JP2016191858A - Heat shrinkable adhesive label, label continuous body and container with label - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a heat shrinkable adhesive label excellent in steam barrier property and having relatively large heat shrinkage factor.SOLUTION: A heat shrinkable adhesive label 1 is a heat shrinkable base material 2 having a front face layer 5, a back face layer 6 and an intermediate layer 7 between the front face layer 5 and back face layer 6. The front face layer 5 and the back face layer 6 are constituted of a resin layer containing a cyclic olefin polymer as a main component resin, and the intermediate layer 7 comprises the heat shrinkable base material 2 having a rein layer containing an olefinic elastomer as a main component resin, and an adhesive layer 3 provided on the back side of the heat shrinkable base material 2.SELECTED DRAWING: Figure 3

Description

  The present invention relates to a heat-shrinkable pressure-sensitive adhesive label that is wound around an eye drop container or a prefilled syringe.

A heat-shrinkable pressure-sensitive adhesive label is wrapped around and attached to a container in which medicines such as eye drops, cosmetics, seasonings, beverages, foods, and the like are stored. For example, an ophthalmic container equipped with a heat-shrinkable pressure-sensitive adhesive label is obtained by winding a heat-shrinkable pressure-sensitive adhesive label across the cap and the container body and then heating.
Such a heat-shrinkable pressure-sensitive adhesive label has a heat-shrinkable base material, a printed layer provided on the front surface side of the heat-shrinkable base material, and a pressure-sensitive adhesive layer provided on the back surface side of the heat-shrinkable base material. .
Conventionally, a polyethylene terephthalate film has been used as a base material for the heat-shrinkable pressure-sensitive adhesive label because of its excellent transparency and strength (for example, Patent Document 1). The waist of the base material can be said to be the rigidity of the base material.
However, a polyester film used as a heat-shrinkable pressure-sensitive adhesive label wound around a container has a low water vapor barrier property. In particular, a polyester film stretched in the MD direction cannot be said to have a sufficiently high heat shrinkage rate. .
In addition, since the polyester film has high rigidity, when the knob is formed on the heat-shrinkable pressure-sensitive adhesive label, the knob becomes too hard due to the heat shrinkage, and the feeling of use becomes worse.

JP-A-4-344222

A first object of the present invention is a heat-shrinkable pressure-sensitive adhesive label having excellent water vapor barrier properties, moderate rigidity, and a relatively large heat shrinkage rate, and a label continuum in which a plurality of the heat-shrinkable pressure-sensitive adhesive labels are arranged on release paper. Is to provide.
The second object of the present invention is to provide a labeled container excellent in water vapor barrier properties.

  The heat-shrinkable pressure-sensitive adhesive label of the present invention is a heat-shrinkable substrate having a surface layer, a back surface layer, and an intermediate layer between the surface layer and the back surface layer, and the surface layer and the back surface layer are cyclic. A heat-shrinkable base material comprising a resin layer containing an olefin polymer as a main component resin, and the intermediate layer having a resin layer containing an olefin-based elastomer as a main component resin; and And an adhesive layer provided on the back side.

According to another aspect of the present invention, a label continuum is provided.
The label continuum of the present invention includes the heat-shrinkable pressure-sensitive adhesive label and a long strip-shaped release paper, and the heat-shrink direction of the pressure-sensitive adhesive label is the longitudinal direction of the release paper, and the heat shrinkage A plurality of adhesive pressure-sensitive adhesive labels are temporarily pasted on the release surface of the release paper via the pressure-sensitive adhesive layer.

According to another aspect of the present invention, a labeled container is provided.
The labeled container of the present invention includes the heat-shrinkable pressure-sensitive adhesive label and a container having a container body, and the heat-shrinkable pressure-sensitive adhesive label is wound around the container body and has an adhesive layer interposed therebetween. While being affixed to the container body, it is in close contact with heat shrinkage.

The heat-shrinkable pressure-sensitive adhesive label of the present invention has appropriate rigidity, the heat-shrinkable base material has a relatively large heat shrinkage rate, and further has a pressure-sensitive adhesive layer, so that it easily adheres to the container when attached to a container. Furthermore, since it has an excellent water vapor barrier property, a container with a label having an excellent water vapor barrier property can be constituted by heat-shrinking the container.
In addition, since the labeled container of the present invention is excellent in water vapor barrier properties, the content is hardly deteriorated by moisture, and when the content contains, for example, moisture, the moisture is also difficult to evaporate.

The top view which looked at the heat-shrinkable adhesive label which concerns on the 1st example of 1st Embodiment from the surface side. The top view which looked at the heat-shrink adhesive label from the back side. FIG. 3 is a cross-sectional view taken along line III-III in FIG. 2. The cross-sectional view of the heat-shrinkable pressure-sensitive adhesive label according to the second example of the first embodiment (the heat-shrinkable pressure-sensitive adhesive label of the second example is cut at the same position as the line III-III in FIG. 2). The cross-sectional view of the heat-shrinkable pressure-sensitive adhesive label according to the third example of the first embodiment (the heat-shrinkable pressure-sensitive adhesive label of the third example is cut at the same position as the line III-III in FIG. 2). It is a reference figure which shows the manufacture procedure of a heat-shrink adhesive label, Comprising: (a) is a side view of the base material raw material temporarily attached to the release paper, (b) is a perforation line and a notch in the base material raw material. The top view of the process of forming a line, (c) is a side view of the process of removing the unnecessary area | region of a base material original fabric, (d) is a top view of the manufactured heat-shrinkable adhesive label. The front view of the labeled container which concerns on 1st Embodiment. The rear view of the container with the label. The top view which looked at the container with the label from the top | upper surface side of the cap part. The bottom view which looked at the container with the label from the bottom face side of the container main body. The front view of the container used for the labeled container which concerns on the modification of 1st Embodiment. The front view of the container with a label which concerns on the modification of 1st Embodiment. The perspective view which looked at the heat-shrinkable adhesive label which concerns on 2nd Embodiment from the back surface side. The front view of the container used for the labeled container which concerns on 2nd Embodiment. The front view which shows the manufacture procedure of the container with the label. (A) is a front view of the container with a label, (b) is the sectional drawing. (A) is a front view of the labeled container which concerns on the modification of 2nd Embodiment, (b) is the sectional drawing.

Hereinafter, the present invention will be specifically described with reference to the drawings.
In the present specification, the “lateral direction” of the heat-shrinkable substrate is a direction that becomes the circumferential direction of the container when the heat-shrinkable adhesive label is wound around the container, and the “longitudinal direction” of the heat-shrinkable substrate. "Is a direction orthogonal to the transverse direction in the plane of the heat-shrinkable substrate. Further, “upper” refers to the first longitudinal side of the heat-shrinkable substrate, “lower” refers to the second longitudinal side of the heat-shrinkable substrate (the opposite side to the first longitudinal direction), “Left” refers to the first lateral side of the heat-shrinkable substrate, and “right” refers to the second lateral side of the heat-shrinkable substrate (the side opposite to the first lateral direction).
Note that the dimensions and scales of the parts and layers shown in each figure are different from the actual ones.

