JPS63164158A - Armoring label for dry cell - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to an improved exterior label for dry batteries, and particularly to an exterior label for dry batteries that is excellent in appearance, robustness of the printed layer, and productivity.

[Conventional technology and its problems]

Conventionally, various types of exterior labels for dry batteries have been proposed. For example, Japanese Patent Laid-Open No. 59-123161 discloses a pressure-sensitive adhesive layer formed on the back surface of a heat-shrinkable resin film as a base material. Wrap it around the battery body using
Both ends of the heat-shrinkable resin film protruding outside the top and bottom of the dry battery body are heated and shrunk to provide an annular covering around the surface periphery of the top and bottom of the dry battery. Proposed.

However, in one of the labels proposed in the above publication, a pressure-sensitive adhesive layer is formed on the back side of a single layer of heat-shrinkable resin film via a gold M vapor deposited layer, while a printing layer is formed on the surface of the film. The label with the formed structure is created by the fact that alkaline or acidic substances that adhere to the outer peripheral surface of the dry battery body as contaminants during the manufacturing process of the dry battery body penetrate into the pressure-sensitive adhesive layer of the label and finally reach the metal vapor deposition layer. In addition, when the printing layer formed on the surface of the film is an ultraviolet curable ink, the adhesion between the film and the printing layer is poor. For example, when peeling off an adhesive label such as a price tag attached during store sales, the printed layer may peel off.
It has drawbacks such as being damaged and reducing its commercial value.

Furthermore, there is another label proposed in the above-mentioned publication, namely, a heat-shrinkable resin film having a pressure-sensitive adhesive layer on the back side and a heat-shrinkable resin film having a metal vapor-deposited layer on one side through a solvent-free adhesive. As in the case described above, a layer with a structure in which a heat-shrinkable resin film is layered with a metal vapor-deposited layer on the adhesive side and a printed layer is formed on the surface of the layer is similar to the above-mentioned case. In addition to insufficient adhesion, the above-mentioned solvent-free adhesive requires a certain amount of aging time to harden, so if a so-called seal cut is performed with a punching blade immediately after forming a printing layer with ultraviolet curable ink, the adhesive will The adhesive, which is still fluid in the cured state, may adhere to the punching blade, causing problems such as peeling off the label that should originally be left on the release paper and removing it from the release paper. Heat shrinkable formed (
When applying adhesive after sufficiently curing the solvent-free adhesive using a H fat film, the release paper combined with the label material may absorb moisture during the storage period for aging of the adhesive. This causes dimensional changes in the label material, making it extremely difficult to achieve dimensional consistency between the printed design and the stamped design. However, it was difficult to match the elongation rates of the two layers of heat-shrinkable resin films, and the resulting label curled significantly in its free state after being peeled off from the release paper. It often happens that it becomes impossible to put it on.

In addition, Japanese Patent Application Laid-open No. 59-158067 discloses that a single-layer heat-shrinkable resin film has an adhesive layer on the back side for adhesion to the dry battery body, and a printed layer is formed on the film surface via a metal vapor deposition layer. An exterior label for dry cell batteries has been proposed.

However, when the heat-shrinkable resin film of this label is made of polyvinyl chloride, the adhesion between the film and the vapor-deposited metal layer is extremely poor, and the vapor-deposited metal easily falls off due to friction etc., destroying the printed design. Furthermore, even if a vapor-deposited undervarnish is applied to the film prior to metal deposition to ensure adhesion between the metal-deposited layer and the film, a printing layer cannot be printed on the top surface of the metal-deposited layer using ultraviolet curing ink. When a pressure-sensitive adhesive label such as the above-mentioned price tag label is peeled off, the printed design is similarly destroyed because the adhesion between the printed layer and the metal vapor-deposited layer is insufficient. Additionally, this publication proposes an exterior label for dry batteries having a structure in which another heat-shrinkable resin film is "arranged" on the top surface of the printed layer of the label obtained as described above. There is no specific description of the method described above, and it is clear that if two layers of the above film were simply stacked and pressed together without using an adhesive, they would be easily separated.

In addition, JP-A-52-13566 discloses a heat-shrinkable resin film with metallic printing formed by forming an anchor coat layer, a metal vapor deposited layer, an ink layer, and a transparent layer in this order on the surface of a heat-shrinkable resin film. In the production of dried 1 fat film,
It has been proposed that the anchor coat layer, printing layer, and transparent layer are all derived from the same type of sealing resin that has adhesive properties to the film and the vapor-deposited metal layer. Examples of such resins include polychlorinated resin. copolymer of vinyl and vinyl acetate,
Nitrified cotton polyester, nitrated cotton acrylic, chlorinated rubber polyamide, or butyral resin, etc. are mentioned, and the anchor coat layer is formed with a resin paint based on one of these materials, and the paint forming the anchor coat layer is also used. It is disclosed that a printing layer is formed using ink of the same quality, and a transparent layer is further formed using a transparent paint of the same quality as the paint forming the anchor coat layer.

