 5% by weight, color development, printing is insufficient and unclear, and if it exceeds 65% by weight, it is not preferable because of an increase in inorganic compounds, resulting in increased costs, brittle printing underlayer, and reduced strength. .

  The laser coloring ink layer preferably has a film thickness of 0.05 to 20 μm, more preferably about 0.1 to 7 μm. If the film thickness is less than 0.05 μm, color development or printing due to a color forming material that develops color by laser beam irradiation may be insufficient or unclear. On the other hand, as the film thickness increases, the color of the print becomes deeper. However, when the film thickness exceeds 20 μm, the color and the color of the color-developing material that develops color by laser irradiation are sufficient, but a large amount of color-developing material is used. For this reason, it is not preferable for the reasons such as cost increase to reduce the strength of the printing base layer, and the pigment color of the coloring material itself that develops color by laser beam irradiation to color the laser coloring ink layer. When the amount of pigment used is the same, the visibility of printing is slightly improved when the additive concentration is higher and the film thickness is thinner.

  A printing layer can be formed by diluting the coloring ink of the laser coloring ink layer of the present invention with a conventional solvent, if necessary, and printing or coating on a heat-shrinkable substrate. When there are many metal oxides as a coloring ink component, the film is easily damaged by laser irradiation. Conversely, if the amount of metal oxide is small, the printed image tends to be unclear.

  In the present invention, when a print image is formed on the laser color ink layer, a colored undercoat layer can be further provided on the laser color ink layer for the purpose of improving the visibility of the image. In this case, colors with greatly different contrasts can be arranged, and the back of the image can be shielded, so that the visibility of the printed image is always ensured regardless of the color, transparency, and lighting condition of the package. Can do.

  As the colored under layer, the color and color of the pigment can be arbitrarily selected so that the print can be clearly seen by the color that develops when the laser color ink layer is irradiated with laser light, the color of the color layer itself by laser light, etc. . For example, when the laser coloring ink layer is highly transparent gray, the laser coloring is black, and the content is black, high visibility can be obtained by selecting a white colorant.

  For example, basic lead carbonate, basic lead sulfate, basic lead silicate, zinc white, zinc sulfide, lithopone, antimony trioxide, anatase-type titanium oxide, rutile-type titanium oxide, calcium carbonate, One type or two or more types of white pigments such as zinc oxide and barium sulfate can be used.

  The colored base layer preferably has a thickness of 0.05 to 20 μm, more preferably 0.1 to 7 μm. When the film thickness is less than 0.05 μm, coloring is insufficient and visibility is also insufficient. On the other hand, as the film thickness increases, the color of the print becomes darker and the visibility is improved. However, if the film thickness exceeds 20 μm, it is not preferable for reasons such as an increase in cost and a decrease in strength of the colored base layer. In addition, when the content of the coloring component with respect to the entire colored base layer is the same, the concentration of coloring and the visibility of printing are improved by decreasing the additive concentration and increasing the film thickness.

  Specific examples of the binder resin constituting the ink include urethane resin, polyester resin, acrylic resin, and cellulose resin. These resins are used alone or in combination of two or more. In particular, in a laser coloring ink used as a laser coloring ink layer, a urethane resin is preferably used as a binder resin. When the binder resin is laminated on the above-mentioned base material, the binder resin gives a preferable laminate strength with the base material, and in the printing by laser light, the components of the coloring ink are appropriately spread between the base layer and the base material. , Can be recognized as a character.

  As long as the laser coloring ink of the present invention contains a laser coloring agent, any metal oxide white ink conventionally used as a printing base can be suitably used. Such a laser coloring ink is diluted with a conventional solvent as necessary, and printed or coated on a substrate to form a printing underlayer. When the laser coloring ink contains a large amount of metal oxide, the film is easily damaged by laser irradiation. Conversely, if the amount of metal oxide is small, the printed image tends to be unclear.

