JP2015127109A - Laminate stick material for packaging, stick for packaging using the same, and laser printed body - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminate stick material for packaging, a laminate stick for packaging, and a printed body comprising the laminate stick, on which a thick, easily readable and sharp print line is formed by irradiation with laser light at a low output level not to damage a film.SOLUTION: The laminate stick material for packaging comprises at least a substrate, a pattern printed layer, a color developing ink layer, and a sealant layer, in which a region comprising only the color-developing ink layer in direct contact with the substrate is used as a laser print region. The color developing ink layer is formed from an ink composition comprising a bismuth compound as a color developer that develops a color by irradiation with laser light, and other inorganic compounds, and is printable as the layer develops a color by laser light. The laminate stick material for packaging is printable by use of a YAG or YVO4 laser or a fiber laser.

Description

  The present invention has strength and waist required as a laminated stick material for packaging, is excellent in gas barrier properties and content resistance against oxygen, water vapor, etc., from pharmaceuticals, cosmetics, toothpaste, mayonnaise, kneaded wasabi, kneaded In addition, it is suitable for seasonings such as ketchup and others, or creams such as whipped cream, food and drink, and other filling and packaging, and a laminated stick material for packaging which can be printed by laser light, and the same. The present invention relates to a packaging stick and a laser printing packaging stick having a laser-printed image on them.

Conventionally, on the surface of packaging containers such as cans, bottles, plastic bottles, packaging bags, and packaging materials for packaging these packages, in addition to forming a pattern such as letters, symbols, drawings, etc. in advance with a printing ink layer, for example, A method of printing additional information such as date of manufacture, manufacturer, product name, expiration date, etc. later with ink or the like 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.
Therefore, 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 required for each packaging material.

  Packaging bodies such as packaging containers, packaging bags, and packaging materials have a printing layer formed in advance on most of the front and back surfaces, and there are fewer margins than containers such as boxes and cans. It is difficult to secure the display area. On the other hand, when the ink layer is displayed on the outer surface of the packaging bag over the existing print layer, the appearance of the packaging bag is impaired, and the ink layer display There are inconveniences such as difficult to read.

In recent years, stick packaging materials such as liquid stick packaging have been used in various fields because the contents can be drunk without water, are easy to drink for the elderly, and are also suitable for carrying. . In particular, it is used mainly in the field where oral medicine is applied.
In addition, from such a use form, easy-openability and easy tearability of the packaging material are required, and furthermore, good printing processability, durability and designability as a packaging material, and low-cost production, etc. Is required.
Laminate for packaging in which a surface polyolefin-based resin layer, an intermediate layer or gas barrier film, and a back-surface polyolefin-based resin layer are sequentially laminated as a packaging laminated stick suitable for filling and packaging contents such as pharmaceuticals, cosmetics, and foods Stick material is known.
And, for example, the surface of the surface polyolefin resin layer that is the outermost layer at both ends of the laminated stick material for packaging and the surface of the back surface polyolefin resin layer that is the innermost layer are overlapped, and the opposite surfaces are heat sealed. A cylindrical body is manufactured, a head composed of a mouth, a shoulder, etc. is formed in one opening of the cylindrical body, and if necessary, a cap is screwed into the mouth and a stick container Manufacture the packaging product consisting of the stick container by filling the contents from the other opening of the cylindrical body constituting the stick container and sealing the opening to form the bottom seal part. doing.

In such a packaging laminated stick, a printing layer for displaying predetermined items such as the product name, manufacturer, seller, date of manufacture, etc. is formed on the outer peripheral surface of the body portion together with a desired pattern. ing. The printing 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 laminate stick container. Thereafter, this and the material constituting the inner surface resin layer and the like are laminated to produce a laminated material, and then a laminated stick container is produced using the laminated material.

As described above, when printing additional information, necessary characters, symbols, etc. are displayed on the surface sealant layer of the packaging laminated stick material or packaging stick, and the binder of the ink layer is the same as that of the heat seal layer. The printing area is limited.
Especially for packaging laminated sticks, which are packaging bodies with a narrow printing area and limited printing layers, for additional packaging, with appropriate information accurately and clearly printed at any position and with improved visibility It is desired to provide a laminated stick material, a stick using the same, and a printed body.
In addition, since the packaging laminated stick is in direct contact with food or the like, when an ink layer is displayed on the outer surface of the stick 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 are 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 predetermined patterns and fixed information on packaging containers and packaging materials, printing layers can be formed between layers by inkjet printing or general-purpose printing methods, but additional information that changes the information is set in advance. May not be possible, and may be printed on the surface of the package. For this reason, printing cannot be performed properly and accurately, for example, due to the dryness of printing, compatibility between the package and ink, contact with the printing surface of the package that moves at high speed, etc. It is a problem.