However, it is clear that both the above-mentioned printed layer and transparent layer are formed from a resin solution whose main material is a resin dissolved in an organic solvent, and it is difficult to form the printed layer and transparent layer using such materials. In this case, a relatively long drying process is required to substantially completely dry the contained organic solvent, and therefore it is not suitable for high-speed label printing. That is,
If 1 m of organic solvent remains, the film will shrink over time, making it impossible to maintain the required heat absorption rate, and this shrinkage over time will often cause uneven dimensional changes, making it difficult to print beautiful designs. .

Therefore, an object of the present invention is to eliminate the various drawbacks of the above-mentioned prior art, to provide a vapor-deposited aluminum layer with high durability, a strong printed layer, and high-speed installation into a dry battery body. The objective is to provide an exterior label for dry batteries with good productivity.

[Means for solving problems]

As a result of intensive research to achieve the above object, the present inventors formed a vapor-deposited aluminum layer on the surface of a heat-shrinkable vinyl chloride film having a pressure-sensitive adhesive layer on the back side via a resin layer. Then, by forming a printing layer using ultraviolet curable ink through the resin layer, the obtained outer label for dry cell battery has great durability due to the vapor-deposited aluminum layer, the printing layer is strong, and it can be attached to the dry cell battery body at high speed. We found that it is possible and highly productive.

The present invention has been made based on the above findings, and includes forming a pressure-sensitive adhesive layer for adhesion to the dry battery body on the back side of a heat-shrinkable vinyl chloride film stretched at least uniaxially, and An exterior label for a dry battery, characterized in that a vapor-deposited aluminum layer is formed on the surface of a vinyl film through a 41 fat layer, and a printing layer made of ultraviolet curable ink is formed on the surface of the vapor-deposited aluminum layer through a resin layer. By providing this, the above objectives have been achieved.

(Example) Hereinafter, the exterior label for a dry battery of the present invention will be described based on an example shown in the drawings.

FIG. 1 is a sectional view of an embodiment of the present invention before being peeled off from the release paper. In the figure, l is a heat-shrinkable vinyl chloride film, 3 is a vapor-deposited aluminum layer formed on the surface of the film l via resin N2, and 5 is a vapor-deposited aluminum layer formed on the surface of the attached aluminum layer 3 via a resin layer 4. A printed layer made of ultraviolet curable ink, 6 a pressure-sensitive adhesive layer formed on the back side of the film 1 for adhesion to the dry battery body, and 7 an overcoat formed on the surface of the printed layer 5 as necessary. The eyebrows and 8 are release paper (release paper).

To explain each part of the embodiment in detail, the heat-shrinkable vinyl chloride film 1 is stretched in at least one direction, and the direction of contraction coincides with the circumferential direction of the outer periphery of the dry cell main body. The shrinkage rate of the film l is related to the width of the annular covering around the top and bottom surfaces of the dry battery,
When the width of the annular covering part is 2.5 mm in an AA battery with a diameter of 14 mm, the width is about 36% or more, and 3IIl
In the case of r@, it is preferably about 43% or more.

In addition, the thickness of the film l is preferably 30 μ to 1 OOp; if it is less than 30 μ, the label will not be self-supporting, and the direction of travel of the label will be constant when it is continuously peeled off from the release paper and sent out using an automatic labeler. This is not preferable because it is difficult to attach the label and tends to reduce the productivity of attaching the label. Further, if the thickness is more than 100 μm, it is not preferable because after the film is attached to the dry battery main body, the end of the label tends to peel off naturally (spring up) at the overlapping portion of the body over time.