[First Embodiment]
In FIG. 1 thru | or FIG. 3, the heat-shrinkable adhesive label 1 of this invention has the heat-shrinkable base material 2 and the adhesive layer 3 provided in the back surface side of the said heat-shrinkable base material 2. FIG. Preferably, the heat-shrinkable pressure-sensitive adhesive label 1 has a heat-shrinkable base material 2, a pressure-sensitive adhesive layer 3, and a design print layer 4. The heat-shrinkable pressure-sensitive adhesive label 1 has other layers (not shown) such as a surface protective layer in addition to the heat-shrinkable base material 2, the pressure-sensitive adhesive layer 3 and the design print layer 4 as necessary. You may do it.
The planar shape of the heat-shrinkable pressure-sensitive adhesive label 1 (heat-shrinkable substrate 2) is usually a substantially rectangular shape (or a substantially square shape). A knob 29 is extended at the first longitudinal end of the heat-shrinkable substrate 2. The knob 29 is formed, for example, in a substantially semicircular shape in plan view.

<Heat-shrinkable substrate>
The heat-shrinkable substrate 2 has a surface layer 5, a back surface layer 6, and an intermediate layer 7 between the surface layer 5 and the back surface layer 6. The intermediate layer 7 is a general term for a resin layer interposed between the front surface layer 5 and the back surface layer 6. The intermediate layer 7 may be composed of one resin layer, or may be composed of two or more resin layers. When the intermediate layer 7 is composed of two or more resin layers, the number of laminated layers is two or more, preferably 3 to 35 layers.
The front surface layer 5 and the back surface layer 6 are each composed of a resin layer containing a cyclic olefin polymer as a main component resin, and the intermediate layer 7 includes a resin layer containing an olefin elastomer as a main component resin. Hereinafter, a resin layer containing a cyclic olefin polymer as a main component resin may be referred to as a “cyclic olefin layer”, and a resin layer containing an olefin elastomer as a main component resin may be referred to as an “elastomer layer”.
Here, in the present specification, the main component resin refers to a resin (mass basis) having the largest amount among resins contained in each resin layer.

When the intermediate layer 7 is composed of one resin layer, the one resin layer is composed of an elastomer layer, and when the intermediate layer 7 is composed of a laminated structure of two or more resin layers, at least one of them is It is composed of an elastomer layer (that is, the intermediate layer 7 composed of one resin layer or two or more resin layers includes an elastomer layer).
When the intermediate layer 7 is composed of two or more resin layers, all the resin layers may be composed of elastomer layers, and one or more of the resin layers are composed of elastomer layers and the remaining resin layers are You may be comprised from resin layers other than an elastomer layer and a cyclic olefin layer. Hereinafter, the resin layer other than the elastomer layer and the cyclic olefin layer (resin layer containing as a main component resin other than the cyclic olefin polymer and the olefin elastomer) is referred to as “other resin layer”. Alternatively, when the intermediate layer 7 is composed of two or more resin layers, one or more of the resin layers may be composed of an elastomer layer, and the remaining resin layer may be composed of a cyclic olefin layer. The cyclic olefin layer included in the intermediate layer 7 may be the same as or different from the cyclic olefin layers that are the front surface layer 5 and the back surface layer 6.
When the intermediate layer 7 is composed of two or more resin layers, it is preferable that the elastomer layer and at least one layer selected from a cyclic olefin layer and another resin layer are alternately laminated.

  Further, when the intermediate layer 7 is composed of two or more resin layers, and when two or more of the resin layers are composed of an elastomer layer, each elastomer layer contains an olefin elastomer content. May be the same, and the content of the olefin-based elastomer may be different. When the two or more resin layers are composed of an elastomer layer, all of the elastomer layers may be an elastomer layer having the same content of the olefin-based elastomer, or include a desired amount of the olefin-based elastomer. You may be comprised from the elastomer layer and the elastomer layer in which content of an olefin type elastomer is smaller than the elastomer layer. Hereinafter, an elastomer layer containing a desired amount of an olefin-based elastomer is sometimes referred to as a “first elastomer layer”, and an elastomer layer having a smaller olefin-based elastomer content than the first elastomer layer is sometimes referred to as a “second elastomer layer”. .

For example, the heat-shrinkable base material 2 in the heat-shrinkable pressure-sensitive adhesive label 1 shown in FIG. 3 is composed of a two-layer / three-layer laminated film of an intermediate layer 71 / back surface layer 6 of a surface layer 5/1 layer. In this case, the intermediate layer 71 is composed of an elastomer layer.
The heat-shrinkable substrate 2 in the heat-shrinkable pressure-sensitive adhesive label 1 shown in FIG. 4 is composed of laminated films of intermediate layers 71, 72, 73 / back surface layer 6 having a surface layer 5/3 layer structure. In this case, examples of combinations of the intermediate layers 71, 72, and 73 (first intermediate layer 71 / second intermediate layer 72 / third intermediate layer 73) having a three-layer structure include the following. Of the following (1) to (6), (1), (3) or (5) is preferable.
(1) first intermediate layer 71 / second intermediate layer 72 / third intermediate layer 73 = second elastomer layer / first elastomer layer / second elastomer layer,
(2) first intermediate layer 71 / second intermediate layer 72 / third intermediate layer 73 = first elastomer layer / second elastomer layer / first elastomer layer,
(3) first intermediate layer 71 / second intermediate layer 72 / third intermediate layer 73 = other resin layer / elastomer layer (first elastomer layer or second elastomer layer) / other resin layer,
(4) first intermediate layer 71 / second intermediate layer 72 / third intermediate layer 73 = elastomer layer (first elastomer layer or second elastomer layer) / other resin layer / elastomer layer (first elastomer layer or second elastomer) layer).
(5) first intermediate layer 71 / second intermediate layer 72 / third intermediate layer 73 = cyclic olefin layer / elastomer layer (first elastomer layer or second elastomer layer) / cyclic olefin layer,
(6) first intermediate layer 71 / second intermediate layer 72 / third intermediate layer 73 = elastomer layer (first elastomer layer or second elastomer layer) / cyclic olefin layer / elastomer layer (first elastomer layer or second elastomer) layer).
In the example shown in FIG. 4, the second intermediate layer 72 is disposed at the center in the thickness direction of the heat-shrinkable substrate 2.