In order to solve these problems, the printing of additional information by laser irradiation has attracted attention.
In laser printing, a laser is directly applied to the surface of a plastic molded product or the like formed on a resin composition in which a color former that develops color by laser light is contained in a resin, or such a resin composition layer is formed on the surface. The printed image is formed, and there is a problem that the printed image is faded or erased by rubbing the surface of the laser printed image.

As a technique for printing with a laser beam, printing on a film by irradiating a YAG laser or a YVO4 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 YVO4 laser. Therefore, it is also known to use such normally used 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.
Therefore, there is a problem that a hole is formed in the base film due to 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 solves a conventional problem in printing additional information at the time of packaging in a packaging material having a wide variety of laminated structures, particularly in a packaging laminated stick material and a packaging laminated stick having a gas barrier property. By irradiating with a low-power laser that is made of an inexpensive material, easy to manufacture, easy to change the printing position, and does not damage the base film A laminated stick material for packaging which has an appropriate thickness and is easy to read, and which clearly and accurately prints additional information at an arbitrary position and has improved visibility. An object of the present invention is to provide a laminated stick for packaging, and a printed body thereof.
In addition, the present invention is a packaging laminate that exhibits good easy-openability and easy tearability, printability, durability and designability as a packaging material, and production at low cost. The purpose is to provide stick materials and the like.

As a result of various researches on laminated stick materials and the like to which gas barrier properties have been imparted, the present inventors have solved the conventional problems in printing additional information while packaging. For example, using a color ink having a low-cost laser coloring material that develops color using a white ink and a low-power laser beam, and a coloring ink as a printing base layer of a printing layer generally applied to a package or a packaging material, that is, The color ink layer is utilized.
And, by forming a region of only the color ink layer that can be printed with low-power laser light, and irradiating the region with the low-power laser light from the base film layer side that is the viewing side, An ink component that has developed a color development area by spreading the colored ink component only on the surface of the printed image area between the print layer and the laser color former that has developed color at an appropriate and accurate position on the color ink layer. Thus, a laminated stick material for packaging capable of forming a clear laser-printed image having an appropriate thick line has been found.

The present invention is a laminated stick material for packaging having a sealant layer on both outermost surfaces of a laminated structure in which a base material, a pattern printing layer, and a color ink layer are laminated in this order and a gas barrier layer is provided.
In the laminated stick material for packaging having a printed layer in which a pattern printed layer and a colored ink layer serving as a laser printed layer overlap each other and a printed layer formed with only a colored ink layer, the colored ink layer is a laser beam. A color ink layer that can be printed by a laser beam containing a color developing material that develops color upon irradiation with, in particular, a bismuth-based compound, and further selected from metal oxides or composite oxides, or copper-based compounds or molybdenum-based compounds. It is a layer made of an ink composition containing one kind or two or more kinds of compounds. And, only on the surface of the color ink layer between the base material and the color ink layer on the visual recognition side of the laminated stick material for packaging, it is a laminated stick material for packaging by forming a color development area by laser light, The above object can be achieved.

The present invention is characterized by the following points.
1. A laminated stick material for packaging having a sealant layer on the outermost surfaces of both sides of a laminated structure in which a substrate, a pattern printing layer, and a color ink layer are laminated in this order, and a gas barrier layer is provided. In the laminated stick material for packaging having a region where only the color ink layer is formed and a layer formed only with the color ink layer, the color ink layer is formed by a laser beam containing a color material that develops color when irradiated with a laser beam. Laminated stick material for packaging, which is a printable layer.
2. The laminated stick material for packaging according to 1 above, wherein the coloring material is a bismuth compound.
3. The laminated stick material for packaging according to 1 or 2 above, wherein the bismuth compound is one or more compounds selected from bismuth hydroxide, bismuth oxide, bismuth carbonate and bismuth nitrate.
4). 4. The laminated stick material for packaging according to any one of 1 to 3 above, wherein the coloring ink layer contains one or more compounds selected from metal oxides or composite oxides or a group thereof.
5. 4. The laminated stick material for packaging according to any one of 1 to 3 above, wherein the color ink layer contains one or more compounds selected from a copper compound, a molybdenum compound, or a group thereof.
6). The laminated stick material for packaging according to any one of 1 to 5 above, 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.
7). 6. The laminated stick material for packaging according to any one of 1 to 5 above, wherein the gas barrier layer is an aluminum metal foil and is located on the side opposite to the substrate of the color ink layer.
8). The laminated stick material for packaging according to any one of 1 to 7 above, which has an easy-open property.
9. A packaging stick using the packaging laminated stick material according to any one of 1 to 8 above. 10. The ink composition colored by irradiating the laminated stick material for packaging according to any one of 1 to 8 or the laminated stick for packaging according to 9 with YAG or YVO4 laser light or fiber laser from the substrate side. Is a stick laser printing body for packaging having a laser print image spreading on the surface of the base material and the coloring ink layer.