Further, the resin layer 2 is made of a heat-shrinkable vinyl chloride film l.
and the vapor-deposited aluminum layer 3 to make them adhere to each other. Vinyl chloride-vinyl acetate copolymer, acrylic copolymer resin, butyral resin, ethylene-vinyl acetate copolymer, ethylene-vinyl acetate copolymer, etc. Carbon oxide copolymers, chlorinated rubber resins, polyester resins, polyamide resins, urethane resins, etc. can be used, but acrylic copolymer resins are preferable.For the formation of resin N2 on the heat-shrinkable vinyl chloride film l, these resins can be used. This can be carried out by dissolving at least one of the above in an organic solvent and adding additives such as a plasticizer as necessary, and then uniformly coating the heat-shrinkable vinyl chloride film 1 with a fine sealing liquid and drying it. In this case, if the organic solvent remains in the heat-shrinkable vinyl chloride film 1, it may shrink over time and cause dimensional changes, it may not be possible to maintain the desired shrinkage rate, and there are various other problems such as difficulty in attaching aluminum. Therefore, it is preferable to use a quick-drying organic solvent such as ethyl acetate or methyl ethyl ketone as the tJl solvent. In addition, as the method of coating and drying, it is preferable to use a gravure printing machine. In this case, there is almost no dimensional shrinkage or change in shrinkage rate due to heating of the heat-shrinkable vinyl chloride film l, and the coating speed can be increased. . The preferred thickness of the resin layer 2 is 0.
It is 5-5μ, more preferably 0.5-3μ, particularly preferably 0.5-1.5μ.

In addition, the above-mentioned violet-plated aluminum layer 3 can be formed by a well-known vacuum deposition method, and its thickness is preferably 200 to 400 mm in order to give a substantially opaque metallic luster to the appearance of the dry battery. If the thickness is less than 200 Å, the transparency will be high and the metallic luster will be insufficient, whereas if the thickness exceeds 400 Å, it will be unnecessary and uneconomical.

The resin layer 4 is interposed between the vapor-deposited aluminum Ji#3 and the printing layer 5 made of ultraviolet curable ink to bring them into close contact, and is made of vinyl chloride-vinyl acetate copolymer, acrylic copolymer resin. , butyral), a quick-drying organic solvent, at least one selected from ethylene-vinyl acetate copolymer, ethylene-vinyl acetate-carbon oxide copolymer, chlorinated rubber resin, polyester resin, polyamide resin, urethane resin, etc. For example, a resin solution dissolved in ethyl acetate, methyl ethyl ketone, etc. and optionally added with additives such as a plasticizer, more preferably a resin solution in which an ultraviolet curable resin is mixed with the resin solution, is added to the stem-attached aluminum. It is preferable to form the coating on the upper surface of the lining 3 using a gravure printing machine.

In particular, when using the latter mixture of ultraviolet curable resin, a chemical bond is formed between the resin layer 4 and the ultraviolet curable ink formed on the upper surface of this resin layer 4, resulting in excellent adhesion. can get. As such an ultraviolet curable resin, those commonly used as ultraviolet curable transparent inks can be used.

The preferred thickness of the resin layer 4 is 0.5-5μ, more preferably 0.5-3μ, particularly preferably 0.5-1.5μ.

In addition, the above pressure sensitive adhesive M6 for adhesion to the dry battery body
Either an acrylic copolymer pressure-sensitive adhesive or a rubber-based pressure-sensitive adhesive prepared by adding a tackifier resin, a plasticizer, etc. to a rubber-based polymer such as natural rubber or synthetic rubber can be used for its formation. It is preferable to use an acrylic copolymer with good aging resistance and a pressure-sensitive adhesive. Among them, in the label punching process described later, the pressure-sensitive adhesive adheres to the punching blade and is left on the release paper. It is preferable to use a pressure-sensitive adhesive that has enough cohesive strength to prevent the trouble of peeling off the label, and is preferably an acrylic adhesive with a curing agent or crosslinking agent such as an amino resin, epoxy resin, polyisocyanate compound, or metal chelate. Copolymer pressure sensitive adhesives are preferred. Further, the thickness of the pressure sensitive adhesive Ff6 is preferably 10 to 50 μm, more preferably 20 to 4 μm.
It is 0μ. Furthermore, in order to form the pressure-sensitive adhesive layer 5 on the surface of the heat-shrinkable vinyl chloride film 1, it is convenient and preferable to use a so-called adhesive processing method. A pressure-sensitive adhesive solution is uniformly applied onto release paper (release paper) 8 coated with silicone resin by baking, and after drying the solvent, heat-shrinkable vinyl chloride is applied to the surface of the resulting pressure-sensitive adhesive layer 6. film 1
All you have to do is paste them together. It is reasonable to form such a pressure-sensitive adhesive layer 6 after forming the resin layer 2, aluminum binding layer 3, and resin layer 4 in this order on the surface of the heat-shrinkable vinyl chloride film l. It is preferable. The laminate 9 with the release paper 8 obtained in this way will be referred to as an adhesive sheet hereinafter.

