JP5956220B2 - Label sheet, method for producing the same, and method for producing an article with a printed pattern - Google Patents

Description

  The present invention relates to a label sheet and a method for producing an article with a printed pattern.

  In recent years, labels have been applied to a wide variety of glass products such as glass bottles, and efforts have been made to enhance the design of glass products by means of labels, not limited to descriptive aspects such as trademarks and product descriptions. Examples of the label applied to the glass product include a trademark-only label, a design-only label, or a label that serves as both.

  Patent Documents 1 to 4 disclose techniques related to a transfer sheet for transferring a pattern to a ceramic product.

  In Patent Document 1, as shown in FIG. 3 of the same document, a yellow layer 21, an intermediate layer 31, a red layer 22, an intermediate layer 32, a blue layer 23, and a black layer 24 are sequentially formed on the printing mount 1 by screen printing. Printing is disclosed (see also FIGS. 1 and 2 of the same document). As shown in FIG. 5 of the same document, it is disclosed that the yellow layer 21 can be flattened by the intermediate layer 31 and thereby the red layer 22 can be printed reliably (see, for example, paragraph 0012 of the same document). . In paragraph 0030 of the same document, it is disclosed that the transfer paper is peeled off from the printing mount, stuck on a glaze material having a different coefficient of thermal expansion, and fired at 800 to 850 ° C.

  Patent Document 2 discloses a transfer sheet 1 in which a release layer 3, a colored layer 4, an adhesive layer 5, and an adhesive layer 6 are laminated on a polyester sheet 2 as shown in FIG. As shown in FIG. 2 of the document, the transfer sheet 1 is bonded onto the ceramic substrate 7 and the polyester sheet 2 is peeled off.

  In Patent Document 3, as shown in FIG. 1 of the same document, a thermal transfer paper 4 is placed on a ceramic substrate 1, hot pressed, peeled off the release paper 5 after cooling, fired in an electric kiln, and decorated ceramic. It is disclosed to obtain a body (see paragraph 0018 of the same document). The thermal transfer paper 4 is obtained by forming the resin layer 6 on the release paper 5 and printing the pattern 2 (see paragraph 0017 of the same document).

  In Patent Document 4, as shown in FIG. 2 of the same document, a release layer 2, a pattern layer 3, and an adhesive layer 4 are laminated on the peelable substrate sheet 1, and as shown in FIG. 3 of the same document. It is disclosed that it is placed on the substrate 6. In paragraph 0020 of the same document, an adhesive layer is formed on the surface of the tile substrate, the transfer sheet is pre-heated and placed on the surface of the tile substrate and thermally transferred, and then the peelable substrate sheet 1 is peeled off. And firing at 1070 ° C. is disclosed.

JP-A-5-139020 JP-A-5-85866 JP 11-48694 A JP-A-7-1894

  At the time of integrating the pattern layer on the adherend through a firing step, no attempt has been made to stick the pattern layer to the adherend with high efficiency.

  The label sheet according to the present invention is a label sheet comprising a release film and one or more island-like labels laminated in a peelable manner on the release film, and the label is laminated on the release film. And an adhesive layer to be peeled from the release film and attached to the adherend from the surface on the release film side, and laminated on the release film through at least the adhesive layer, and fired on the adherend. A printed pattern layer to be fixed.

  The label may further include a protective layer laminated on the printed pattern layer.

  The glass transition temperature of the protective layer is preferably 40 ° C. or higher.

  The calculated value of tensile elastic modulus x layer thickness of the protective layer is preferably 40 N / mm or more.

  The label may further include at least a barrier layer that ensures a barrier property between the adhesive layer and the printed pattern layer.

  It is preferable that the calculated value of tensile elastic modulus × total layer thickness of a portion where the protective layer and the barrier layer are laminated without using the printed pattern layer is 40 N / mm or more.

  The printed pattern layer is a layer in which at least one kind of ink is deposited so as to form a pattern, and the ink includes at least a pigment, a material that can be welded to the adherend, and a material that can be removed by baking. And good. The release film may include a base material and a release agent layer formed on the base material.

  The adherend is preferably an article made of glass or ceramic.

  A method for producing an article with a printed pattern according to the present invention is a label sheet comprising a release film and a row of labels laminated in a peelable manner on the release film, wherein the label includes at least an adhesive layer and a printed pattern layer. In this order, the label sheet on the release film is fed, the label is peeled off from the release film in the process of feeding the label sheet, and the label is attached to the adherend from the surface of the adhesive layer on the release film side. It sticks and the said adherend to which the said label stuck is baked.

  The step of peeling the label from the release film in the process of feeding the label sheet may include a step of feeding the label from the release film toward the adherend at a change position in the feeding direction of the label sheet. .

  According to the present invention, it is possible to attach a label including a printed pattern layer to an adherend with high efficiency. In addition, according to the present invention, it is possible to obtain a printed pattern that can be attached to an article having a non-flat surface and has high positional accuracy.

It is a schematic perspective view of the label sheet concerning a 1st embodiment of the present invention, and shows the state where one end was pulled out from the portion where the label sheet was wound around the reel. It is a schematic cross-sectional schematic diagram of the width direction of the label sheet which concerns on 1st Embodiment of this invention, and shows the schematic cross-sectional structure between XII-XII of FIG. It is a schematic cross-sectional schematic diagram of the longitudinal direction of the label sheet which concerns on 1st Embodiment of this invention, and shows the schematic cross-sectional structure between XIII-XIII of FIG. It is process drawing which shows the sticking process of the label which concerns on 1st Embodiment of this invention. It is explanatory drawing which shows typically the delivery aspect of the label in the sticking process of the label which concerns on 1st Embodiment of this invention. It is a schematic end view in the predetermined height position of the glass bottle after baking which concerns on 1st Embodiment of this invention. It is a schematic process drawing which shows the manufacturing process of the label sheet which concerns on 1st Embodiment of this invention. It is a schematic process drawing which shows the manufacturing process of the label sheet which concerns on 1st Embodiment of this invention. It is a schematic process drawing which shows the manufacturing process of the label sheet which concerns on 1st Embodiment of this invention. It is a schematic process drawing which shows the manufacturing process of the label sheet which concerns on 1st Embodiment of this invention. It is a schematic process drawing which shows the manufacturing process of the label sheet which concerns on 1st Embodiment of this invention. It is a schematic process drawing which shows the manufacturing process of the label sheet which concerns on 1st Embodiment of this invention. It is a rough cross-sectional schematic diagram of the label sheet which concerns on 2nd Embodiment of this invention. It is a rough cross-sectional schematic diagram of the label sheet which concerns on 3rd Embodiment of this invention. It is process drawing which shows the sticking process of the label which concerns on 4th Embodiment of this invention.