The packaging laminated stick material of the present invention does not need to use expensive special ink for laser printing. For example, it uses a general-purpose white ink that is commonly used as a base for printing a packaging film, and has a low A colored ink layer formed as a white ink layer that can be printed by the output laser beam is formed on the entire area of the laminated sticky material for packaging, and the required pattern printing layer is layered on the substrate side of the colored ink layer. By forming a laminated stick material for packaging in which a laser printing layer is formed by the laminated structure, it is possible to provide a region of only the color ink layer, that is, the printing underlayer, at an arbitrary position, and a low-power laser in the region. To develop a laser print area.
The present invention uses a color developing material, particularly a color developing ink layer containing a bismuth-based compound, or a metal oxide, a composite oxide, copper, or the like for a commonly used white ink pigment as a base for printing a package. By containing a compound based on tungsten or a compound based on tungsten, it is possible to develop color with a low-power laser. Further, since the additional information is laser-printed, the coloring ink layer can function as a base layer of the pattern printing layer, and the packaging laminated stick can be efficiently manufactured from an inexpensive material.

By irradiating the packaging laminated stick material of the present invention with YAG or YVO4 laser light or fiber laser from the substrate side, the ink component containing the coloring material that forms the printed layer is colored by low-power laser irradiation. Since it is partially carbonized and the color development area spreads at the boundary between the base material and the color ink layer, the output is weak, that is, it is not necessary to increase the laser output until the entire print layer is evaporated, and as a base. Due to the contrast with the white ink base, a laser-printed image with excellent visibility from the substrate side can be clearly formed.
Further, in the printed body of the present invention, the laser printed image is formed not inside the film surface but inside, that is, between the substrate and the printing layer. Therefore, since this image is excellent in wear resistance, disappearance due to rubbing or the like can be effectively prevented, and change of the additional information can be prevented.

From these points, according to the laminated stick material for packaging of the present invention and the packaging stick using the same, additional information can be formed in an area other than the heat-sealed portion of the stick. 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.
Ink contact with the surface of the laminated sticky material for packaging by forming the printable underlayer of the colored ink of at least the inner layer other than the layer in contact with the contents of the laminated sticker for packaging into a printable layer by laser light irradiation It is possible to print without sacrificing, and it is possible to obtain a product excellent in hygiene without dissolving the ink printed by the oil and fat derived from the contents of the packaging laminated stick material.
Moreover, the manufacturing process of the laminated stick material for packaging is the same as a normal printing process, and it is not necessary to provide an additional layer for laser printing, so that the manufacturing process can be simplified.

It is a schematic sectional drawing which shows the example about the laminated constitution of the laminated stick material for packaging of this invention. It is a schematic sectional drawing which shows another example about the laminated constitution of the laminated stick material for packaging of this invention. FIG. 1 is a schematic cross-sectional view showing an example of the layer structure of a printed body in which the laminated stick material for packaging according to the present invention shown in FIG. is there.

  The laminated stick material for packaging according to the present invention, the laminated stick 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.

As shown in FIG. 1, the laminated stick material for packaging of the present invention has a sealant layer on the outermost surfaces on both sides of a laminated structure in which a base material, a pattern printing layer, and a coloring ink layer are laminated in this order, and a gas barrier layer is provided. A packaging laminated stick material having a printed layer and a printed layer in which only a colored ink layer is formed in a region where the color printing ink layer that becomes the pattern printing layer and the laser printing layer is overlapped, The color ink layer is basically composed of a laminated stick material for packaging, which is a white ink layer that can be printed by laser light.
In another embodiment, as shown in FIG. 2, the pattern printing layer may be a pattern printing layer having the same or different ink and excellent in 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 stick material of the present invention with a YAG or YVO4 laser from the substrate side. On the surface, there is a printed part 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 laminate strength (adhesion strength) with the printing foundation layer is a pattern printing layer. Any resin film that is somewhat smaller than the laminate strength can be used.
Specifically, it becomes a basic material, and after printing, it forms a surface protective layer and can be seen through a laser-printed image, etc., so it has excellent mechanical, physical, and chemical strength. It is possible to use a resin film that has excellent puncture resistance and the like, and is excellent in heat resistance, moisture resistance, transparency, and the like.