In order to adjust the laminate strength between the substrate and the printing layer to a desired range, an optional additive may be added to the ink as necessary. Examples of this include addition of a lubricant, an antiblocking agent, a filler, a curing agent, and the like. In addition, various additives such as pigment dispersants, antifoaming agents, leveling agents, waxes, silane coupling agents, preservatives, antioxidants, UV absorbers, rust inhibitors, plasticizers, flame retardants, color developers, etc. It can also be added. These additives are used particularly for the purpose of improving printability, printing effect, and the like, and the type and amount used can be appropriately selected depending on the printing method, printing substrate, and printing conditions.
In addition, the laminate strength may be adjusted by performing a surface treatment such as corona treatment on the laminated surface of the base material, or by laminating a printing layer on an untreated surface.

  In the present invention, the base printing layer may have a structure in which two or more printing layers made of the same or different inks are laminated. Here, a laser color ink printing layer is formed on the side in contact with the substrate. The type, content, and lamination method of the binder resin are selected so that the lamination strength between the laser color ink printing layer and the base material is the weakest among the printing layers constituting the laminated tube material for packaging. .

The total thickness of the printed layer, the coating amount of the ink, it is preferable 1.5~4.5g / m ^2, more preferably from 2.7~3.3g / m ² The coating amount after drying. If the printing layer is thicker than this, the film is easily damaged by laser irradiation. Conversely, if it is thinner than this, the printed image tends to be unclear.

  In addition, in order to obtain the laminate strength defined in the present invention between the substrate and the printing layer (the pattern printing layer and the printing underlayer), and between the printing layer and another layer such as an aluminum foil or a sealant layer, the pattern printing is performed. Although it is possible to make the layer or the printed base layer multi-layered, it is possible to more reliably obtain the strength specified by the one-layer printing layer.

  In addition to printing by a known method such as gravure roll coating, reverse roll coating method, knife coating method, kiss coating method, etc., the method of laminating the printing layer can use methods such as inkjet, immersion, spin coating, In the present invention, a method of laminating by printing is preferable. If a printing machine capable of winding a film after printing is used in a printing system in which white ink is present, any of gravure printing, offset printing, letterpress printing, and flexographic printing may be used. In particular, the production process can be simplified by solid printing on the entire surface or part of the printing substrate. The gravure can be easily applied in large quantities, and solid printing can be performed on the entire surface or part of the printing base, thereby improving the concealment and simplifying the manufacturing process. The printing method is suitable.

In the present invention, in order to obtain a laminated tube material for packaging which is clear by laser light and does not cause printing unevenness, the coating amount of the ink is 1.5 to 4.5 g / m ² as the coating amount after drying. Is suitable.

(Sealant layer)
In the present invention, the sealant layer is provided in the innermost layer and the outermost layer of the laminated tube material for packaging, and is a layer made of a conventional thermoplastic resin or a layer made of a film of the resin as the sealant layer.

  The sealant layer is a heat-sealable resin used for the heat-sealable resin layer, and specifically, a resin film or sheet that can be melted by heat and fused to each other can be used. Low density polyethylene, medium density polyethylene, high density polyethylene, linear (linear) low density polyethylene polymerized using a metallocene catalyst, ethylene-α / olefin copolymer polymerized using a metallocene catalyst, Polypropylene, ethylene-vinyl acetate copolymer, ionomer resin, ethylene-acrylic acid copolymer, ethylene-ethyl acrylate copolymer, ethylene-methacrylic acid copolymer, ethylene-methyl methacrylate copolymer, ethylene-propylene Copolymer, methylpentene polymer, polybutene polymer, polyethylene or polymer Polyolefin resins such as pyrene modified with unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, polyvinyl acetate resins, poly (meta ) Acrylic resins, polyvinyl chloride resins, and other resins can be used alone or in admixture of two or more.