  Hereinafter, embodiments of the present invention will be described with reference to the drawings. The embodiments are not individually independent, and need not be overexplained. Those skilled in the art can appropriately combine the embodiments, and can also grasp the synergistic effect of the combination. In principle, duplicate descriptions between the embodiments are omitted.

  The reference drawings are mainly intended to explain the invention and are simplified as appropriate. In the description with reference to these drawings, the terms “width direction” and “longitudinal direction” may be used on the premise / reference of a label sheet having a predetermined width and length. Further, the term “stacking direction” may be used on the basis of the stack structure of the label sheet. Further, the direction in which the label sheet is fed may be referred to as “feed direction”. The direction in which the adherend to which the label of the label sheet is attached is sometimes referred to as the “transport direction”. The direction in which the label is fed from the release sheet may be referred to as the “feeding direction”.

<First Embodiment>
The first embodiment will be described with reference to FIGS. FIG. 1 is a schematic perspective view of a label sheet, showing a state in which one end is pulled out from a portion where the label sheet is wound around a reel. FIG. 2 shows a schematic cross-sectional configuration between XII and XII in FIG. FIG. 3 shows a schematic cross-sectional configuration along XIII-XIII in FIG. FIG. 4 is a process diagram showing a label attaching process. FIG. 5 is an explanatory view schematically showing a label feeding mode in the label sticking step. FIG. 6 is a schematic end view of the glass bottle after firing at a predetermined height position. 7 to 12 are schematic process diagrams showing the manufacturing process of the label sheet.

  First, the configuration of the label sheet 100 will be described with reference to FIGS. 1 to 3. As shown in FIG. 1, the label sheet 100 is a long body having a predetermined width and is wound around a reel. The label sheet 100 includes a long release film 50 and a row of labels 60 laminated on the release film 50 so as to be peelable. The labels 60 are partitioned into rectangular islands on the release film 50, and are provided at regular intervals along the longitudinal direction of the release film 50. One surface of the release film 50 is exposed between the adjacent labels 60. The label sheet 100 has a single structure having only the release film 50 in the range R50 shown in FIG. 1, and has a composite structure in which the label 60 is laminated on the release film 50 in the range R60 shown in FIG.

  FIG. 2 shows a schematic cross-sectional configuration between XII and XII in FIG. 1, and FIG. 3 shows a schematic cross-sectional configuration between XIII and XIII in FIG. As shown in FIGS. 2 and 3, the label 60 partitioned into rectangular islands is a laminate in which an adhesive layer 61, a printed pattern layer 62, and a protective layer 63 are laminated in this order. In the range where the printed pattern layer 62 is not formed, the protective layer 63 is laminated directly on the adhesive layer 61.

  As will be apparent from the following description, the laminate on the release film 50 is selectively removed, and a rectangular island-shaped label 60 remains as shown in FIG. Typically, the selective removal described above is performed utilizing slit processing. On the side surface of the label 60 exposed through such a removing step, the label constituent layers (here, the adhesive layer 61 and the protective layer 63) may be exposed. The specific manufacturing method of the label sheet 100 having the cross-sectional configuration shown in FIGS. 2 and 3 is arbitrary, and can be manufactured using, for example, a coating method or a printing method. For selective removal of unnecessary portions, it is easy to use any kind of slitter device.

  The release film 50 is a long single-layer thin layer having sufficient flexibility and sufficient mechanical strength. The constituent material of the release film 50 is a plastic such as polyethylene, polyimide, polyethylene terephthalate, or acrylic. In addition to plastic, the release film 50 may be configured using paper or a composite thereof. The layer thickness of the release film 50 is preferably 25 to 250 μm, more preferably 35 to 75 μm. Although the length of the peeling film 50 is not specifically limited, About 500 m is preferable on handling in manufacture. The case where the release film 50 has a multilayer structure will be described in the third embodiment. In addition, the adhesiveness of the peeling film 50 and the adhesion layer 61 can be adjusted by selection of each structural material.

  As described above, the adhesive layer 61, which is a constituent layer of the label 60, is a layer made of an acrylic or rubber adhesive. The layer thickness of the adhesive layer 61 is preferably 1 to 20 μm, more preferably 2 to 10 μm. As will be apparent from the description below, the adhesive layer 61 is thermally decomposed and gasified in the firing step. Therefore, it is desirable to make the adhesive layer 61 a thin layer in order to suppress the occurrence of firing defects such as pinholes and color irregularities in the printed pattern layer 62. If the thickness of the adhesive layer 61 is less than 1 μm, the adhesive force of the adhesive layer 61 may not be sufficient to sufficiently adhere the label 60 to the glass bottle (adhered body). If the thickness of the pressure-sensitive adhesive layer 61 exceeds 20 μm, there is a possibility that the probability of firing defects occurring in the printed pattern layer 62 is increased due to the effect of pyrolysis gas during firing.

  By appropriately adjusting the layer thickness and material of the adhesive layer 61, the peel strength determined by the release film 50 and the adhesive layer 61 can be adjusted. A peeling agent may be adjusted by adding a curing agent to the adhesive layer 61. Preferably, the adhesion strength between the adhesive layer 61 and the release film 50 is 0.1 to 3 mN / mm. More preferably, it is 0.5 to 1.5 mN / mm. If the adhesion strength exceeds 3 mN / mm, the label 60 may be difficult to peel from the release film 50. If it is less than 0.1 mN / mm, the label 60 is peeled off from the release film 50 during the feeding process of the label sheet 100, which may cause problems such as misalignment, wrinkles, and loss.