The resin film in the present invention may be selected from various resin films such as polyolefin resin such as polyethylene resin and polypropylene resin, cyclic polyolefin resin, fluororesin, polystyrene resin, polyester resin, polyamide resin and cellulose resin. it can.
When forming a film 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, mold release, etc. Various plastic compounding agents and additives can be added for the purpose of improving and modifying properties, flame retardancy, antibacterial properties, electrical properties, strength, laminate strength, etc. Depending on the purpose, from a very small amount to several tens of weight% can be arbitrarily added.
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 coloring ink layer and the substrate, a desired surface treatment can be applied to any surface 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 above resin film, for example, one or more of the above resins are used, and a film forming method such as an extrusion method, a cast molding method, a T-die method, a cutting method, an inflation method, etc. Films of various resins are produced by a method of forming a film of each of the above resins alone, and further by using two or more types of resins and mixing and forming a film before forming the film, Furthermore, for example, any of a stretched film stretched in a uniaxial direction or a biaxial direction using a tenter system, a stickler system, or the like can be used.

Further, 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, etc., and if it is too thick, there is also a disadvantage that the cost increases, If it is too thin, the strength, puncture resistance, etc. will decrease, which is not preferable.
In the present invention, considering the above points, 10 μm to 100 μm, preferably 10 μm 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., especially 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.

(Give easy opening and tearing)
Since the laminated stick material for packaging of the present invention is required to be easily opened and tearable when used, a material suitable for such a demand can be used as the substrate.
As such a material, for example, it is preferable to use an easily openable film that can be adjusted so that the peel strength at a test speed of 100 mm / min is less than 5 N / 15 mm. As such an easy-open film, a polyolefin film mainly composed of polyethylene and / or polypropylene can be preferably used.
In particular, a single layer structure packaging material made of heat-sealable polyethylene terephthalate, or a multilayer structure packaging material in which a heat-sealable polyethylene terephthalate film and another film are laminated, or a multilayer structure packaging in which the intermediate layer is also a polyethylene terephthalate film Materials are preferably used.
In addition, an ionomer resin can be combined to improve the tearability of the ethylene polymer.
Furthermore, as an easy-opening means, a half-cut line, a notch at the end, or a large number of fine holes may be formed at the opening position on the tip side of the spout.

(Print layer)
In the present invention, the printing layer includes at least a pattern printing layer and a coloring ink layer, and is a layer provided by laminating a commonly used color ink and laser coloring ink by printing or coating on a substrate. is there.
In the present invention, the pattern printing layer is formed by forming a desired printing pattern such as a character, a figure, a symbol, a pattern, or a pattern on a base material using a normal printing method.
On the other hand, the coloring ink layer of the present invention is one that develops color with laser light, and the coloring ink layer is preferably a coloring ink containing a coloring material that develops color with a low-power laser beam. An inorganic compound is used as the component. A preferable pigment component includes an inorganic compound such as a white pigment.
The colored ink layer can also provide a clear printed image by providing another colored ink layer on the colored ink layer and multilayering the printing foundation layer.

  Various materials can be used as the coloring material that develops color with the laser beam used in the present invention. Colorants such as dyes and pigments, clays, etc. can be used. Specifically, yellow iron oxide, inorganic lead compounds, manganese violet, cobalt violet, mercury, cobalt, copper, nickel and other metal compounds, pearls Luster pigment, silicon compound, mica, kaolin, silica sand, diatomaceous earth, talc, titanium oxide coated mica, tin dioxide coated mica, antimony coated mica, tin + antimony coated mica, tin + antimony + titanium oxide One kind or two or more kinds of coated mica can be used.

In the present invention, a bismuth-based compound is particularly essential as a coloring material that develops color with a low-power laser beam.
Examples of the bismuth compounds include bismuth nitrates such as bismuth oxide, bismuth nitrate and bismuth oxynitrate, bismuth halides such as bismuth chloride, bismuth oxychloride, bismuth sulfate, bismuth acetate, bismuth citrate, bismuth hydroxide, Examples thereof include bismuth titanate, and among them, bismuth nitrate and bismuth hydroxide are desirable from the viewpoint that they are easily available and inexpensive.
A bismuth-type compound can contain 1 type, or 2 or more types of compounds. In addition, the present invention uses a color developing material containing at least a bismuth compound, and other than the bismuth compound may be used in combination as long as it is a color developing material that develops color by laser light.