  Among the heat-sealable resins that make up the above sealant layer, those in which linear (linear) low-density polyethylene is polymerized using a single site catalyst such as a metallocene catalyst have a narrow molecular weight distribution and are copolymerized. Since the ratio is also stable, in addition to heat seal stability, it is excellent in content resistance, stress cracking resistance, low-temperature heat sealability, hot sealability, and the laminated tube material for liquid packaging of the present invention It can be suitably used for the sealant layer.

  In addition to the above-mentioned linear (linear) low density polyethylene, the heat seal resin layer includes CPP (unstretched polypropylene), LDPE, depending on the contents to be filled, the heat treatment after filling, the distribution conditions, and the like. Select an appropriate film or extruded coating layer such as ethylene / α-olefin copolymer, ethylene / vinyl acetate copolymer, ethylene / acrylic acid copolymer, ethylene / acrylic acid ester copolymer, ionomer, and polyester resin. Can be used.

  Although the lamination | stacking method of a sealant layer is not specifically limited, It can laminate | stack by extrusion-coating the thermoplastic resin which forms a sealant layer on a printing layer. Further, the film made of the thermoplastic resin may be laminated by a dry lamination method or a sandwich lamination method.

  As an adhesive for dry lamination, urethane adhesive, polyester polyurethane adhesive, polyester adhesive, polyether adhesive, vinyl adhesive, acrylic adhesive, epoxy adhesive, and the like can be used. . Further, any thermoplastic resin can be used as the adhesive resin for sandwich lamination.

In the present invention, the sealant layer can be formed by using the heat sealable resin as described above and extruding and laminating by an extrusion laminating method or the like.
In the present invention, the thickness of the sealant layer can be appropriately set according to the contents filled in the laminated tube material for packaging, but is preferably about 20 to 200 μm, more preferably 100 to 150 μm.

In addition, for example, a primer coat layer, an undercoat layer, an anchor coat layer, or the like may be provided between the printing base layer and the sealant layer.
As the anchor coat layer constituting the laminated tube material for packaging of the present invention, either a solvent type or an aqueous type can be used.

Therefore, (chlorinated) polypropylene, modified polyolefin, ethyl vinyl alcohol, polyethylene imine, polybutadiene, polyurethane, polyester polyurethane emulsion, polyvinyl chloride emulsion, urethane acrylic emulsion, silicon acrylic emulsion, vinyl acetate acrylic emulsion , Acrylic emulsion, styrene-butadiene copolymer latex, acrylonitrile-butadiene copolymer latex, methyl methacrylate-butadiene copolymer latex, chloroprene latex, polybutadiene latex rubber latex, polyacrylate latex, polyacrylate Vinylidene chloride latex, polybutadiene latex, or carboxyl modification of these latexes And water-soluble substances such as polyvinyl alcohol, water-soluble ethylene-vinyl acetate copolymer, polyethylene oxide, aqueous acrylic resin, aqueous apoxy resin, aqueous cellulose derivative, aqueous polyester and aqueous lignin derivative, etc. An emulsion or dispersion anchor coat agent is used. For example, when the outermost layer is a polyethylene-based melt-extruded resin layer, a polyethylene-based or modified polyolefin-based emulsion or dispersion is preferable in consideration of adhesiveness to the substrate.
In the use as a packaging material, when it becomes the innermost layer in contact with the contents, polyolefin resins such as polyethylene and polypropylene are preferably used.

  In particular, when the substrate is made of a PET film and a urethane resin is used as the binder resin in the ink, polyethylene is used as the resin for forming the sealant layer, and this is applied to the printing base layer. By forming a laminated tube material for packaging having a layer structure laminated by the dry laminating method (DL), a suitable laminate strength relationship between the base material or the sealant layer and the printed layer, that is, the laminated tube material for packaging is used for the tube. Due to the strength of the laminate to be formed, the adhesion of the tube material does not occur when printing with laser light, and a convex shape is formed between the substrate and the printed layer so that a clear printed image can be obtained by laser irradiation. It is necessary to set the strength so that it can be raised.