  The printed pattern layer 62 is laminated on the release film 50 via the adhesive layer 61. The printed pattern layer 62 is finally integrated on the surface of the glass bottle, and the surface has a display function and / or design properties. The printed pattern layer 62 is preferably a layer patterned with ink by screen printing or the like, and typically contains at least an inorganic pigment, glass powder, and organic matter.

  As an example, a printing pattern layer 62 is formed by printing ink obtained by mixing inorganic pigments, glass powders, and organic substances on a substrate (in this example, the protective layer 63) by screen printing. To do. Although the specific cross-sectional structure of the printing pattern layer 62 is arbitrary, it consists of one or more ink patterns, for example. When the printed pattern layer 62 is constituted by two ink patterns, the inks constituting each ink pattern may be laminated at the overlapping portions of the respective ink patterns. The pattern displayed by the printed pattern layer 62 can be exemplified by characters, figures, photographs, and the like.

The inorganic pigment contained in the printed pattern layer 62 is one of pigments such as white, blue, yellow, red, and black, or any combination thereof. The white pigment is illustratively TiO ₂ or Al ₂ O ₃ . The blue pigment is illustratively a Co—Al-based oxide or a Co—Cr—Al-based oxide. The yellow pigment is, for example, a Ti—Sb—Ni-based oxide or a Cr—Ti-based oxide. The red pigment is, for example, Zn—Fe—Cr oxide or Fe ₂ O ₃ . The black pigment is illustratively a Cu—Cr-based oxide or a Cu—Cr—Mn-based oxide.

Examples of the glass powder contained in the printed pattern layer 62 include SiO ₂ , ZrO ₂ , Al ₂ O ₃ , TiO ₂ , CeO ₂ , B ₂ O ₃ , Bi ₂ O ₃ , Na ₂ O, K ₂ O, and ZnO. The thing containing components, such as these, can be used. The glass powder contained in the printed pattern layer 62 is preferably a glass powder having a softening temperature of 500 to 600 ° C. containing SiO ₂ , ZrO ₂ , and Bi ₂ O ₃ components.

  The organic substance (sometimes referred to as an organic binder) included in the printed pattern layer 62 is, for example, a methacrylic acid resin, but is not limited thereto. The organic matter in the printed pattern layer 62 is released out of the printed pattern layer 62 as a pyrolysis gas by a baking process described later. By including an organic substance in the printed pattern layer 62, stable printing can be performed, and adhesion with the adhesive layer 61 and the protective layer 63 can be improved.

  The weight ratio of the inorganic powder (mixture of inorganic pigment and glass powder) to the resin is 80:20 to 97: 3, preferably 90:10 to 97: 3. If the weight part ratio of the resin exceeds 20, there may be a risk of firing defects such as residual carbon, pinholes, and color unevenness in the resin contained in the printed pattern layer. On the other hand, when the weight part ratio of the resin is less than 3, the resin content contained in the printed pattern layer is small, so that the coating layer cohesive force of the printed pattern layer is reduced and the base layer is formed when the printed pattern layer is formed. Adhesion with the protective layer may be reduced, and defects such as cracks and peeling may occur before firing. In particular, when the label sheet is in the form of a reel, there is a risk that defects such as cracks and peeling will occur on the label. Even when a label is attached to a glass bottle with a tack labeler, there is a possibility that defects such as cracks and peeling may occur on the label.

The protective layer 63 is a layer made of an organic material having a thickness sufficient to ensure the mechanical strength of the label 60. Preferably, the tensile elastic modulus of the protective layer 63 is 1000 to 5000 N / mm ² , and the layer thickness is 5 to 50 μm. Preferably, the tensile elastic modulus × layer thickness of the protective layer 63 is 40 N / mm or more.

The protective layer 63 is a layer made of a polymer containing, for example, 50 wt% or more of the polymer of the methacrylic acid ester monomer shown in Chemical formula 1. Methacrylic ester fine particles may be added to the protective layer 63 made of a methacrylic ester polymer. When fine particles are added to the protective layer 63, the tensile elastic modulus of the protective layer 63 can be improved. Further, since the methacrylic acid ester polymer constituting the protective layer 63 and the fine particles are of the same type, the fine particles can be uniformly dispersed in the protective layer, and it is preferable in that there is no great difference in thermal decomposability between the polymer and the fine particles.

  Since the methacrylic acid ester polymer has good thermal decomposability during firing, no residual carbon is produced, firing rupture hardly occurs, and firing defects such as pinholes and color unevenness hardly occur in the printed pattern layer. The protective layer 63 preferably contains 80 wt% or more of a methacrylic acid ester polymer. More preferably, the protective layer 63 may be a methacrylic acid ester homopolymer or a copolymer of different methacrylic acid ester monomers.

  The glass transition temperature of the protective layer 63 is preferably 40 ° C. or higher. By setting the temperature at 40 ° C. or higher, when the label sheet 100 is stacked and stored in the form of a reel, the protective layer 63 and the release film 50 can be prevented from adhering. The glass transition temperature of the protective layer 63 is preferably 40 ° C. or higher and 100 ° C. or lower.

  The thickness of the protective layer 63 is preferably 5 to 50 μm. When the thickness is less than 5 μm, the impact resistance is poor, and when it exceeds 50 μm, there is a possibility that the air path of the pyrolysis gas emitted from the printed pattern layer 62 and the layers below the layer is blocked during firing. More preferably, the layer thickness of the protective layer 63 is 10 to 20 μm.

  Since the printed pattern layer 62 contains a relatively small proportion of organic matter, the film quality before firing tends to be hard and brittle. For this reason, if the label sheet 100 is bent, the printed pattern layer 62 may be cracked. When the exposed printed pattern layer 62 is attached to the glass bottle, the printed pattern layer 62 is easily damaged. By providing the protective layer 63, it is possible to prevent the above-described cracks and suppress the generation of scratches. The protective layer 63 is removed as a pyrolysis gas by a firing process described later.