The present invention uses a coloring material containing at least a bismuth-based compound, and further uses a coloring material that develops color by laser light and / or an inorganic compound to increase coloring efficiency.
As the inorganic compound, a metal oxide, a composite oxide, a metal salt, or one or more compounds thereof are used.
Even with low-power laser light irradiation, by using an inorganic compound in combination, the inorganic compound also functions as a coloring material, increasing the heat generation efficiency and helping the coloring material to develop color, or white that contains the coloring material and white pigment It is preferable to add an inorganic compound because it functions to increase the whiteness of the ink.

In the present invention, a white ink pigment used as a general-purpose printing foundation layer can be used. Preferably, the metal oxide may 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. it can.
A particularly preferred metal oxide is titanium oxide.

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 be suitably used because they also function as color forming materials. it can.
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 material containing a bismuth-based compound as a color forming material of the color developing ink layer, and a material containing 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, color development and printing are insufficient and unclear. Also, as the content increases, the color of the print becomes deeper. However, even if it is 30% by weight or more, the difference in visibility due to the increase in density is not recognizable. It is not preferable because the base layer becomes hard, cracks, strength is reduced, and the pigment color of the coloring material itself that develops color by irradiation with laser light colors the printing base layer.

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 and printing are inadequate and unclear, and if it exceeds 65% by weight, the increase in the inorganic compound increases the cost, and the printing underlayer becomes brittle, leading to a decrease in strength.

The color developing ink layer preferably has a thickness of 0.05 to 20 μm, more preferably about 0.1 to 7 μm. When the film thickness is less than 0.05 μm, color development or printing due to a color developing material that develops color by laser light irradiation may be insufficient or unclear.
On the other hand, as the film thickness increases, the color of the print becomes darker. However, if the film thickness exceeds 20 μm, the color development and printing by the color development material that develops color by laser light irradiation is sufficient, but a large amount of color development material is used. For this reason, it is not preferable for reasons such as an increase in cost, a reduction in the strength of the printing base layer, and a pigment color of the coloring material itself that develops color by laser light irradiation. 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.

The coloring ink of the coloring ink layer of the present invention can be formed by diluting with a conventional solvent as 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 printed image is formed on the color ink layer, a colored underlayer can be further provided on the 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 underlayer, the color and the type of pigment are arbitrarily selected so that the print can be clearly seen by the color that develops when the color ink layer is irradiated with laser light, the color of the color layer itself by laser light, and the like. For example, when the color ink layer is highly transparent gray, the color developed by the laser 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. 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 a coloring ink layer can be formed by printing or coating on a substrate. 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, and a lubricant, an anti-blocking agent, a filler, and a curing agent. Add agent.
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 colored ink layer is formed on the side in contact with the substrate. For the color ink layer, the type, content, lamination method, and the like of the binder resin are selected so that the laminate strength between the color ink layer and the base material is the weakest in the printed layer constituting the packaging laminated stick material.

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 (pattern printing layer and printing base layer) and between the printing layer and other layers 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.

The printing layer can be laminated by gravure roll coating, reverse roll coating, knife coating, kiss coating, and other known methods, as well as inkjet, dipping, spin coating, etc. In the invention, a method of laminating by printing is preferable.
If a printing machine capable of winding a film after printing is used for printing white ink, 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 packaging laminated stick material that is clear and does not cause printing unevenness by laser light, 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 packaging laminated stick material, and is a layer made of a conventional thermoplastic resin or a layer made 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.
For example, 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 Polymer, polypropylene, ethylene-vinyl acetate copolymer, ionomer resin, ethylene-acrylic acid copolymer, ethylene-ethyl acrylate copolymer, ethylene-methacrylic acid copolymer, ethylene-methyl methacrylate copolymer, ethylene -Unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, and other polyolefin resins such as propylene copolymer, methylpentene polymer, polybutene polymer, polyethylene or polypropylene. Acid-modified polyolefin resin modified with Polyvinyl acetate-based resins, poly (meth) acrylic resin, polyvinyl chloride resin, a resin other like can be used alone or two or more thereof.
Among the heat-sealable resins constituting the sealant layer, those obtained by polymerizing linear (linear) low-density polyethylene 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, it excels in heat seal stability, content resistance, stress cracking resistance, low-temperature heat sealability, and hot sealability. The liquid, paste, and jelly content of the present invention It can be suitably used for a laminated stick material for packaging products, particularly a sealant layer of a laminated stick material for packaging liquids.