The heat-shrinkable base material 2 in the heat-shrinkable pressure-sensitive adhesive label 1 shown in FIG. 5 is composed of laminated films of intermediate layers 71, 72, 73, 74, 75 / back surface layer 6 having a surface layer 5/5 layer structure. . In this case, the intermediate layers 71, 72, 73, 74, 75 having the five-layer structure (first intermediate layer 71 / second intermediate layer 72 / third intermediate layer 73 / fourth intermediate layer 74 / fifth intermediate layer 75) Examples of combinations include the following.
(1) First intermediate layer 71 / second intermediate layer 72 / third intermediate layer 73 / fourth intermediate layer 74 / fifth intermediate layer 75 = first elastomer layer / second elastomer layer / first elastomer layer / second Elastomer layer / first elastomer layer,
(2) first intermediate layer 71 / second intermediate layer 72 / third intermediate layer 73 / fourth intermediate layer 74 / fifth intermediate layer 75 = second elastomer layer / first elastomer layer / second elastomer layer / first Elastomer layer / second elastomer layer,
(3) First intermediate layer 71 / second intermediate layer 72 / third intermediate layer 73 / fourth intermediate layer 74 / fifth intermediate layer 75 = elastomer layer (first elastomer layer or second elastomer layer) / other resin layer / Elastomer layer (first elastomer layer or second elastomer layer) / Other resin layer / Elastomer layer (first elastomer layer or second elastomer layer),
(4) first intermediate layer 71 / second intermediate layer 72 / third intermediate layer 73 / fourth intermediate layer 74 / fifth intermediate layer 75 = other resin layer / elastomer layer (first elastomer layer or second elastomer layer) / Other resin layer / Elastomer layer (first elastomer layer or second elastomer layer) / Other resin layer.
(5) first intermediate layer 71 / second intermediate layer 72 / third intermediate layer 73 / fourth intermediate layer 74 / fifth intermediate layer 75 = elastomer layer (first elastomer layer or second elastomer layer) / cyclic olefin layer / Elastomer layer (first elastomer layer or second elastomer layer) / cyclic olefin layer / elastomer layer (first elastomer layer or second elastomer layer),
(6) first intermediate layer 71 / second intermediate layer 72 / third intermediate layer 73 / fourth intermediate layer 74 / fifth intermediate layer 75 = cyclic olefin layer / elastomer layer (first elastomer layer or second elastomer layer) / Cyclic olefin layer / elastomer layer (first elastomer layer or second elastomer layer) / cyclic olefin layer.
In the example shown in FIG. 5, the third intermediate layer 73 is disposed at the center in the thickness direction of the heat-shrinkable substrate 2.

The thickness of the heat-shrinkable substrate 2 is not particularly limited, and is, for example, 20 μm to 100 μm, preferably 25 μm to 60 μm.
Although the thickness of the surface layer 5 and the back surface layer 6 is not specifically limited, 1 micrometer-20 micrometers are preferable each independently, More preferably, they are 1.5 micrometers-10 micrometers, More preferably, they are 2 micrometers-8 micrometers. When the thickness of the surface layer 5 and the back surface layer 6 exceeds 20 μm, the thickness of the intermediate layer 7 becomes relatively small, and the heat shrinkability of the heat shrinkable substrate 2 may be lowered. If the thickness of the surface layer 5 and the back surface layer 6 is less than 1 μm, the waist of the heat-shrinkable substrate 2 may be lowered.
The total thickness of the intermediate layer 7 is not particularly limited, but is preferably 8 to 90 μm, more preferably 10 to 50 μm, and still more preferably 11 to 45 μm. The total thickness of the intermediate layer 7 is the thickness of the resin layer when the intermediate layer 7 is composed of one resin layer, and when the intermediate layer 7 is composed of two or more resin layers. Is the total thickness of those resin layers.
When the intermediate layer 7 is composed of two or more resin layers, the thickness of each resin layer is not particularly limited, but is, for example, 0.5 μm to 40 μm, and preferably 1 μm to 20 μm. Note that these resin layers may have the same or a part of the thickness, or may be different from each other.

The ratio of the thickness of the surface layer 5 to the total thickness of the intermediate layer 7 (thickness of the surface layer 5: total thickness of the intermediate layer 7) is not particularly limited, but is preferably 5: 1 to 1:20, more preferably 1: It is 1-1: 10, More preferably, it is 1: 2-1: 8. The ratio of the thickness of the back layer 6 and the total thickness of the intermediate layer 7 is also the same as the ratio of the thickness of the surface layer 5 and the total thickness of the intermediate layer 7.
Each thickness of the surface layer 5 and the back surface layer 6 with respect to the thickness of the heat-shrinkable base material 2 (the total thickness of the surface layer 5, the back surface layer 6 and the intermediate layer 7) is not particularly limited. It is 2% to 35%, preferably 3% to 25%, more preferably 5% to 20%.
The thickness of the elastomer layer relative to the thickness of the heat-shrinkable substrate 2 (the total thickness of the front surface layer 5, the back surface layer 6 and the intermediate layer 7) (the total thickness when a plurality of the elastomer layers are provided) is particularly limited. Although not performed, for example, it is 5% to 75%, preferably 10% to 65%, and more preferably 20 to 60%.

The heat-shrinkable substrate 2 is a substrate having a property (heat-shrinkability) that at least heat-shrinks in the lateral direction (main heat-shrink direction) when heated to a desired temperature (for example, 70 to 100 ° C.). Moreover, the heat-shrinkable base material 2 may be slightly heat-shrinked or stretched in the vertical direction (the vertical direction is the direction perpendicular to the horizontal direction in the film plane). The heat shrinkage rate of the heat-shrinkable substrate 2 is not particularly limited as long as it can be adhered to the container. For example, the heat shrinkage rate in the lateral direction when heated to 90 ° C. is 40% or more, preferably Is 45% or more, more preferably 50% or more. By providing the intermediate layer 7 with an elastomer layer, the heat-shrinkable substrate 2 having a heat shrinkage rate of 50% or more can be formed as described above.
In addition, when the heat-shrinkable base material 2 is slightly heat-shrinked or stretched in the vertical direction, the heat-shrink rate in the vertical direction when heated to 90 ° C. is, for example, −5% to 15%, preferably Is -3% to 10%. The minus of the thermal contraction rate means thermal extension. The heat shrinkage rate when heated to 90 ° C. is the length of the base material before heating (original length) and the length of the base material after dipping the base material in warm water at 90 ° C. for 10 seconds ( It is a ratio of the length after immersion) and is obtained by substituting into the following formula.
Formula: heat shrinkage rate (%) = [{(original length in horizontal direction (or vertical direction)) − (length after immersion in horizontal direction (or vertical direction))} / (horizontal direction (or vertical direction) ) Original length)] × 100.

The heat-shrinkable substrate can be produced by, for example, a melt film forming method.
Specifically, the surface layer forming material, the intermediate layer forming material and the back layer forming material are melted and coextruded to form an unstretched laminated film, and then stretched by stretching the unstretched laminated film. A laminated film is produced. In addition, extrusion temperature is suitably set according to the kind of forming material (raw material) of each layer. The stretching direction of the unstretched laminated film is not particularly limited, but is preferably stretched at least in the MD direction. Examples of the stretching in at least the MD direction include uniaxial stretching that stretches in the MD direction of the unstretched laminated film, and biaxial stretching that stretches in the MD direction and the TD direction of the unstretched laminated film. The MD direction is the direction of the film production line and the longitudinal direction of the stretched laminated film to be produced. The TD direction is a direction orthogonal to the MD direction and is a short direction of the stretched laminated film to be produced. As the stretching method, any method such as a roll method, a tenter method, and a tube method may be used. The stretching conditions are appropriately set according to the type of forming material of each layer, the required characteristics of the heat-shrinkable substrate, and the like. For example, at a stretching temperature of 70 to 110 ° C., preferably 80 to 95 ° C., at least in the MD direction. It is preferable to carry out at a draw ratio of about 2 to 8 times.

By stretching the unstretched laminated film, a stretched laminated film in which the surface layer, the intermediate layer, and the back surface layer are laminated is obtained. This stretched laminated film has heat shrinkability that mainly heat shrinks in the MD direction, and the surface layer, intermediate layer, and back layer constituting the stretched laminated film also have heat shrinkability that mainly heat shrinks in the MD direction, respectively. .
The obtained stretched laminated film has a long shape, and the heat-shrinkable substrate of the present invention can be obtained by cutting it into a desired size. In addition, the heat-shrinkable base material which has the property to heat-shrink in the above-mentioned at least horizontal direction by cut | disconnecting the said extending | stretching laminated film so that MD direction of a stretched laminated film may turn into the horizontal direction of a heat-shrinkable base material. Can be obtained.