(Gas barrier layer)
In the present invention, a metal foil or a metal oxide vapor deposition layer can be used as the barrier layer. As the barrier layer, a base film with a transparent vapor deposition layer in which a transparent vapor deposition layer of an inorganic oxide is formed on the base film layer can also be used. A vapor deposition layer may be formed and provided, or a resin film having a transparent vapor deposition layer may be laminated and used. Moreover, when using metal foil, such as aluminum foil, as a barrier layer, metal foil can be arrange | positioned on the opposite side to the base material of a printing foundation layer. As the barrier layer, a barrier resin coating film such as vinylidene chloride resin or ethylene vinyl alcohol copolymer resin can be used on the base film 2 as necessary.

As the inorganic oxide vapor-deposited film, any transparent thin film obtained by making a metal oxide amorphous can be used. For example, silicon (Si), aluminum (Al), magnesium (Mg), calcium (Ca), potassium (K), tin (Sn), sodium (Na), boron (B), titanium (Ti), lead (Pb ), Zirconium (Zr), yttrium (Y), and other metal oxides that are made amorphous (amorphous) can be used.
Examples of suitable materials for packaging materials include thin films obtained by making metal oxides such as silicon (Si) and aluminum (Al) amorphous.

  The vapor deposition layer which comprises the gas barrier layer of this invention is demonstrated. In the present invention, the vapor deposition layer may be, for example, a physical vapor deposition method (Physical Vapor Deposition method, PVD method) such as a vacuum vapor deposition method, a sputtering method, an ion plating method, an ion cluster beam method, or a plasma chemical vapor deposition method. It can be formed using a chemical vapor deposition method (Chemical Vapor Deposition method, CVD method) such as a thermal chemical vapor deposition method or a photochemical vapor deposition method.

  In the present invention, the inorganic oxide vapor deposition film is specifically a vacuum vapor deposition method in which a metal oxide is used as a raw material, and this is heated and vapor deposited on a resin film or sheet, or a metal as a raw material. Or oxidation reaction vapor deposition method that uses metal oxide, oxidizes by introducing oxygen and deposits on resin film or sheet, plasma-assisted oxidation reaction vapor deposition method that promotes oxidation reaction with plasma, etc. Can be used to form an amorphous thin film of inorganic oxide. In the above, the heating method of the vapor deposition material can be performed by, for example, a resistance heating method, a high frequency induction heating method, an electron beam heating method (EB), or the like.

In the present invention, the thickness of the metal or metal oxide thin film layer varies depending on the type of metal or metal oxide used, but is, for example, in the range of 50 to 3000 mm, preferably in the range of 100 to 1000 mm. It is desirable to select and form arbitrarily. In the present invention, the thin film layer of metal or metal oxide may be not only one layer but also a laminated body in which two or more layers are laminated, and the metal or metal oxide to be used Can be used as a single type or a mixture of two or more types to form a thin film layer made of different materials.
For the laminated tube material for packaging of the present invention, a silicon oxide vapor-deposited film, particularly a silicon oxide vapor-deposited film formed by a CVD method can be preferably used.

(Printing with laser light)
In the present invention, printing is performed using a YAG (yttrium (Y), aluminum (A), garnet (G)) laser beam (wavelength = 1.064 μm) or a YVO ₄ (yttrium vanadate) laser beam (wavelength = 1.64 μm). It is preferable to perform using. These lasers have the property of transmitting through a transparent body, and by utilizing this property, the generation of smoke and the like during printing can be suppressed, and the color density and the effect on the film can be adjusted. . As a result, it is possible to form a very clear laser-printed image having no holes or the like even when a laser-printed image is formed.