In addition, the transparent overcoat layer 7 formed as necessary is for improving the surface gloss of the printed layer 5 when the surface gloss is insufficient, and is an uncolored transparent overcoat layer 7 that is cured by ultraviolet rays. It can be easily formed using a rotary printing press using mold ink. The thickness of the overcoat layer 7 is
Preferably it is 1-15μ, more preferably 3-1Oμ.

Therefore, in order to form the outer label for dry cell batteries of the present invention,
For example, first, after forming the adhesive sheet 9 as described above,
A printing layer 5 is formed on the resin layer 4 of the adhesive sheet 9 using an ultraviolet curable ink using a rotary printing press 10 as shown in FIG. Ultraviolet curable ink does not contain organic solvents and does not generate residual solvent on the printing substrate, so there is no dimensional change over time of the heat-shrinkable vinyl chloride film 1, no change in the 2g shrinkage rate, and there is no change in the 2g shrinkage rate when irradiated with ultraviolet rays. Since the heat generated by heating or reaction curing is extremely small, the dimensions and heat shrinkage rate of the film can be maintained.

According to a rotary printing press 1O as shown in FIG. 2, printing of almost any design and color is possible using five plate cylinders 1). In particular, by performing cut-out printing and seeing through the vapor-deposited aluminum layer 3 from the outside, f! 7, it is possible to impart a metallic luster to the appearance of the dry battery, and if transparent yellow ink is used, it is also possible to impart a gold-tone metallic luster to the appearance of the dry battery.

The ultraviolet curable ink transferred to the adhesive sheet 9 by the plate cylinder 1) is irradiated with ultraviolet rays by the ultraviolet irradiators 13 and 14 to be cured, thereby completing the formation of the printed Fij 5.

The printed layer 5 obtained as described above usually has a sufficiently beautiful appearance and is free from friction or impact during handling, such as during the dry cell manufacturing process, packaging process, IL transport, and loading into equipment using dry cell batteries. Not only will it not peel off, but even if you peel off adhesive labels such as price tags affixed during store sales, the ink or vapor-deposited aluminum will not peel off or transfer, and the printed design will be completely preserved. Can be retained.

In addition, when forming the overcoat layer 7 on the surface of the printing N5 using an uncolored transparent ultraviolet curable ink, the transparent ultraviolet curable ink is applied to the semi-finished printing using the printing cylinder 12 shown in FIG. After it is uniformly transferred onto the upper surface of the layer 5, it may be cured by irradiating ultraviolet rays with the ultraviolet irradiator 14.

After forming the printed layer 5 on the surface of the adhesive sheet 9 with release paper 8 as described above and, if necessary, further forming the overcoat layer 7 on the surface of the adhesive sheet 9', this adhesive sheet 9 is cut into a predetermined size using a punching blade using a punching machine (not shown) that operates in conjunction with the rotary printing press 10 without cutting the release paper 8 immediately following the printing process, By removing unnecessary portions, a dry battery exterior label with the surface of the pressure-sensitive adhesive layer 6 protected by the release paper 8 can be obtained. Note that it is extremely easy to match the printed design and the punched design.

Next, the present invention will be explained in more detail with reference to manufacturing examples.

Production Example 1 Methyl methacrylate/butyl acrylate (70/30) copolymer resin was applied to the surface of a heat-shrinkable vinyl chloride film with a thickness of 40μ and a heat shrinkage rate of 50%, stretched uniaxially in the flow direction of the machine. An ethyl acetate-toluene mixed solvent solution was applied and dried using a gravure printer. The coating thickness was approximately 1 μm. When aluminum was deposited on this resin-coated surface to a thickness of approximately 200 mm using the vacuum deposition method, the aluminum deposited layer had a uniform metallic luster, and Sellotape was pasted on top of it, and the reprint was made. However, the bonded aluminum did not fall off and was firmly adhered.

Next, a resin liquid having the following composition was coated on the upper surface of this aluminum vapor deposited layer using a gravure printing machine and dried.

The coating thickness was approximately 1.5 microns.

[Resin liquid composition]

・Methyl methacrylate/butyl acrylate (70/30) composite resin 10 parts by weight ・Ultraviolet curing ink (manufactured by Toka Shiki ■, Best Cure M
lo LTP FL OP varnish) 5 parts by weight Ethyl acetate-toluene (8/2) mixed solvent 85 parts by weight On the other hand, polyethylene was melt-coated to a thickness of 20μ on the surface of 70 g/nr glassine paper, and further coated on the surface. On the release surface of release paper made by applying and curing silicone resin, apply Olivine BPS-3233 (acrylic adhesive manufactured by Toyo Ink Manufacturing Co., Ltd.) uniformly to a dry thickness of 25 μm and dry. The surface of the pressure-sensitive adhesive layer obtained by drying is laminated with the non-aluminum-deposited side of the aluminum-deposited heat-shrinkable vinyl chloride film described in +ii, and a sheet with release paper 8 as shown in FIG. Adhesive sheet 9
I got it.