In order to adhere the label 60 to the glass bottle 70 (see FIG. 4) without any problem, it is desirable that the value represented by the tensile elastic modulus × layer thickness of the protective layer 63 is 40 N / mm or more. If the value shown by tensile modulus × layer thickness is 40 N / mm or more, wrinkles can be prevented from occurring on the label 60 attached to the glass bottle 70. In the case of less than 40 N / mm, after the label 60 is peeled from the release film 50, the label 60 is bent and there is a possibility that wrinkles are likely to occur when the label 60 is attached to the glass bottle 70. Here, the tensile elastic modulus is a tensile elastic modulus defined by JIS K7113. The tensile modulus is calculated by the following equation using the first linear part of the tensile stress-strain curve.
Em = Δσ / Δε
(Em: tensile modulus, Δσ: difference in stress due to the original average cross-sectional area between two points on a straight line, Δε: difference in strain between the same two points)

  Hereinafter, the label attaching step and the firing step will be described with reference to FIGS. A label 60 is attached to the glass bottle 70 by the apparatus 200 shown in FIG. In addition, the apparatus 200 combines the tack labeler 10 with the conveyance apparatus of a glass bottle. The transport device includes a rotary transport mechanism 41 and stock yards 42 and 43, but the specific configuration thereof is arbitrary.

  The tack labeler 10 includes a label sheet supply unit 11, a peel plate 12, and a release film collection unit 13. The label sheet supply unit 11 rotatably holds the label sheet 100 wound around a reel, and sequentially feeds the label sheets 100 by rotating the reel shaft. The peel plate 12 is a flat plate whose position is fixed, and intervenes the feeding of the label sheet 100 (release film) between the label sheet supply unit 11 and the release film collection unit 13. The peeling film collection | recovery part 13 collect | recovers the peeling film after label peeling with a reel. The label sheet 100 is in a state of being stretched between the label sheet supply unit 11 and the release film collection unit 13. Each operation | movement of the label sheet supply part 11 and the peeling film collection | recovery part 13 is performed in synchronization with conveyance of the glass bottle 70. FIG.

  A process in which the label 60 is attached to the glass bottle 70 will be described. First, the glass bottle 70 is thrown from the stock yard 42 to the rotary conveyance mechanism 41 by any means. Next, the glass bottle 70 is conveyed clockwise by the rotation conveyance mechanism 41. In this conveyance process, the glass bottle 70 itself is controlled to rotate clockwise. Next, when the glass bottle 70 reaches the label supply position of the tack labeler 10, the label 60 supplied from the tack labeler 10 adheres to the outer surface of the glass bottle 70. Since the glass bottle 70 is rotating, the label 60 is suitably wound and temporarily attached to the outer surface of the glass bottle 70. Thereafter, the glass bottle 70 is extruded from the rotary transport mechanism 41 to the stock yard 43 by any means.

  As schematically shown in FIG. 5, the feeding direction of the label sheet 100 is reversed at the label feeding position of the tack labeler 10. When the release film 50 passes through the tip of the peel plate 12 while bending in the reverse direction, the label 60 gradually warps from the release film 50 from the tip, and the label 60 is fed toward the glass bottle 70. As schematically shown in FIG. 4, the label 60 is fed toward the glass bottle 70, and the lower surface (the surface on the release film 50 side) of the adhesive layer 61 adheres to the outer surface of the glass bottle 70. Desirably, before the label 60 completely peels from the release film 50, the leading end of the label 60 in the feeding direction of the label 60 adheres to the outer surface of the glass bottle 70. After the adhesion, the label 60 is wound around and temporarily attached to the outer surface of the glass bottle 70 by the rotation of the glass bottle 70. The release film 50 from which the label 60 has been peeled off via the peel plate 12 is wound up by the release film collection unit 13.

  A group of glass bottles 70 temporarily attached to the stock yard 43 after being temporarily attached to the label 60 is put into a baking furnace all at once or sequentially, and is fired at a temperature condition (for example, 500 ° C. to 700 ° C.) above the glass softening point. . In this firing step, the adhesive layer 61 is gasified and removed, the protective layer 63 is gasified and removed, and the organic matter in the printed pattern layer 62 is also gasified and removed. As schematically shown in FIG. 6, the printed pattern layer 62 is sintered and integrated on the outer surface of the glass bottle 70.

  Finally, the label sheet manufacturing process will be supplementarily described with reference to FIGS. First, as shown in FIG. 7A, the protective layer 63 is formed on the release sheet 71. Preferably, the protective layer 63 is formed using any type of coating apparatus exemplified by a gravure coater. Thereafter, the protective layer 63 is dried using any kind of drying apparatus.

  Next, as shown in FIG. 7B, the printed pattern layer 62 is formed by an arbitrary printing method exemplified by screen printing or the like. Thereafter, the printed pattern layer 62 is dried using any type of drying device.

  On the other hand, an adhesive layer 61 is formed on the release film 50 as shown in FIG. Preferably, the adhesive layer 61 is formed using any kind of coating apparatus exemplified by a gravure coater. Thereafter, the adhesive layer 61 is dried using any type of drying device.

  Next, as schematically shown in FIG. 8, the laminate of FIG. 7B and the laminate of FIG. 7C are bonded together. Thereby, the laminated body shown in FIG. 9 is obtained. Preferably, the laminator device is used to bond the two together. You may pressurize both suitably. Then, as schematically shown in FIG. 10, the release sheet 71 is peeled off. Thereby, the label sheet 100 is obtained. Next, as shown in FIG. 11, the laminated body 60 on the release film 50 is cut so as to partition the range indicated by the region R <b> 10, and is unnecessary partitioned by the cut line as schematically shown by the arrows in FIG. 11. Remove the part. At this time, it is desirable to utilize a slitter device. Next, as shown in FIG. 12, the label sheet 100 is cut along the cut line CL. The reel-shaped label sheet 100 shown in FIGS. 1 to 3 can be obtained by winding a strip obtained by cutting around a reel.