<Cyclic olefin layer>
The cyclic olefin layer constitutes the surface layer 5 and the back surface layer 6 of the heat-shrinkable substrate 2. In addition, as described above, the cyclic olefin layer may constitute the resin layer of the intermediate layer 7. The cyclic olefin layer may contain a resin other than the main component resin on the condition that the cyclic olefin polymer is included as the main component resin.
The surface layer 5 and the back surface layer 6 may have different compositions on the condition that they contain a cyclic olefin polymer as a main component, but the surface layer 5 and the back surface layer 6 are the same cyclic olefin layer. It is preferable that it is comprised.

Examples of the cyclic olefin polymer include a copolymer of an α olefin such as ethylene, propylene, 1-butene, 1-hexene, 4-methyl-1-pentene and at least one cyclic olefin (“cyclic olefin”). A ring-opening polymer of a cyclic olefin or a hydrogenated product thereof (sometimes referred to as “a ring-opening polymer of a cyclic olefin or a hydrogenated product thereof”). The cyclic olefin copolymer and the cyclic olefin ring-opening polymer or hydrogenated product thereof also include graft-modified products thereof.
Examples of the cyclic olefin used in the cyclic olefin polymer include, for example, bicyclo [2.2.1] hept-2-ene (norbornene), tetracyclo [4.4.0.12, 5.17,10]- 3-dodecene, hexacyclo [6.6.1.13, 6.110, 13.02, 7.09,14] -4-heptadecene, octacyclo [8.8.0.12, 9.14, 7.111 , 18.113, 16.03, 8.012, 17] -5-docosene, pentacyclo [6.6.1.13, 6.02, 7.09,14] -4-hexadecene, heptacyclo-5-icosene , Heptacyclo-5-henicocene, tricyclo [4.3.0.12,5] -3-decene, tricyclo [4.4.0.12,5] -3-undecene, pentacyclo [6.5.1.13 , .02, 7.09,13] -4-pentadecene, pentacyclopentadecadiene, pentacyclo [4.7.0.12,5.08,13.19,12] -3-pentadecene, nonacyclo [9.10] 1.14, 7.113, 20.115, 18.02, 10.12, 21.014, 19] -5-pentacocene and the like, and the like. Of these, norbornene is preferable. These cyclic olefins may have substituents such as ester groups such as methoxycarbonyl and ethoxycarbonyl groups, alkyl groups such as methyl groups, haloalkyl groups, cyano groups, and halogen atoms in the ring.

The cyclic olefin copolymer is, for example, a catalyst such as a so-called Ziegler catalyst or a metallocene catalyst in a hydrocarbon solvent such as hexane, heptane, octane, cyclohexane, benzene, toluene, xylene, and the like. It can obtain by superposing | polymerizing using. Such cyclic olefin copolymers are commercially available, and for example, “Apel” manufactured by Mitsui Chemicals, Inc., “TOPAS” manufactured by Polyplastics Co., Ltd., and the like can be used.
The ring-opening polymer of the cyclic olefin or the hydrogenated product thereof is usually obtained by subjecting one or more of the cyclic olefins to metathesis polymerization (ring-opening polymerization) using a molybdenum compound or a tungsten compound as a catalyst. The polymer obtained can be further hydrogenated. Such ring-opened polymers of cyclic olefins or hydrogenated products thereof are commercially available. For example, “Arton” manufactured by JSR Corporation, “Zeonex” manufactured by Nippon Zeon Co., Ltd., “Zeonor”, and the like can be used.
Although it does not specifically limit as a cyclic olefin type polymer, A cyclic olefin copolymer is more preferable. Since the cyclic olefin copolymer has high miscibility and compatibility with the acyclic olefin resin, the cyclic olefin layer containing the cyclic olefin copolymer and the acyclic olefin resin is used as the surface layer 5 and the back surface layer 6. By doing so, the heat-shrinkable substrate 2 that is more excellent in transparency and impact resistance can be configured.

The glass transition temperature (Tg) of the cyclic olefin polymer is not particularly limited, but is preferably 30 to 180 ° C, more preferably 50 to 80 ° C, and still more preferably 60 to 80 ° C, from the viewpoint of stretchability. Preferably it is 65-75 degreeC (especially about 70 degreeC). The glass transition temperature of the cyclic olefin polymer can be adjusted by the type of monomer component (for example, cyclic olefin) and the blending ratio thereof.
When the cyclic olefin-based polymer is a cyclic olefin copolymer, the content of the structural unit derived from the cyclic olefin (for example, norbornene) in the cyclic olefin copolymer is not particularly limited. From a viewpoint, 50 to 75 mass% is preferable with respect to the total mass (100 mass%) of a cyclic olefin copolymer, More preferably, it is 60 to 70 mass%. For example, when the cyclic olefin copolymer contains norbornene, the norbornene content in the cyclic olefin copolymer (Norbornene content in COC) is preferably in the above range.

When the cyclic olefin layer contains a resin other than the cyclic olefin polymer, the resin is not particularly limited. For example, a polyester resin, a polystyrene resin, an acyclic olefin resin, a vinyl chloride resin, or a polycarbonate resin. Examples thereof include resins, polyamide resins, and thermoplastic elastomers (for example, olefin elastomers, styrene elastomers, polyester elastomers, etc.). Preferably, the cyclic olefin layer includes a cyclic olefin polymer as a main component, and further includes an acyclic olefin resin.
The acyclic olefin resin is a polymer composed of an acyclic olefin as an essential monomer component, that is, a polymer containing at least an acyclic olefin in a molecule (in one molecule). . The acyclic olefin is not particularly limited, and examples thereof include ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene and 1-nonene. And α-olefins such as 1-decene.

Examples of the acyclic olefin-based resin include a polymer (α-olefin-based resin) including at least one α-olefin as a main component of a monomer. Examples of the α-olefin resin include a polymer containing ethylene as a main component of a monomer (polyethylene resin) and a polymer containing propylene as a main component of a monomer (polypropylene resin). The acyclic olefin resin is not particularly limited, but a polyethylene resin or a polypropylene resin is preferable, and a polyethylene resin is more preferable.
The polyethylene resin is a polymer composed of ethylene as a main component of a monomer. Examples of the polyethylene-based resin include ethylene homopolymers; copolymers composed of ethylene and one or more monomer components (monomer components other than ethylene) as the main monomer components (ethylene copolymer). Polymer) and the like.

  Examples of monomer components other than ethylene include α-olefins as described above (excluding ethylene); vinyl monomers such as vinyl chloride; (meth) acrylic acid, maleic acid, fumaric acid, crotonic acid, Unsaturated carboxylic acids such as itaconic acid, citraconic acid, 5-norbornene-2,3-dicarboxylic acid; maleic anhydride, citraconic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, tetrahydrophthalic anhydride, etc. Unsaturated carboxylic anhydride; methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (meth) acrylic acid 2- Hydroxyethyl, 3-hydroxypropyl (meth) acrylate, glycidyl (meth) acrylate, male Unsaturated carboxylic acid esters such as monoethyl acid and diethyl maleate; unsaturated amides or imides such as acrylamide, methacrylamide and maleimide; unsaturated carboxylic acid salts such as sodium (meth) acrylate and zinc (meth) acrylate; Examples include vinyl acetate. Only one type of monomer component other than ethylene may be used, or two or more types may be used.