  By irradiating these lasers from the base material side of the laminated tube material for packaging, the output of the laminated tube material for packaging is low output, and the ink component of the printing layer is gasified while minimizing damage to the film. Carbonization is performed to form a gap between the substrate and the printing layer, and a laser printing image can be efficiently formed on the surface of the printing layer. And the thing excellent in the visibility from the base-material side is obtained by forming a laser-printed image on the printing layer surface.

In the present invention, the pulse condition for performing such printing is, for example, an average output of 0.8 to 5.0 W, more preferably 1.5 to 3.0 W, Q in a YVO ₄ laser machine (Keyence MD-V9600). Pulse conditions with a switch frequency of 10 to 30 KHz and a scan speed of 300 to 4000 mm / s, more preferably 2500 to 3500 mm / s are used. By performing printing under these conditions, high-speed printing is possible without making holes in the multilayer laminated film for laser printing, and a clear printed image can be obtained.

(Printed body with laser light)
In the printing process on the laminated tube material for packaging according to the present invention, even if the average output of the laser is set low or the scan speed is set high, a clear print image, for example, a thick and clear character is printed. be able to.

  In the printed body of the present invention, the diameter of the gap formed between the substrate and the printed layer by laser spot irradiation is desirably 40 μm to 1 mm, more preferably 400 to 700 μm. A clear printed image can be obtained by spreading the carbonized ink component in the gap and using the white ink of the printing base layer as a background. If the diameter of the air gap is smaller than this, the printed image is lost or the line width is reduced, and visibility is lost. Conversely, if it is larger than this, it is not preferable because the image is crushed.

In the present invention, the laser-printed image includes, but is not limited to, letters, numbers, symbols, patterns, and the like.
The printed body obtained by printing on the laminated tube material for packaging and the packaging tube of the present invention can be suitably applied as the laminated tube printed body for packaging having the laminated structure of the present invention.

  In the laminated tube material for packaging according to the present invention, the printed layer is printed on a region composed only of white ink that functions as a printing underlayer that can be printed by laser light, and the printed layer is not printed by the laser light. The area where the pattern printing layer provided with the desired color printing layer and the printing ground part are superposed is adhesive to the substrate even in an atmosphere under wet heat, has a high lamination strength, and peels off as a laminated tube material for packaging. In combination with the fact that no occurrence occurs, clear prints can be reliably obtained in the print area.

(Packaging tube)
A packaging tube using the above laminated tube material for packaging will be described. A bag-like container body made of a packaging tube uses a laminated material made of the above-mentioned laminated tube material for packaging, folds the laminated material, and stacks the heat-sealable resin layers facing each other. The package can be manufactured by heat-sealing the end portion to form a cylindrical package, then sealing the bottom to fill the contents, and sealing the top.

  As the bag making method, the laminated material as described above is folded or overlapped so that the inner layer faces to face each other, and the peripheral end portion thereof is, for example, a side seal type, a two-side seal type, a palm joint attachment. The packaging tube can be manufactured by heat sealing in a heat sealing form such as a sealing type (pillow sealing type) or a pleated sealing type. In the above, as a heat sealing method, for example, a known method such as a bar seal, a rotary roll seal, a belt seal, an impulse seal, a high frequency seal, and an ultrasonic seal can be used.

EXAMPLES The present invention will be specifically described below with reference to examples, but these do not limit the present invention.
[Example 1]
On the side surface of one vapor deposition layer of a polyethylene terephthalate film (base material) having a transparent silicon oxide vapor deposition layer having a thickness of 12 μm, a pattern printing layer was applied using a color ink by a gravure roll coating method. On top of that, a laser coloring ink containing 5% by weight of bismuth oxide (in terms of the solid content of the ink composition) as a coloring material and 15% by weight of titanium dioxide as a white ink pigment was applied to the entire surface by a gravure roll coating method. A laser color ink printing layer was provided. Next, an adhesive layer is provided on the printed layer by a dry lamination method (DL) using a two-component curable polyester polyurethane adhesive, and a 150 μm thick linear low density polyethylene film is laminated as a sealant layer. did. Similarly, a linear low-density polyethylene film sealant layer having a thickness of 150 μm was laminated as an outermost layer on the side opposite to the printed layer of the PET film by the DL method. Thereby, the linear low density polyethylene film sealant layer / adhesive layer / PET film / transparent silicon oxide vapor deposition layer / picture color ink printing layer / laser color ink printing layer / adhesive layer / linear low density of the present invention. A laminated tube material for packaging having a layer structure of a polyethylene film sealant layer was obtained.