  As is clear from the above description, in this embodiment, the label sheet 100 is set on the tack labeler 10 and the label 60 is attached to the outer surface of the glass bottle 70. At this time, by configuring the label sheet 100 as described above, the label 60 can be suitably peeled from the release film 50 and the labels 60 can be fed out sequentially. In order to stabilize the feeding of the label 60 and / or to prevent wrinkles from occurring on the label 60 attached to the glass bottle 70, it is desirable to give the label 60 a predetermined mechanical strength. From this point of view, in this embodiment, the label strength is ensured by the protective layer 63 that can be removed by baking. Moreover, in this embodiment, the bad influence at the time of the baking is reduced by making thin the layer thickness of the adhesion layer by baking removal.

  The object to which the label 60 is affixed is not limited to a glass bottle, and may be a ceramic body with glaze applied to the surface. In addition, when using the label sheet 100 which concerns on this embodiment, it is not necessary to make a big change to the structure of the conveyance mechanism of the existing tack labeler 10 or the glass bottle 70, and affinity with the existing equipment can also be ensured. Moreover, a pattern with high descriptive power can be transferred to a glass bottle by utilizing screen printing. In the field of glass bottles, it has not been possible to transfer high-resolution patterns such as gradations and photographs. This can be realized by utilizing the label seal and the manufacturing method of the present embodiment.

Second Embodiment
A second embodiment will be described with reference to FIG. FIG. 13 is a schematic cross-sectional schematic diagram of a label sheet. In the present embodiment, as shown in FIG. 13, a barrier layer 64 is provided between the adhesive layer 61 and the printed pattern layer 62, and a barrier property is ensured between the adhesive layer 61 and the printed pattern layer 62. Even in such a case, the label sheet 100 can be used as in the first embodiment, and the same effect as in the first embodiment can be obtained. An intermediate layer other than the barrier layer may be inserted between the adhesive layer 61 and the printed pattern layer 62.

  The barrier layer 64 is not particularly limited as long as it is an organic substance that can be removed by baking. Resins such as polyester can be used alone or as a mixture thereof. In particular, it is preferable to use a polymer resin having a glass transition temperature of 40 ° C. or higher because of high barrier effect. By providing the barrier layer 64, it is possible to prevent the solvent or organic matter contained in the paste for forming the printed pattern layer 62 from entering the adhesive layer 61.

  You may add a plasticizer with respect to the barrier layer 64 as another organic substance in order to provide flexibility to the coating film before baking. The plasticizer can be appropriately selected from fatty acid esters, phosphate esters, and the like. The layer thickness of the barrier layer 64 is preferably in the range of 5 to 25 μm. If the thickness is less than 5 μm, there is no barrier property, and if it exceeds 25 μm, the amount of pyrolysis gas generated increases, so that there is a possibility that firing defects such as pinholes and color irregularities are likely to occur in the printed pattern layer. Considering firing defects, the thickness of the barrier layer is preferably 10 to 20 μm.

  The laminated body shown in FIG. 13 is obtained through the following procedure, for example. The pressure-sensitive adhesive layer 61 is formed on the release film 50, the barrier layer 64 is formed on the sacrificial release film, and each of these laminates is bonded together, whereby the release film 50, the pressure-sensitive adhesive layer 61, the barrier layer 64, and the sacrificial release A film laminate is obtained. Next, the sacrificial release film is peeled off and removed. Next, the printed pattern layer 62 is formed on the barrier layer 64 by screen printing or the like, and the protective layer 63 is formed on the printed pattern layer 62 and the barrier layer 64. In consideration of the long release film 50, the thin film is preferably formed using any kind of coating apparatus. It is preferable to use any type of laminator device for laminating the laminates.

In order to attach the label 60 to the glass bottle 70 without any problem, the value indicated by the tensile elastic modulus × total layer thickness of the portion where the protective layer 63 and the barrier layer 64 are laminated without the printed pattern layer 62 is 40 N / mm. The above is desirable. If the value shown by the tensile modulus × total layer thickness is 40 N / mm or more, the generation of wrinkles on the label 60 stuck to the glass bottle 70 can be suppressed. In the case of less than 40 N / mm, after the label 60 is peeled from the release film 50, the label 60 is bent, and wrinkles are easily generated when the label 60 is attached to the glass bottle 70. Here, the tensile elastic modulus is a tensile elastic modulus defined by JIS K7113. The tensile modulus is calculated by the following equation using the first linear part of the tensile stress-strain curve.
Em = Δσ / Δε
(Em: tensile modulus, Δσ: difference in stress due to the original average cross-sectional area between two points on a straight line, Δε: difference in strain between the same two points)

The tensile elastic modulus of the portion where the protective layer 63 and the barrier layer 64 are laminated without the printed pattern layer 62 interposed therebetween is preferably 1000 to 5000 N / mm ² and the total layer thickness is preferably 5 to 50 μm. Moreover, it is good that tensile elasticity modulus x total layer thickness is 40 N / mm or more.

<Third Embodiment>
A third embodiment will be described with reference to FIG. FIG. 14 is a schematic cross-sectional schematic diagram of a label sheet. In the present embodiment, as shown in FIG. 14, the release film 50 has a two-layer structure in which a release agent layer 52 is provided on a base material 51. Even in such a case, the same effects as those of the above-described embodiment can be obtained. The release agent layer 52 is a layer in which a release agent exemplified by silicone, alkyd resin, etc. is deposited in a predetermined layer thickness. By selecting the layer thickness and material of the release agent layer 52, the peel strength determined by the release film 50 and the adhesive layer 61 can be adjusted. The substrate 51 is, for example, a resin film, but should not be limited to this.

<Fourth embodiment>
A fourth embodiment will be described with reference to FIG. FIG. 15 is a process diagram showing a label attaching process. In this embodiment, as shown in FIG. 15, the glass bottle 70 is sent linearly. Even in such a case, the same effect as that of the above-described embodiment can be obtained.

(Example)
The following examples are disclosed solely for purposes of illustration / reference. The following examples have been tried under specific conditions and are not allowed to limit the invention with the following disclosure.