Examples of the α olefin include α having 4 to 20 carbon atoms such as 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene and 1-decene. Olefins (preferably α-olefins having 4 to 8 carbon atoms) are preferred. Only 1 type may be used for the said alpha olefin, and 2 or more types may be used for it.
Examples of the ethylene copolymer include a copolymer composed of ethylene and one or more α-olefins as essential monomer components (ethylene-α-olefin copolymer); an ethylene-vinyl acetate copolymer. (EVA); ethylene-carboxylic acid copolymer such as ethylene-acrylic acid copolymer (EAA), ethylene-methacrylic acid copolymer (EMAA); ethylene-ethyl acrylate copolymer (EEA), And ethylene-carboxylic acid ester copolymers such as ethylene-methyl methacrylate copolymer (EMMA). Among these, an ethylene-α olefin copolymer is particularly preferable.

Examples of the polyethylene resin include low-density polyethylene (LDPE) and linear low-density polyethylene (LLDPE), and are not particularly limited, but LLDPE is particularly preferable from the viewpoint of heat shrinkability. The LDPE refers to polyethylene having a low density of about 0.850 to 0.945 g / cm ³ that includes a structural unit derived from ethylene as a main component and is manufactured by a high-pressure method. The LLDPE is a low-density polyethylene of about 0.850 to 0.945 g / cm ³ that contains a structural unit derived from ethylene as a main component, is produced by a medium / low pressure method, and has a short chain branch.
The polyethylene resin is not particularly limited, but a polyethylene resin obtained by polymerization using a metallocene catalyst, particularly a linear low density polyethylene (LLDPE) obtained by polymerization using a metallocene catalyst is preferable. . As the metallocene catalyst, a known or conventional metallocene catalyst for olefin polymerization can be used. The polymerization method (copolymerization method) of the polyethylene resin is not particularly limited, and examples thereof include known polymerization methods such as a slurry method, a solution polymerization method, and a gas phase method.

Although the density of the said polyethylene-type resin is not specifically limited, 0.850-0.950 g / cm < ³ > is preferable, More preferably, it is 0.870-0.935 g / cm < ³ >. Further, the melt flow rate (MFR) (temperature 190 ° C., load 2.16 kg) of the polyethylene resin is not particularly limited, but is preferably 1 to 30 g / 10 minutes from the viewpoint of melt extrusion suitability and productivity, Preferably it is 1-10 g / 10min.
Commercially available products may be used as the polyethylene resin. For example, “Umerit 4540F”, “Umerit 3540F”, “Umerit 2540F”, “Umerit 1540F”, “Umerit 0540F”, “Umerit 5540F”, “ "Umerit 2040FC", "Umerit 0520F", "Umerit 1520F", "Umerit 0520F", "Umerit 715FT", made by Prime Polymer Co., Ltd., "Evolue SP1520", "Evolue SP2040" (and above, metallocene catalyst LLDPE), Japan “Kernel KF260T”, “Kernel KF360T”, “Kernel KF380”, “Kernel KS340T” (the above, metallocene catalyst ethylene / α-olefin copolymer) manufactured by Polyethylene Co., Ltd., Ube Good polyethylene (Ltd.) "F234" (LDPE), Ube Maruzen Polyethylene Co., Ltd. "V206", Japan polyethylene Co., Ltd. "Novatec EVA Series" (or more, EVA) is and available in the market.

The content of the cyclic olefin polymer in the cyclic olefin layer is not particularly limited on the condition that the cyclic olefin polymer is a main component, but it is 50% relative to the total mass (100% by mass) of the cyclic olefin layer. It is preferably at least 50% by mass, more preferably more than 50% by mass, further preferably at least 60% by mass, particularly preferably at least 70% by mass, and most preferably at least 80% by mass. The upper limit of the content is not particularly limited, and may be 100% by mass.
The cyclic olefin layer may contain various additives within a range not impairing the effects of the present invention. Examples of additives include pigments, dyes, lubricants, fillers, antiblocking agents (such as inorganic particles), antioxidants, ultraviolet absorbers, deodorants, flame retardants, antistatic agents, antifogging agents, and pinning agents. (Alkaline earth metal), heat stabilizers and the like. The additive amount of these additives is preferably less than 3% by mass relative to the total mass of the cyclic olefin layer.
It is preferable that the cyclic olefin layer which comprises the surface layer 5 and the back surface layer 6 contains 70 mass%-90 mass% of cyclic olefin polymers, and 10 mass%-30 mass% of polyethylene-type resins.
On the other hand, the cyclic olefin layer constituting the resin layer of the intermediate layer preferably includes a cyclic olefin polymer as a main component and includes an olefin elastomer, and includes a cyclic olefin polymer as a main component and includes an olefin elastomer and It is more preferable to include an acyclic olefin resin, and it is more preferable to include a cyclic olefin polymer as a main component and to include an olefin elastomer, a polyethylene resin, and a polypropylene resin.

<Elastomer layer>
The elastomer layer constitutes all or part of the intermediate layer 7. The elastomer layer may contain a resin other than the main component resin on the condition that the main component resin contains an olefin elastomer. When the elastomer layer contains a resin other than the olefin elastomer, the resin is not particularly limited. For example, a cyclic olefin polymer, a polyester resin, a polystyrene resin, an acyclic olefin resin, a vinyl chloride resin. And thermoplastic elastomers other than polycarbonate resins, polyamide resins, and olefin elastomers. Preferably, the resin other than the main component resin contained in the elastomer layer is a cyclic olefin polymer and an acyclic olefin resin. In addition, as a cyclic olefin type polymer and acyclic olefin type resin of an elastomer layer, what was illustrated to the said cyclic olefin layer can be used. Preferably, the cyclic olefin polymer of the elastomer layer is the same as the cyclic olefin polymer constituting the cyclic olefin layer constituting the front surface layer and the back surface layer. Preferably, the acyclic olefin resin of the elastomer layer is the same as the acyclic olefin resin that may be blended in the cyclic olefin layer.

Examples of the olefin elastomer include an ethylene elastomer having ethylene as a main component and a propylene elastomer having propylene as a main component. Examples of the ethylene-based elastomer include ethylene-α olefin copolymer elastomers such as ethylene-propylene copolymer elastomers (however, α-olefins in ethylene-α-olefin copolymer elastomers are α-olefins other than ethylene). It is done. Examples of the propylene-based elastomer include propylene-α olefin copolymer elastomers such as propylene-ethylene copolymer elastomer (provided that the α olefin of the propylene-α olefin copolymer elastomer is an α olefin excluding propylene). It is done. Among these, a propylene-based elastomer is preferable, a propylene-α olefin copolymer elastomer is more preferable, and a propylene-α olefin graft copolymer elastomer or a propylene-α olefin random copolymer elastomer is further preferable. Only 1 type may be used for the said polyolefin-type elastomer, and 2 or more types may be used for it.
The propylene-α olefin copolymer elastomer, propylene-α olefin graft copolymer elastomer or propylene-α olefin random copolymer elastomer is a propylene-ethylene copolymer elastomer, propylene-ethylene graft copolymer elastomer or propylene- An ethylene random copolymer elastomer is preferred. These copolymer elastomers may contain α-olefins other than ethylene and propylene as necessary. In addition, these copolymer elastomers may contain a diene component as necessary. Examples of the diene component include 1,3-butadiene, isoprene (2-methyl-1,3-butadiene), 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, and 1,3-hexadiene. And chloroprene. The diene component may be used alone or in combination of two or more.