  In addition to the above linear (linear) low density polyethylene, the above 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 a film or extruded coating layer of ethylene / α-olefin copolymer, ethylene / vinyl acetate copolymer, ethylene / acrylic acid copolymer, ethylene / acrylic acid ester copolymer, ionomer, polyester resin, etc. 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 this invention, although the thickness of the said sealant layer can be suitably set according to the content with which the lamination stick material for packaging is filled, about 5 micrometers-200 micrometers are preferable, and 10 micrometers-50 micrometers are more preferable.

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 stick material for packaging of the present invention, either a solvent type or an aqueous type can be used.
Examples include (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 ester latex , Polyvinylidene chloride latex, polybutadiene latex, or the carboxy of these latexes Modified or 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, aqueous lignin derivative, etc. A dispersion type emulsion or a dispersion anchor coating 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 laminated stick material having a layer structure laminated by the dry lamination method (DL), a suitable laminate strength relationship between the substrate or the sealant layer and the printed layer, that is, the laminated laminated stick material for packaging Since the strength of the laminate to be formed is increased, the stick material is not peeled off when printed by laser light. In order to obtain a clear printed image by laser irradiation, it is necessary to set the strength so that it can protrude in a convex shape between the substrate and the printed layer.

(Gas barrier layer)
In the present invention, a metal foil or a deposited layer of metal oxide can be used as the gas barrier layer. As the gas 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.
Further, a transparent vapor-deposited layer of inorganic oxide can be formed on the laminated constitution layer of the laminated stick material for packaging, or a resin film having a transparent vapor-deposited layer can be laminated and used.
Moreover, when using metal foil, such as aluminum foil, as a gas barrier layer, metal foil can be arrange | positioned on the opposite side to the base material of a printing foundation layer. Further, as the gas barrier layer, a gas 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. Further, 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 metal or metal oxide thin film layer may be a laminate of not only one layer but also two or more layers, and the metal or metal oxide used is 1 It is also possible to use a seed or a mixture of two or more to form a thin film layer made of a material mixed with different materials.
The laminated stick material for packaging of the present invention is preferably a silicon oxide vapor-deposited film, particularly a silicon oxide vapor-deposited film formed by a CVD method.

(Printing with laser light)
In the present invention, printing is performed using YAG (yttrium (Y) / aluminum (A) / garnet (G)) laser light (wavelength = 1.064 μm) or YVO4 (yttrium vanadate) laser light (wavelength = 1.064 μm). ) And fiber laser (wavelength = 1.06 to 1.07 μm).
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 stick material for packaging, the output of the laminated stick 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 YVO4 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)
Even if the average output of the laser is set low or the scan speed is set high in the printing process on the laminated stick material for packaging of the present invention, 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 laminated stick material for packaging and the printed body obtained by printing on the packaging stick of the present invention can be suitably applied as the laminated stick printed body for packaging having the laminated structure of the present invention.
In the laminated sticky material for packaging according to the present invention, printing with a laser beam is performed on an area composed only of a color ink layer. And, the area where the pattern printing layer with the desired color printing layer and the color ink layer that are not subjected to printing by laser light is superposed is adhesive to the base material even in a moist heat atmosphere, and the laminate strength is high. In combination with the fact that peeling does not occur as a large laminated stick material for packaging, it is possible to reliably obtain clear printing in the printing area.

(Stick for packaging)
A packaging stick using the above laminated sticking material for packaging will be described. A bag-shaped container body made of a packaging stick is made of a laminated material made of the above-mentioned laminated stick material for packaging, and the laminated material is folded in two, and the heat-sealable resin layer faces are overlapped, 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. A stick for packaging can be manufactured by heat sealing in a heat sealing form such as a seal type (pillow seal type) or a pleated seal 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]
A pattern printing layer was applied to one surface of a 12 μm thick easily cut polyethylene terephthalate (PET) film (base material) using a color ink by a gravure roll coating method.
On top of that, laser-printed color ink containing 5% by weight of bismuth oxide (converted to the solid content of the ink composition) as a color developing material and 15% by weight of titanium dioxide as a white ink pigment is applied to the entire surface by the gravure roll coating method. And a color ink layer was provided.
Next, an adhesive layer was provided on the color ink layer by a dry lamination method (DL) using a two-component curable polyester adhesive, and an aluminum foil having a thickness of 7 μm was further laminated.
Next, an adhesive layer is provided by a dry lamination method using a two-component curable polyester-based adhesive, and an easy-cut polyethylene terephthalate film having a thickness of 12 μm and a linear low-density polyethylene film having a thickness of 40 μm are formed by a dry lamination method. Laminated.
Thereby, the easy-cut PET film / image printing layer / coloring ink layer / adhesive layer / AL (barrier layer) / adhesive layer / easy-cut PET film / adhesive layer / linear low density polyethylene of the present invention. A laminated liquid stick material for packaging having a layer structure of a film sealant layer was obtained.