  The measurement of the layer thickness described later was performed as follows. The measurement was performed using an electronic micrometer (manufactured by Anritsu, K-107C) in accordance with JIS K5600-1-7. Specifically, for a PET film (A31) with a film width of 250 mm and a film length of 100 m, sample the coating start part after setting the conditions, and measure any three locations (near both ends and near the center) in the film width direction. . Next, the coating end part was also sampled and measured in the same manner as the coating start part, and the average value of the measured values at a total of six places was calculated to obtain the layer thickness. The thicknesses of the embodiments and examples disclosed in the present application are desirably determined in accordance with this measurement method.

Example 1
(Production of label sheet)
A label sheet was prepared by the following procedure. The release film is a PET film “A31” (manufactured by Teijin DuPont Films Co., Ltd.) provided with a silicone release layer, having a film size width of 250 mm, a length of 100 m, and a thickness of 38 μm. An acrylic adhesive “SK1451” (manufactured by Soken Chemical Industry Co., Ltd.) was prepared as an adhesive layer. The ink constituting the printed pattern layer was produced as follows. Methacrylic acid resin “Likabond SA200” (solid content 40%, with respect to the total weight of the inorganic powder in a ratio of 20 parts by weight of the color pigment powder and 80 parts by weight of the glass powder (Si: Bi = 100 at%: 40 at%) Chuo Rika Kogyo Co., Ltd.) was mixed at a weight ratio (inorganic powder: resin) of 95: 5. Next, the mixture was dispersed with a planetary stirrer until uniform, and then diluted with water so that the solid content became 70 wt%. Thereby, an ink containing a color pigment was obtained. The colored pigment powder is blue pigment powder 42-250A (Toukan Material), red pigment powder 42-129A (Toukan Material), yellow pigment powder 42-401A (Toukan Material), black pigment powder 42 Colored pigment inks of blue, red, yellow and black were prepared using -302A (Toukan Materials). As a protective layer, a 40% solution in which i-BMA homopolymer (weight average molecular weight 100,000) was dissolved in a mixed solvent of ethyl acetate and toluene was prepared.

  A protective layer was applied on the release film using a gravure coater. The protective layer was formed so that the layer thickness after drying was 30 μm. Next, the printing pattern layer of the desired pattern which consists of colored pigment ink was formed on the protective layer using the screen printer. The printed pattern layer was formed so that the thickness after drying was 10 μm. Thus, a film laminate A was produced.

  Another release film was prepared, and an adhesive layer was applied on the release film using a gravure coater. The pressure-sensitive adhesive layer was formed so that the layer thickness after drying was 5 μm. Thus, a film laminate B was produced.

  Thereafter, the film laminate A and the film laminate B were bonded using a laminating machine, and the release film of the film laminate A was peeled off. Thus, the label which consists of an adhesion layer, a printing pattern layer, and a protective layer was formed on the peeling film, and the label original fabric was obtained.

  Finally, label processing was performed on the original label. A half-cut is formed in a 70 mm long label and a 15 mm long gap centered on the pattern of the printed pattern layer, and the gap is removed and removed, and then slitted to a width of 60 mm to produce a reeled label sheet did.

(Evaluation of label sheet)
Various evaluations of the produced label sheets were performed by the following methods.

(Labeling suitability)
A glass bottle “Bordeaux Slim 500PP” (manufactured by Nippon Yamamura Glass Co., Ltd.) was prepared as an adherend. The label sheet was affixed on the glass bottle surface using the rotary type tack labeler currently used for the general tack label. Adhesion speed was 100 sheets / minute, everything that could be applied without any wrinkles (adhesion yield 100%) ◎, almost everything that could be applied without wrinkles (adhesion yield 90% or more, less than 100%) Was marked with ◯, and when wrinkles were occasionally generated (sticking yield: 50% or more, less than 90%) was marked with Δ. Tack labeler is configured so that a glass bottle can be set on a transport rail and transported, and at the same time, a reel-like baked label is unwound from a supported state so that it can be applied to a glass bottle while peeling the label from the release film with a peel plate. Has been. In addition, since the printed pattern layer produces defects, such as cracks, when a label with a wrinkle is fired on a label attached to a glass bottle, the wrinkled label is excluded from the firing process.

(Measurement of tensile modulus)
A film in which only a protective layer was formed on a release film was prepared and cut using a mold of No. 2 type test piece, and then the protective layer was peeled off from the release film to obtain a test piece. Regarding the test method, it measured based on JISK7133.

(Measurement of peel strength)
Make a film with only the protective layer on the release film and a film with only the adhesive layer on the other release film. After bonding the protective layer surface and the adhesive layer surface, peel the release film on the protective layer side. The test piece was cut to a width of 25 mm and a length of 200 mm. The test method was measured according to JIS K 6854-2. At this time, a double-sided PSA sheet was attached to the surface of the test stand, the protective layer side was attached to the double-sided PSA sheet, and the release film was peeled off for evaluation.

(Measurement of scratch hardness)
The peeling film was peeled off from the label sheet, and the measurement was performed in accordance with JIS K 5600-5-4 with the adhesive layer surface of the label attached to the test bench.

(Adhesion after firing)
The labeled glass bottle affixed with labeling suitability was heated from room temperature to 670 ° C. at a heating rate of 20 ° C./min, maintained at that temperature for 10 minutes, and then cooled to 100 ° C. or lower by standing in the furnace. And the glass bottle with the sintered body of the printed pattern layer cooled was taken out from the baking furnace. When cellotape (registered trademark) is affixed to the fired body formed on the glass bottle and peeled 90 degrees from the glass bottle, the case where the fired body is peeled off 10% or more from the glass bottle is Δ, and the peeled part is less than 10% ○, those that did not peel were marked with ◎.

(Examples 2 to 7)
In the same procedure as in Example 1, organic substances used for the protective layer and labels having different layer thicknesses were produced, and the tensile modulus and the layer thickness were examined. Table 1 shows the organic substances and the layer thickness used for the protective layer.

注：「−」は、焼成試験をしていないことを示す。 Table 2 shows the results of evaluating the protective layer thickness, tensile elastic modulus, tensile elastic modulus × protective layer thickness, peel strength, labeling suitability, and adhesion after firing in Examples 1 to 7.

Note: “-” indicates that no firing test was performed.