Examples of the α-olefin used as a copolymerization component of the ethylene-α-olefin copolymer elastomer include propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1 -C3-C20 alpha olefins (preferably C3-C8 alpha olefins), such as octene, 1-nonene, 1-decene, etc. are mentioned. Only 1 type may be used for the said alpha olefin, and 2 or more types may be used for it. The ethylene-α olefin copolymer elastomer may be a block copolymer, a random copolymer, or a graft copolymer.
Content of structural unit derived from α-olefin in the ethylene-α-olefin copolymer elastomer (100% by mass), that is, all monomer components constituting the ethylene-α-olefin copolymer elastomer (100% by mass) The content of the α-olefin in () is not particularly limited, but is preferably 1 to 40% by mass, more preferably 2 to 30% by mass, and still more preferably 3 to 25% by mass. Furthermore, in the said ethylene-alpha olefin copolymer elastomer, although total content of an ethylene component and an alpha olefin component is not specifically limited, In ethylene-alpha olefin copolymer elastomer (100 mass%), it is 90 mass% or more. Preferably, it is 95% by mass or more, and more preferably 98% by mass or more.

  Examples of the α-olefin used as a copolymerization component of the propylene-α-olefin copolymer elastomer include ethylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1 -C2-C20 alpha olefins (however, except propylene), such as octene, 1-nonene, 1-decene, etc. are mentioned. Only 1 type may be used for the said alpha olefin, and 2 or more types may be used for it. The propylene-α olefin copolymer elastomer may be a block copolymer, a random copolymer, or a graft copolymer. Among these, a random copolymer is preferable.

Although content of the alpha olefin in all the monomer components (100 mass%) which comprises the said propylene-alpha olefin copolymer elastomer is not specifically limited, 1-40 mass% is preferable, More preferably, it is 2-30. It is 3 mass%, More preferably, it is 3-25 mass%. In the propylene-α-olefin copolymer elastomer, the total content of the propylene component and the α-olefin component is not particularly limited, but is 90% by mass or more in the propylene-α-olefin copolymer elastomer (100% by mass). Is preferable, 95 mass% or more is more preferable, and 98 mass% or more is further more preferable.
The content of ethylene in the propylene-ethylene copolymer elastomer is preferably 5% by mass to 30% by mass, more preferably 6% by mass to 25% by mass, further preferably 7% by mass to 20% by mass, and 8% by mass. % To 12% by mass is particularly preferable. When the propylene-ethylene copolymer elastomer contains an α-olefin other than ethylene and propylene, the content is, for example, 15% or less, preferably 10% or less. Moreover, when a propylene-ethylene copolymer elastomer contains a diene component, the content is 15% or less, for example, Preferably it is 10% or less.

  The polypropylene elastomer preferably has a heat of fusion (Hf) of 75 J / g or less. This heat of fusion can be lowered by incorporating a monomer component other than propylene such as a stereo error, regio error, and α-olefin and diene. When the polypropylene elastomer is a propylene-α-olefin copolymer elastomer, the heat of fusion of the propylene-α-olefin copolymer elastomer is preferably 0.5 to 50 J / g. The heat of fusion can be measured according to ASTM E-794-95 (version E-794-01).

The polypropylene elastomer preferably has a triad tacticity (triad tacticity) composed of three propylene units of 75% or more (preferably 90% or more). The triplet stereoregularity can be obtained by using ¹³ C-NMR measurement. Specifically, for example, it can be calculated by the method described in US Patent Application Publication No. 2004/0236042.

In particular, the polypropylene elastomer preferably has a heat of fusion of 75 J / g or less and a triplet stereoregularity composed of three propylene units of 75% or more.
Wherein the polypropylene-based elastomer (particularly, propylene -α- olefin copolymer elastomer), the Mooney viscosity _{ML (1 + 4)} at 125 ° C., is not particularly limited, preferably less than 100, more preferably below 60, more preferably 30 Is less than. The Mooney viscosity can be measured according to ASTM D1646.
The molecular weight distribution (Mw / Mn) of the polypropylene-based elastomer (particularly, propylene-α-olefin copolymer elastomer) is not particularly limited, but is preferably 1.8 to 3. The molecular weight distribution can be measured using GPC.

  A known or conventional polypropylene elastomer can be used as the polypropylene elastomer. The polypropylene-based elastomer includes a bridged metallocene catalyst (see, for example, International Publication No. 1999/007788), a pyridine amine catalyst (see, for example, International Publication No. 2003/040201), and a non-bridged metallocene catalyst (see, for example, US Pat. It can be prepared preferably by solution polymerization using various types of single-site catalysts such as No. 5969070).

Density of the polypropylene-based elastomer is not particularly limited, but is preferably 0.800 g / cm ³ or more, more preferably 0.830 g / cm ³ or more, more preferably 0.840 g / cm ³ or more, particularly preferably 0. It is 850 g / cm ³ or more. The upper limit of the density is not particularly limited, but is preferably 0.950 g / cm ³ or less, more preferably less than 0.900 g / cm ³ , still more preferably less than 0.895 g / cm ³ , and particularly preferably 0.890 g / cm ^3. Less than cm ³ , most preferably 0.885 g / cm ³ or less.

  Commercially available products may be used as the propylene-α-olefin copolymer elastomer, such as “Tough Selenium Series” manufactured by Sumitomo Chemical Co., Ltd., “VISTAMAX Series” manufactured by ExxonMobil Chemical Co., Ltd., The Dow Chemical.・ The company's “VERSIFY series” is available on the market.

The content of the olefin-based elastomer in the elastomer layer is not particularly limited as a condition that the olefin-based elastomer is a main component, but is preferably 30% by mass or more, more preferably based on the total mass (100% by mass) of the elastomer layer. Is 40% by mass or more, more preferably 50% by mass or more, particularly preferably 60% by mass or more, and most preferably 80% by mass or more. The upper limit of the content is not particularly limited, and may be 100% by mass.
The elastomer layer may contain various additives within a range not impairing the effects of the present invention. Examples of the additive include those described above. The addition amount of the additive is preferably less than 5% by mass with respect to the total mass of the elastomer layer.

(A) The intermediate layer 7 is composed of one resin layer (elastomer layer) or the intermediate layer 7 is composed of two or more resin layers, and two or more of the resin layers are the same elastomer When composed of layers, the content of the olefinic elastomer in the elastomer layer is preferably 80% by mass or more, more preferably 90% by mass or more, with respect to the total mass (100% by mass) of the elastomer layer. Yes, more preferably 100% by mass. By using the elastomer layer containing a relatively large amount of the olefin-based elastomer as the intermediate layer 7, the heat-shrinkable substrate 2 having excellent water vapor barrier properties and excellent heat-shrinkability can be configured.