[Example 2]
As in Example 1, a pattern printing layer and a laser coloring ink layer were sequentially applied to one surface of a PET film having a thickness of 12 μm by using a gravure roll coating method using a color ink and a laser coloring ink layer. Was provided. Next, an aluminum foil having a thickness of 9 μm and a linear low density polyethylene film sealant layer having a thickness of 130 μm were sequentially laminated on the printed layer by the DL method. Further, a linear low density polyethylene sealant layer having a thickness of 130 μm was laminated on the side opposite to the printed layer of the PET substrate by the DL method. Thereby, the linear low-density polyethylene film sealant layer / adhesive layer / PET film / pattern color ink printing layer / laser color ink printing layer / adhesive layer / AL (barrier layer) / adhesive layer / straight of the present invention. The laminated tube material for packaging of the present invention was produced in the same manner as in Example 1 except that a laminated tube material for packaging having a layer structure of a chain-like low density polyethylene film sealant layer was obtained.

[Examples 3 and 4]
A laser color ink layer was applied by the gravure roll coating method in the same manner as in Example 1 or 2 using a laser color ink in which 3% by weight of copper / molybdenum composite oxide was further added to the laser color ink in Example 1 or 2. The linear low density polyethylene film sealant layer / adhesive layer / PET film / transparent silicon oxide vapor deposition layer / pattern color ink printing layer / Laminated tube material for packaging having a layer structure of laser color ink printing layer / adhesive layer / linear low density polyethylene film sealant layer, or linear low density polyethylene film sealant layer / adhesive layer / PET film / pattern Color ink printing layer / Laser color ink printing layer / Adhesive layer / AL (barrier layer) / Adhesive layer / Linear low density To obtain a packaging laminate tube material having a layer structure of polyethylene film sealant layer.

[Comparative Example 1]
Instead of the laser coloring ink in Example 1, CLIOS (urethane-based resin binder) manufactured by DIC Graphics Co., Ltd. and white ink of Lamic FB701 white (D) (urethane-based resin binder) manufactured by Dainichi Seika Kogyo Co., Ltd. were used. In the same manner as in Example 1, unstretched linear low-density polyethylene film sealant layer / adhesive layer / PET film / transparent silicon oxide vapor deposition layer / pattern color ink printing layer / laser color ink printing layer / adhesive layer / Two types of laminated tube materials for packaging having a layer structure of an unstretched linear low density polyethylene film sealant layer were produced.

[Comparative Example 2]
Instead of using laser coloring ink in Example 2, CLIOS (urethane-based resin binder) manufactured by DIC Graphics Corporation and white ink of Lamic FB701 white (D) (urethane-based resin binder) manufactured by Dainichi Seika Kogyo Co., Ltd. were used. In the same manner as in Example 2, unstretched linear low-density polyethylene film sealant layer / adhesive layer / PET film / picture color ink printing layer / laser color ink printing layer / adhesive layer / AL (barrier layer) A laminated tube material for packaging having a layer structure of / adhesive layer / unstretched linear low density polyethylene film sealant layer was produced.