[Example 2]
A pattern printing layer was coated on one surface of a 12 μm thick easily-cut PET film using a color ink by a gravure roll coating method.
On top of this, laser-printed color ink containing 5% by weight of bismuth oxide as a color developing material (converted to the solid content of the ink composition) and 15% by weight of titanium dioxide as a white ink pigment is applied to the entire surface by the gravure roll coating method. And a color ink layer was provided.
Next, an anchor coat layer was formed on the color ink layer, and an aluminum foil having a thickness of 7 μm was laminated thereon using polyethylene by extrusion coating.
Next, an anchor coat layer was further provided, and a linear low density polyethylene film having a thickness of 35 μm was laminated by an extrusion coating method.
Thereby, the layer configuration of the easy-cut PET / picture printing layer / coloring ink layer / anchor coat layer / PE / AL (barrier layer) / anchor coat layer / PE / linear low density polyethylene film sealant layer of the present invention is obtained. A laminated liquid stick material for packaging was obtained.

[Example 3]
A pattern printing layer was applied to one surface of a 40 μm thick biaxially stretched polypropylene film using a color ink by a gravure roll coating method. On top of this, laser-printed color ink containing 5% by weight of bismuth oxide as a color developing material (converted to the solid content of the ink composition) and 15% by weight of titanium dioxide as a white ink pigment is applied to the entire surface by the gravure roll coating method. And a color ink layer was provided.
Next, an adhesive layer was provided on the colored ink layer by a dry lamination method using a two-component curable polyester adhesive, and an aluminum foil having a thickness of 7 μm was laminated.
Next, an adhesive layer was provided by a dry lamination method using a two-component curable polyester adhesive, and an unstretched polypropylene film sealant layer having a thickness of 40 μm was laminated.
Thereby, a laminated liquid stick material for packaging having a layer structure of the polypropylene film / picture printing layer / coloring ink layer / adhesive layer / AL / adhesive layer / unstretched polypropylene film sealant layer of the present invention was obtained.

[Example 4]
A pattern printing layer was applied to one surface of a PET film having a thickness of 12 μm using a color ink by a gravure roll coating method.
On top of this, laser-printed color ink containing 5% by weight of bismuth oxide as a color developing material (converted to the solid content of the ink composition) and 15% by weight of titanium dioxide as a white ink pigment is applied to the entire surface by the gravure roll coating method. And a color ink 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 adhesive, a 12 μm-thick transparent deposited PET film, and a 40 μm-thick linear low density A polyethylene film was laminated by the DL method.
Thereby, the laminated stick material for packaging having the layer structure of the PET film / pattern printing layer / coloring ink layer / adhesive layer / transparent deposited PET film / adhesive layer / linear low density polyethylene film sealant layer of the present invention is obtained. Obtained.

[Example 5]
A pattern printing layer was applied to one surface of a PET film having a thickness of 12 μm using a color ink by a gravure roll coating method.
On top of this, laser-printed color ink containing 5% by weight of bismuth oxide as a color developing material (converted to the solid content of the ink composition) and 15% by weight of titanium dioxide as a white ink pigment is applied to the entire surface by the gravure roll coating method. And a color ink printing layer was provided. At the same time, perforation is performed to provide an opening in the width direction of the PET. Next, an adhesive layer is provided on the printed layer by a dry lamination method (DL) using a two-component curable polyester adhesive, an aluminum foil having a thickness of 7 μm is laminated, and then a two-component curable polyester An adhesive layer was provided by a DL method using a system adhesive, and a PET film having a thickness of 12 μm and a linear low-density polyethylene film having a thickness of 40 μm were laminated by the DL method.
Thus, the layer structure of the PET film / pattern printing layer / coloring ink layer / adhesive layer / AL (barrier layer) / adhesive layer / PET film / adhesive layer / linear low density polyethylene film sealant layer of the present invention. A laminated stick material for packaging having