(Contrast)
From Examples 1 and 2 and Examples 5 and 6, it was confirmed that the labeling suitability was improved by setting the layer thickness to 30 μm or more even with the same tensile modulus. Further, from Examples 3 and 4 and Example 7, it was confirmed that the labeling suitability was improved by setting the layer thickness to 20 μm or more even with the same elastic modulus. Next, it was confirmed that the labeling suitability was better when the elastic modulus was higher than those of Example 3 and Example 6 even with the same layer thickness. Therefore, the relationship between the tensile elastic modulus and the protective layer thickness is important for labeling suitability, and if the tensile elastic modulus × protective layer thickness = 40 N / mm or more, the labeling suitability can be improved. More preferably, it is 46.5 N / mm or more.

(Examples 8 to 10)
Labels having different types of release films and adhesive layer thicknesses were prepared in the same procedure as in Example 1, and the relationship between the peel strengths was examined. Table 3 shows the thicknesses of the release film and the adhesive layer used.

注：「−」は、焼成試験をしていないことを示す。 Table 4 shows the results of evaluating the protective layer thickness, tensile elastic modulus, tensile elastic modulus × layer thickness, peel strength, labeling suitability, and adhesion after firing of Examples 1, 8, 9, and 10.

Note: “-” indicates that no firing test was performed.

(Contrast)
According to Examples 1, 8, 9, and 10, the labeling suitability was good when the peel strength was in the range of 0.5 to 3 mN / mm. It has been found that even when the elastic modulus × layer thickness is 46.5 N / mm, when the peel strength is 4 mN / mm, the feeding of the label may not be sufficient. It was particularly advantageous with respect to labeling suitability that the elastic modulus × layer thickness = 46.5 N / mm or more and the peel strength was 3 mN / mm or less.

(Example 11)
The same release film and adhesive layer as in Example 1 were prepared. As a protective layer, a 40% solution in which i-BMA homopolymer (weight average molecular weight 100,000) was dissolved in a hydrocarbon solvent (Sorvesso 150, manufactured by ExxonMobil) was prepared. As a barrier layer, an 18% solution prepared by dissolving an acrylic resin “KC-7000” (Kyoeisha Chemical Co., Ltd.) in a mixed solution of toluene: MEK = 50: 50 was prepared. The ink constituting the printed pattern layer was produced as follows. Ethylcellulose STD20 (manufactured by Nihon Kasei Co., Ltd.) is α- with respect to the total weight of inorganic powder in a ratio of 20 parts by weight of pigment powder and 80 parts by weight of glass powder (Si: Bi = 100 at%: 40 at%). A 15% solution dissolved in terpineol (manufactured by Kanto Chemical Co., Inc.) is mixed at a weight ratio (inorganic powder: resin) of 95: 5, dispersed with a planetary stirrer until uniform, and then solid The ink was diluted with diethylene glycol dibutyl ether (Wako Pure Chemical Industries, Ltd.) so that the content was 70 wt%, and an ink containing a colored pigment was prepared. Color pigments include blue pigment powder 42-250A (Toukan Material), red pigment powder 42-129A (Toukan Material), yellow pigment powder 42-401A (Toukan Material), black pigment powder 42- Using 302A (manufactured by Toukan Material), colored pigment inks of blue, red, yellow, and black were prepared.

  A barrier layer was coated on the release film using a gravure coater, dried with a hot air dryer, and then formed to have a thickness of 15 μm. In this way, a film laminate C was produced. The adhesion layer was apply | coated using the gravure coater on another peeling film. The pressure-sensitive adhesive layer was formed so that the layer thickness after drying was 5 μm. In this way, a film laminate D was produced. Thereafter, the film laminates C and D were bonded together using a laminating machine, and the release film of the film laminate C was peeled off. Next, a printed pattern layer having a desired pattern made of a color pigment was formed on the barrier layer using a screen printer, and a protective layer was further formed so as to cover the printed pattern layer. The thickness of the printed pattern layer and the protective layer after drying was formed to be 10 μm and 15 μm, respectively. Thereafter, the same processing as in Example 1 was performed to form a reel, and a label composed of an adhesive layer, a barrier layer, a printed pattern layer, and a protective layer was formed on the release film.

(Examples 12, 13, and 14)
As a protective layer, acrylic fine particle chemisnow MR-1HG (manufactured by Soken Chemical Co., Ltd.) was added to a 40% solution of i-BMA homopolymer (weight average molecular weight 100,000) dissolved in a hydrocarbon solvent (Solvesso 150 manufactured by ExxonMobil). Was added at a solid content ratio of 10 wt%. A fired label was produced in the same procedure as in Example 11 except that the layer thickness was 10 μm and the barrier layer was 5 μm. As another example, label sheets having different barrier layer and protective layer thicknesses were produced in the same procedure as in Example 11. Example 13 had a barrier layer of 5 μm and a protective layer of 10 μm, and Example 14 had a barrier layer of 15 μm and no protective layer.

Table 5 shows the evaluation results of Examples 11 to 14 and Example 6. In the evaluation, the tensile modulus was measured by forming a barrier layer and a protective layer on the release film, and using the laminate of the barrier layer and the protective layer as a test piece.

(Contrast)
In the case of the protective layer of 20 μm of Example 6, the tensile modulus × layer thickness = 31.0 N / mm, which is less than 40 N / mm, so the labeling suitability was not good. On the other hand, as in Example 11, the labeling suitability could be improved by increasing the tensile elastic modulus × layer thickness by inserting a barrier layer. Further, according to Example 12 and Example 13, as in Example 13, when the total layer thickness of tensile elastic modulus × barrier layer and protective layer was 26.3 N / mm, the labeling suitability was not good. As in Example 12, when the tensile modulus × the total thickness of the barrier layer and the protective layer was 40.0 N / mm, the labeling suitability was good. Even with the same thickness, if the tensile modulus × barrier layer was 40 N / mm or more, the labeling suitability could be improved.