  In the case of (a), (a-1) an elastomer layer containing an olefin elastomer as a main component and containing a cyclic olefin polymer, or (a-2) containing an olefin elastomer as a main component and acyclic An elastomer layer containing an olefin resin is preferred, and (a-3) an elastomer layer containing an olefin elastomer as a main component and containing a cyclic olefin polymer and an acyclic olefin resin is more preferred. The content of the olefin elastomer in the elastomer layer (a-1) or (a-3) is, for example, 40% by mass to 90% by mass, preferably 50% by mass to 85% by mass, and more preferably. Is 55% by mass to 80% by mass, and the content of the cyclic olefin polymer is, for example, 5% by mass to 49% by mass, preferably 10% by mass to 45% by mass, and more preferably 15% by mass. % To 40% by mass. The content of the olefin elastomer in the elastomer layer (a-2) or (a-3) is, for example, 40% by mass to 90% by mass, preferably 50% by mass to 85% by mass, and more preferably. Is 55% by mass to 80% by mass, and the content of the acyclic olefin-based resin is, for example, 1% by mass to 40% by mass, and preferably 3% by mass to 35% by mass. As the acyclic olefin resin, a polyethylene resin or a polypropylene resin is preferably used.

(B) When the intermediate layer 7 includes the first elastomer layer and the second elastomer layer, the content of the olefin-based elastomer in the first elastomer layer is the total mass (100% by mass) of the first elastomer layer. Is preferably 80% by mass or more, more preferably 90% by mass or more, still more preferably 100% by mass, and the content of the olefin-based elastomer in the second elastomer layer is that of the first elastomer layer. On the condition that it is smaller than that, the total mass (100% by mass) of the second elastomer layer is preferably 40% by mass or more, more preferably 45% by mass or more, and further preferably 50% by mass. That's it.
Preferably, the first elastomer layer includes only an olefinic elastomer as a main component resin, and more preferably, the first elastomer layer is composed of only an olefinic elastomer.

  Preferably, the second elastomer layer contains (b-1) an olefin elastomer as a main component and an elastomer layer containing a cyclic olefin polymer, or (b-2) an olefin elastomer as a main component, and An elastomer layer containing an acyclic olefin resin is preferred, and an elastomer layer containing (b-3) an olefin elastomer as a main component and containing a cyclic olefin polymer and an acyclic olefin resin is more preferred. The content of the olefin elastomer in the elastomer layer (b-1) or (b-3) is, for example, 40% by mass to 90% by mass, preferably 50% by mass to 85% by mass, and more preferably. Is 55% by mass to 80% by mass, and the content of the cyclic olefin polymer is, for example, 5% by mass to 49% by mass, preferably 10% by mass to 45% by mass, and more preferably 15% by mass. % To 40% by mass. The content of the olefin elastomer in the elastomer layer (b-2) or (b-3) is, for example, 40% by mass to 90% by mass, preferably 50% by mass to 85% by mass, and more preferably. Is 55% by mass to 80% by mass, and the content of the acyclic olefin-based resin is, for example, 1% by mass to 40% by mass, and preferably 3% by mass to 35% by mass. As the acyclic olefin resin, a polyethylene resin or a polypropylene resin is preferably used.

<Other resin layers>
As other resin layers, for example, a resin layer containing a polyester resin as a main component resin, a resin layer containing a polystyrene resin as a main component resin, a resin layer containing an acyclic olefin resin as a main component resin, a vinyl chloride type Resin layer containing resin as main component resin, resin layer containing polycarbonate resin as main component resin, resin layer containing polyamide resin as main component resin, resin layer containing acrylic resin as main component resin, urethane resin Examples thereof include a resin layer containing the main component resin and a resin layer containing a thermoplastic elastomer other than the olefin elastomer as the main component resin.
As said other resin layer, the resin layer which has an acyclic olefin resin as a main component is preferable, and the thing containing an acyclic olefin resin as a main component and containing an olefin elastomer and a cyclic olefin polymer is preferable. As the acyclic olefin resin, a polyethylene resin or a polypropylene resin is preferably used.

<Opening auxiliary line>
In the surface of the heat-shrinkable substrate 2, opening assist lines 25 and 26 are formed. In addition, the heat-shrinkable adhesive label 1 of this invention may be comprised from the heat-shrinkable base material 2 which does not have the said auxiliary wire for opening.
The auxiliary opening lines 25 and 26 are not particularly limited as long as the heat-shrinkable base material 2 can be easily divided along the lines. For example, perforation lines and half-cut lines can be used. These can be used alone or in combination.
In the present specification, the perforation line is a set of through-holes in which a plurality of through-holes penetrating the front and back surfaces of the heat-shrinkable base material 2 are formed at predetermined intervals like a sewing mark of a sewing needle. Such a perforation line has a non-penetrating part (a film part not subjected to a penetrating process) between adjacent through holes. Examples of the front view shape of one through hole include an elongated linear shape, a needle hole shape (a punched substantially circular shape or a substantially elliptical shape), and the like. Since the heat-shrinkable base material 2 is easily cut along the perforation line, the perforation hole of the perforation line is preferably an elongated straight line.
Moreover, a half cut line is a line in which the notch part cut in the substantially V shape in the thickness direction of the base material 2 (it does not penetrate the front and back surfaces of the base material 2) continues.
From the viewpoint of easily cutting the heat-shrinkable substrate 2 mounted on the container along the opening auxiliary line, the opening auxiliary lines 25 and 26 are preferably perforated lines. On the other hand, from the viewpoint that the heat-shrinkable base material 2 particularly excellent in water vapor barrier properties can be constructed, the auxiliary opening lines 25 and 26 for opening are half-cut lines (because they do not penetrate the front and back surfaces of the base material). It is preferable.

In the example of illustration, the case where the perforation line is formed in the heat-shrinkable base material 2 as the auxiliary opening lines 25 and 26 is illustrated.
That is, the heat-shrinkable base material 2 has a horizontal perforation line 25 extending in the horizontal direction in the middle in the vertical direction, a diagonal perforation line 26 that is connected to a part of the horizontal perforation line 25 and extends at an upper left inclination, Is formed. In addition, it is preferable that the perforation line is not formed in the lower area | region (area | region below the horizontal perforation line 25) among the heat-shrinkable base materials 2. FIG. Since the lower region does not have a perforation line, the barrier property against the container body can be improved when the heat-shrinkable pressure-sensitive adhesive label 1 is attached to the container as will be described later.
The formation position of the horizontal perforation line 25 is not particularly limited. Usually, the heat-shrinkable pressure-sensitive adhesive label 1 is attached to the container so that the horizontal perforation line 25 coincides with the boundary portion between the container main body and the cap portion or in the vicinity thereof. Therefore, the formation position of the horizontal perforation line 25 is appropriately designed according to the type of container. However, the heat-shrinkable pressure-sensitive adhesive label 1 of the present invention is limited to the packaging form attached to the container so that the horizontal perforation line 25 coincides with the boundary portion of the container body and the cap portion or the vicinity thereof. is not.
The oblique perforation line 26 is an upper end portion of the heat-shrinkable base material 2 and starts from the left base portion of the knob 29 and extends from the start point to a part of the horizontal perforation line 25 with a downward slope.