[Comparative example]
A pattern printing layer was provided on one surface of an easily cut PET film having a thickness of 12 μm by a gravure roll coating method using ink.
Next, an adhesive layer is provided on the printed layer by a dry lamination method (DL) using a two-component curable polyester adhesive, an aluminum foil having a thickness of 7 μm is laminated, and then a two-component curable polyester An adhesive layer was provided by a DL method using a system adhesive, and an easy-cut PET film having a thickness of 12 μm and a linear low-density polyethylene film having a thickness of 40 μm were laminated by the DL method.
Thereby, easy-cut PET film / pattern printing layer / printing ink underlayer / adhesive layer / AL (barrier layer) / adhesive layer / easy-cut PET film / adhesive layer / linear low density polyethylene film sealant A laminated stick material for packaging having a layer structure of layers was obtained.

[Laser printing method]
About each laminated stick material for packaging obtained in the Examples, YVO4 laser light was irradiated from the base material side under the following conditions to form a laser print image to obtain a printed body.
・ Laser irradiation conditions YVO4 laser machine (manufactured by Keyence Co., Ltd. MD-V9600)
For Examples 1 and 5, the average output is 1.6 W, the Q switch frequency is 20 KHz, and the scan speed is 1000 mm / s. For Examples 2 and 3, the average output is 1.1 W, the Q switch frequency is 20 KHz, and the scan speed is 1000 mm / s. In Example 4, irradiation was performed at an average output of 1.5 W, a Q switch frequency of 20 kHz, and a scan speed of 1000 mm / s.

[Evaluation method]
For each laminated stick material for packaging shown in Examples 1 to 5, the expiration date is printed on the laser color ink base layer by actually irradiating the laser beam, and the clarity and character of the characters printed there The printed characters such as the thickness and color depth were comprehensively evaluated, the printed state was evaluated by visibility, and the appearance after laser irradiation was confirmed.
In addition, for comparative examples, printing is performed by inkjet, and the printed characters such as the sharpness, thickness, and color density of the printed characters are comprehensively evaluated, and the printing state is evaluated by visibility. did.

[Evaluation results]
The laminated stick materials for packaging of Examples 1 to 5 have a thick line width even when printed with low irradiation energy (1.6 W, scan speed 1000 mm / s), and the print density is high and does not disappear even when rubbed. In this way, laser printing with clear and clear discrimination and high visibility was obtained.
On the other hand, since the laminated sticky material for packaging of the comparative example is printed by inkjet, the characters disappear due to rubbing or disappear due to adhesion of a solvent or contents.

1. Base material 2. Gas barrier layer (transparent vapor deposition layer)
3. Print layer 3a. Pattern printing layer 3b. Colored ink layers 4a, 4b. 4. Sealant layer Metal foil A. Print section

Claims (10)

A laminated stick material for packaging having a sealant layer on both surfaces of a laminated structure in which a base material, a picture printing layer, and a color ink layer are laminated in this order and having a gas barrier layer, and is laser-printed with the picture printing layer In the laminated stick material for packaging having a region in which the color ink layer overlaps and a layer in which only the color ink layer is formed,
The colored ink layer is a laminated stick material for packaging, which is a layer that can be printed with a laser beam containing a coloring material that develops color when irradiated with a laser beam.   The laminated stick material for packaging according to claim 1, wherein the coloring material is a bismuth-based compound.   The laminated stick 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 stick material for packaging according to any one of claims 1 to 3, wherein the colored ink layer contains one or more compounds selected from a metal oxide, a composite oxide, or a group thereof.   The laminated stick material for packaging according to any one of claims 1 to 3, wherein the coloring ink layer contains one or more compounds selected from a copper compound, a molybdenum compound, or a group thereof.   The laminated stick 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 stick material for packaging according to any one of claims 1 to 5, wherein the gas barrier layer is an aluminum metal foil and is located on the side opposite to the base of the color ink layer.   The laminated stick material for packaging according to any one of claims 1 to 7, which has an easy-open property.   A packaging stick using the packaging laminated stick material according to any one of claims 1 to 8.   The laminated stick material for packaging according to any one of claims 1 to 8 or the packaging stick according to claim 9 is colored by irradiating YAG or YVO4 laser light or fiber laser from the substrate side. A stick laser printing body for packaging, in which an ink composition spreads on the surface of the base material and the coloring ink layer and has a laser print image.

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