  According to Example 12 and Example 13, the elastic modulus of the protective layer could be improved by adding fine particles composed of acrylic resin to the protective layer in order to increase the tensile elastic modulus. Moreover, when there was no protective layer like Example 14, the pencil scratch hardness which is an impact test was 6B or less. This is because the printed pattern layer is formed of a layer containing a large amount of inorganic powder, and there are few organic substances that bind the inorganic powder. The impact resistance can be improved by covering the printed pattern layer with a protective layer.

  Based on the above teaching, those skilled in the art can make various modifications to the embodiments. A glass bottle is an example of an article having a non-flat surface. The release film may be a sheet having flexibility, and its specific configuration and material are arbitrary. The shape of the island-shaped label on the release film as viewed from above is arbitrary, and examples thereof include a rectangular shape, a circular shape, and a star shape. Examples of the pattern printed on the printed pattern layer include characters, photographs, and arbitrary patterns.

  In the above disclosure, there is provided a method for producing a label sheet, the step of producing a laminate in which at least an adhesive layer and a printed pattern layer are laminated in this order on a release film, and the laminate on the release film. And a step of leaving a plurality of island-like labels spaced apart from each other on the release film by selective removal.

100: Label sheet

50: Release film 52: Release agent layer

60: Label 61: Adhesive layer 62: Print pattern layer 63: Protective layer 64: Barrier layer

70: Glass bottle

10: Tack labeler 11: Label sheet supply unit 12: Peel plate 13: Release film recovery unit

41: Rotation conveyance mechanism 42: Stock yard 43: Stock yard

Claims (15)

A label sheet comprising a release film and two or more island-like labels laminated in a peelable manner on the release film,
Each label
With laminated on the release film, the adhered peeled from the release film to the surface of the release film side to the adherend, and Rubeki adhesive layer is removed by firing,
While laminated on at least the adhesive layer and the release film on the via, and the printed pattern layer to be affixed to the adherend by the firing,
Laminating on the release film via at least the adhesive layer and the printed pattern layer, and comprising a protective layer to be removed by the firing ,
The calculated value of the tensile elastic modulus × thickness of the protective layer is Ru der than 40N / mm, the label sheet. A label sheet comprising a release film and two or more island-like labels laminated in a peelable manner on the release film,
Each label
Laminate on the release film, peel from the release film and adhere to the adherend from the surface on the release film side, and an adhesive layer to be removed by firing;
Laminate on the release film through at least the adhesive layer, and a printed pattern layer to be fixed to the adherend by the firing,
Laminating on the release film via at least the adhesive layer and the printed pattern layer, and a protective layer to be removed by the firing,
Including a barrier layer to be removed by the firing , ensuring at least a barrier property between the adhesive layer and the printed pattern layer ;
A label sheet in which a calculated value of tensile elastic modulus × total layer thickness of a portion where the protective layer and the barrier layer are laminated is 40 N / mm or more . The printed pattern layer is a layer in which one or more inks are deposited so as to form a pattern,
The inks, inorganic pigments, wherein the weldable glass powder to the adherend, and including at least a removable organics by the firing, the label sheet according to claim 1 or 2. The label sheet according to claim 3, wherein the glass powder contained in the ink contains bismuth-based glass. The label sheet according to claim 1, wherein the protective layer includes a methacrylic acid ester polymer. The glass transition temperature of the protective layer is Ri der 40 ° C. or higher, the protective layer has a 5~50μm thickness, the adhesive layer has a thickness of 1 to 20 [mu] m, any one of claims 1 to 5 The label sheet according to one item . The label sheet according to any one of claims 1 to 6 , wherein the release film includes a base material and a release agent layer formed on the base material. The label sheet according to any one of claims 1 to 7 , wherein the adherend is an article made of glass or ceramic. The label sheet according to any one of claims 1 to 8 is fed,
And peeling the label from the release film at a feed course of the label sheet, it adhered the label to the adherend from the surface of the release film side of the adhesive layer,
A method for producing an article with a printed pattern, wherein the adherend to which the label is attached is fired. The step of peeling the label from the release film in the process of feeding the label sheet includes a step of feeding the label from the release film toward the adherend at a change position in the feeding direction of the label sheet. 10. A method for producing an article with a printed pattern according to 9 . In the step of manufacturing a laminate in which at least an adhesive layer, a printed pattern layer, and a protective layer are laminated in this order on a release film, the adhesive layer is peeled off from the release film from the surface on the release film side. It is a layer that adheres to the adherend and should be removed by firing, the printed pattern layer is a layer that should adhere to the adherend by firing, and the protective layer should be removed by firing Producing a laminate, which is a layer;
Selectively removing unnecessary portions that divide the laminate on the release film into island-like labels, thereby leaving a plurality of island-like labels spaced apart from each other on the release film;
A method for producing a label sheet, wherein the calculated value of tensile elastic modulus x layer thickness of the protective layer is 40 N / mm or more. In the step of manufacturing a laminate in which at least an adhesive layer, a barrier layer, a printed pattern layer, and a protective layer are laminated in this order on the release film, the adhesive layer is peeled from the release film and the release film side It is a layer that adheres to the adherend from the surface and should be removed by firing, and the barrier layer is a layer that should be removed by firing to ensure at least a barrier property between the adhesive layer and the printed pattern layer. The printed pattern layer is a layer to be fixed to the adherend by the baking, and the protective layer is a layer to be removed by the baking;
Selectively removing unnecessary portions that divide the laminate on the release film into island-like labels, thereby leaving a plurality of island-like labels spaced apart from each other on the release film;
A method for producing a label sheet, wherein a calculated value of tensile elastic modulus x total layer thickness of a portion where the protective layer and the barrier layer are laminated is 40 N / mm or more. The printed pattern layer is a layer in which one or more inks are deposited so as to form a pattern,
The method for producing a label sheet according to claim 11 or 12, wherein the ink includes at least an inorganic pigment, a glass powder that can be welded to the adherend, and an organic substance that can be removed by the baking. The method for producing a label sheet according to claim 13, wherein the glass powder contained in the ink contains bismuth-based glass. The said protective layer is a manufacturing method of the label sheet as described in any one of Claims 11 thru | or 14 containing a methacrylate ester polymer.

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