Next, printing was performed using a 5KP250A label printing machine manufactured by Sanki Kikai ■. During printing, white, black, red, blue, and yellow inks for Guicure MV seals manufactured by Dainippon Ink and Chemicals were used as ultraviolet curable inks. Even when cellophane tape was attached to the top surface of the printed layer that had been cured by ultraviolet irradiation and then peeled off, the ink remained firmly adhered to the layer without peeling off.

Next, on the top surface of the above-mentioned printing layer, apply UV curable transparent ink of Toka Shiki I'hlOLTPFL.
When overcoated with OP varnish, the surface gloss of the printed layer improved and became even more beautiful.

Immediately thereafter, the label was punched out using a die cutter installed in the label printing machine described above. The label, which was released 21) from the release paper and became free, was flat and independent.

Next, the length of the heat-shrinkable vinyl chloride film in the machine direction is 3 mm longer than the circumferential length of the battery body, and the length of the film in the lJ force direction is 6 mm (
(To make each 31 protrude from the top and bottom of the battery) 1 stamp the above label 1 into a large rectangle.
6 was wrapped around the battery body 15 and glued as shown in FIG.
As shown in b), the end of the label shrinks and wraps uniformly around the surface periphery of the head and bottom to create an annular cover with a good appearance.17
was gotten.

〔Effect of the invention〕

The effects of the outer label for dry batteries of the present invention are listed below.

(a) The deposited aluminum layer and the printed layer are robust against friction and peeling effects.

(b) The thin aluminum layer may be damaged by alkaline or acidic contaminants.

(c) Since labels that stand up flat and free-standing can be obtained, the operation of the automatic labeler is stable.

(d) Since punching can be performed immediately after printing, it is easy to match the dimensions of the printed design and the punched design.

(e) Label productivity is high.

[Brief explanation of the drawing]

FIG. 1 is an enlarged vertical cross-sectional view of an exterior label for a dry battery according to an embodiment of the present invention before peeling off the separate paper pattern, FIG. 2 is a schematic diagram of the process of forming a printing layer and an overcoat layer using a rotary printing machine,
Figure 3 (al and (bl) are perspective views showing the process of attaching the label to the dry battery body in order of process. ]... Heat-shrinkable vinyl chloride film 2... fathom) Vapor-deposited aluminum layer 4...Resin layer 5...Printed layer 6...Pressure sensitive adhesive layer 7...Overcoat layer 8...Release paper 9...Adhesive sheet 9'' -Printed adhesive sheet 10... Rotary printing press 1) Printing cylinder 12 Overcoat cylinder 13, 14 Ultraviolet irradiator 15 Dry battery 1G Battery exterior label 17 Annular cover Patent applicant Nippon Karhide Kogyo Co., Ltd. Figure 3 Figure 4 Procedural Amendment (Method) December 23, 1985 Director General of the Patent Office Kunio Ogawa 1, Indication of Case Patent Application No. 1981-308146 2, Name of Invention Exterior for Dry Battery Label 3, Relationship with the case of a person who commits negligent correction Patent applicant address: 3-3-1-5 Marunouchi, Chiyoda-ku, Tokyo, column for a brief explanation of the drawing of the statement of subject matter of the amendment. 6. Contents (1) “Figure 3 fa” from page 20, line 20 to page 21, line 2
t... is. '' to ``Figure 3 is a perspective view showing the form at the stage where the label is wrapped around the battery body and adhered, and Figure 4 is a perspective view showing the dry battery with the label attached.'' December 23rd

Claims (2)

[Claims] (1) A pressure-sensitive adhesive layer is formed on the back side of a heat-shrinkable vinyl chloride film stretched at least uniaxially for adhesion to the dry battery body, and a pressure-sensitive adhesive layer is formed on the surface of the heat-shrinkable vinyl chloride film via a resin layer. An exterior label for a dry battery, characterized in that a vapor-deposited aluminum layer is formed, and a printing layer made of ultraviolet curable ink is formed on the surface of the vapor-deposited aluminum layer via a resin layer. (2) A transparent overcoat layer made of ultraviolet curable ink is formed on the surface of the printing layer.
Exterior label for dry cell batteries as described in section 1).