[Laser printing method]
About each laminated tube material for packaging obtained in Examples 1 to 4 and Comparative Examples 1 and 2, YVO ₄ laser light was irradiated from the base material side under the following conditions to form a laser print image to obtain a printed body. Obtained.
・ Laser irradiation condition YVO ₄ laser machine (manufactured by Keyence Co., Ltd., MD-V9600) For example, average output 1.8W, Q switch frequency 10KHz, scan speed 3000mm / s, comparative example average output 3.0W, Q switch frequency 10KHz, scan speed 1000mm / s.

(Evaluation method)
For each laminated tube material for packaging shown in the Examples and Comparative Examples, the expiration date is printed on the laser color ink base layer by actually irradiating the laser beam, and the clarity and retention of the characters printed there The print characters such as the thickness and color density were comprehensively evaluated, the print state was evaluated by visibility, and the appearance after laser irradiation was confirmed.

[Evaluation]
In both Examples and Comparative Examples, the printed state of the laser printed image obtained under the above laser irradiation conditions was evaluated by visibility. Moreover, the external appearance after laser irradiation was confirmed.

  In the laminated tube material for packaging of the example, even when printing is performed with low irradiation energy (1.8 W, scan speed 3000 mm / s), the print density is high and does not disappear even if it is rubbed. A laser printing with good visibility was obtained. In particular, the system in which the copper / molybdenum composite oxides of Examples 3 and 4 were added showed a color development superior to the system of the color developing material alone, and the copper / molybdenum composite oxide serves as the color developing material and further functions as a color developing aid. Laser printing with good properties and good visibility was obtained.

  On the other hand, the packaging laminated tube materials of Comparative Examples 1 and 2 could not obtain a print with good visibility even when the white ink base print layer was irradiated with laser. When laser irradiation was performed with high energy (3 W, scan speed 1000 mm / s), color was developed so that a visible print could be obtained. However, the printing was blurred, the packaging material was damaged, the visibility was inferior, and the proper printing range was narrow.

1. Base material 2. 2. Transparent vapor deposition layer Print layer 3a. Pattern printing layer 3b. Print base layers 4a, 4b. 4. Sealant layer Metal foil A. Print section

Claims (9)

A laminated tube material for packaging having a sealant layer on both outermost surfaces of a laminated structure having a gas barrier layer and laminated in the order of a substrate, a pattern printing layer, and a printing base layer, the pattern printing layer and the laser printing layer In the laminated tube material for packaging having a printed layer in which a region where only the printing foundation layer is overlapped and a region where only the printing foundation layer is formed,
The printing underlayer is a laminated tube material for packaging, which is a coloring ink layer that can be printed with laser light, including a coloring material that develops color when irradiated with laser light.   The laminated tube material for packaging according to claim 1, wherein the coloring material is a bismuth-based compound.   The laminated tube material for packaging according to claim 1 or 2, wherein the bismuth compound is one or more compounds selected from bismuth hydroxide, bismuth oxide, bismuth carbonate and bismuth nitrate.   The laminated tube material for packaging according to any one of claims 1 to 3, wherein the color ink contains one or more compounds selected from a metal oxide or a composite oxide or a group thereof.   The laminated tube material for packaging according to any one of claims 1 to 3, wherein the color ink contains one or more compounds selected from a copper compound, a molybdenum compound, or a group thereof.   The laminated tube material for packaging according to any one of claims 1 to 5, wherein the gas barrier layer is a gas barrier transparent vapor deposition layer, and is a transparent vapor deposition film having a gas barrier transparent vapor deposition layer on a substrate. .   The laminated tube material for packaging according to any one of claims 1 to 5, wherein the gas barrier layer is an aluminum metal layer and is located on the side opposite to the substrate of the printing base layer.   The packaging tube using the laminated tube material for packaging of any one of Claims 1-7. The ink which developed color by irradiating the laminated tube material for packaging according to any one of claims 1 to 7 or the laminated tube for packaging according to claim 8 with YAG or YVO ₄ laser light from the substrate side. A tube laser printing body for packaging having a laser-printed image in which a color development region of the composition extends to a boundary between the base material and the printing base layer.

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