<Adhesive layer>
The pressure-sensitive adhesive layer 3 is composed of a pressure-sensitive adhesive applied to the back surface of the heat-shrinkable substrate 2. A conventionally well-known thing can be used as said adhesive, for example, a pressure sensitive adhesive, a heat sensitive adhesive, etc. are mentioned. Examples of the pressure-sensitive adhesive include synthetic rubbers such as styrene-isoprene-styrene block copolymers and styrene-butadiene-styrene block copolymers, acrylic resins, olefin resins, urethane resins, and ethylene-vinyl acetate copolymers. An adhesive such as a polymer can be used. Since the pressure-sensitive adhesive has a desired adhesive force even at room temperature, it is preferable to use a pressure-sensitive adhesive.
A portion where the back surface of the pressure-sensitive adhesive layer 3 is exposed is an adhesive portion 31 that can be attached to the container.
In FIG. 2, in order to illustrate the bonding portion 31 in an easy-to-understand manner, the portion is shaded.
Referring to FIG. 2, for example, the bonding portion 31 includes an entire lower region of the heat-shrinkable substrate 2 that does not include the horizontal perforation line 25, a right end portion of the heat-shrinkable substrate 2, and a heat-shrinkable substrate. 2 is provided in a part of the left end of 2 above the horizontal perforation line 25.
The formation method of the adhesion part 31 is not specifically limited, (1) Applying an adhesive only to the range which provides an adhesion part among the back surfaces of the heat-shrinkable base material 2, (2) Heat-shrinkable base material 2 After the pressure-sensitive adhesive is applied to the entire back surface to form the pressure-sensitive adhesive layer 3, a masking agent that conceals the pressure-sensitive adhesive force of the pressure-sensitive adhesive is applied to the back surface of the pressure-sensitive adhesive layer 3 other than the range where the adhesive portion is provided. And the masking layer 32 is formed. Examples of the masking agent include printing ink added with transparent medium ink, silicone resin, wax and the like. Examples of the masking agent coating method include printing methods such as gravure printing and flexographic printing.
In the example of illustration, the adhesion part formed by the method of (2) is shown in figure.

<Design printing layer>
The design print layer 4 is a print layer on which various design displays such as a trade name, a pattern, a component display, and a cautionary note are displayed. The design printing layer 4 can be formed using a conventionally known printing ink. When the design print layer 4 is provided on the surface of the heat-shrinkable substrate 2, it is preferable to use an ultraviolet curable ink because a print layer having excellent friction resistance can be formed. The design printing layer 4 may be entirely or partially light transmissive, or may be entirely opaque.
The design print layer 4 is provided on the front surface or the back surface of the heat-shrinkable substrate 2 or the front and back surfaces. In the illustrated example, the design print layer 4 is provided on the surface of the heat-shrinkable substrate 2.

<Method for producing heat-shrinkable pressure-sensitive adhesive label>
The heat-shrinkable pressure-sensitive adhesive label 1 is usually manufactured in a state where a plurality of the heat-shrinkable pressure-sensitive adhesive labels 1 are temporarily pasted on a release paper and supplied to the user.
Such a heat-shrinkable pressure-sensitive adhesive label 1 can be produced by the following method, for example.
As shown in FIG. 6 (a), a long strip-shaped base material C laminated on the release surface of the long strip-shaped release paper A via an adhesive layer B is prepared. In addition, the adhesive layer B is provided on the entire back surface of the base material C. The base material C is a stretched laminated film described in the method for producing a heat-shrinkable base material or a film obtained by cutting the stretched laminated film into a desired width and length. The main heat shrinkage direction is the longitudinal direction (MD direction of the stretched laminated film).
After this base material C is peeled off from the release surface of the release paper A and a masking agent is applied to a predetermined range (a range other than the range where the adhesive portion is provided) on the back surface of the pressure-sensitive adhesive layer B to form a masking layer The base material C is again laminated on the release surface of the release paper A. In addition, since the masking layer is not provided in part of the back surface of the adhesive layer 3, the base material web C can be temporarily attached to the release paper A again at that portion.

Next, as shown in FIG. 6 (b), only the base material web C is formed with an oblique perforation line 26 at a predetermined interval in the longitudinal direction, and the horizontal perforation line 25 along the longitudinal direction. Form. Furthermore, a cut line D having the same shape as the outer shape of the heat-shrinkable base material 2 is formed only on the base material C. The perforation lines 25 and 26 and the cut line D may be formed first, or both may be formed simultaneously. It is preferable to form the perforation lines 25 and 26 and the cut line D at the same time because they can be formed with high accuracy.
Finally, as shown in FIG. 6 (c), the area C1 (unnecessary area) other than the area surrounded by the cut line in the base material C is peeled off from the release paper A and removed. As shown in 6 (d), a label continuum is obtained.
This label continuum has a long strip-shaped release paper A and a plurality of heat-shrinkable pressure-sensitive adhesive labels 1 temporarily attached to the release surface of the release paper A at predetermined intervals. The plurality of heat-shrinkable pressure-sensitive adhesive labels 1 are arranged with their lateral direction (main heat-shrink direction) substantially parallel to the longitudinal direction of the strip-shaped release paper A, and are provided on the back surface of the pressure-sensitive adhesive label 1. The layer 3 is temporarily pasted on the release surface of the release paper A.

<Applications of heat-shrinkable adhesive labels>
The heat-shrinkable pressure-sensitive adhesive label 1 of the present invention is used by being mounted on a container, for example.
A container is not specifically limited, The container in which arbitrary contents, such as a pharmaceutical, cosmetics, a seasoning, a foodstuff, a drink, and a machine part, were accommodated is mentioned.
The material of the container is not particularly limited, and synthetic resin, glass, metal and the like can be mentioned.
Since the heat-shrinkable pressure-sensitive adhesive label 1 of the present invention is excellent in water vapor barrier properties, it is preferable to attach it to a synthetic resin container. That is, by attaching the heat-shrinkable pressure-sensitive adhesive label 1 of the present invention to a synthetic resin container having a high water vapor permeability as compared with a glass or metal container, moisture from outside enters the inside of the container. And it can prevent that the water | moisture content inside a container is discharge | released outside the container.

Examples of the container body of the synthetic resin container include polyvinyl chloride resin, polyamide resin, polystyrene resin, polyester resin, polyolefin resin (for example, cyclic olefin resin, polyethylene resin, polypropylene resin, etc. ) And the like. In particular, it is preferable to attach the heat-shrinkable pressure-sensitive adhesive label 1 of the present invention to a container having a container body made of polyolefin resin. In addition, although the material of the cap part of the container which has the said container body made from a synthetic resin is not specifically limited, For example, the above synthetic resins are mentioned. In one example, it is preferable that the container main body and the cap portion of the container are formed of a polyolefin resin.
In addition, a relatively thin synthetic resin container body (for example, a synthetic resin container body having a thickness of 0.3 mm to 1.5 mm) tends to have high water vapor permeability.

For example, an eye drop container containing eye drops may use a polyolefin resin container as described above (for example, a container body made of a polyolefin resin such as a polyethylene resin).
For example, the case where the heat-shrinkable pressure-sensitive adhesive label 1 is attached to an eye drop container having a straight barrel-shaped container body will be described.
7 to 10, the first container 91 includes a container body 911 for containing contents, and a cap portion 912 that closes the spout of the container body 911 and is detachably attached to the container body 911 by a screw action. And having. For example, the cap portion 912 is screwed into the container main body 911 by turning clockwise when viewed from the upper side of the container, and can be removed from the container main body 911 by turning counterclockwise.
The container main body 911 in the illustrated example has a barrel portion that stores the contents, and a threaded cylinder portion (not shown) formed above the barrel portion. The outer shape of the body portion is a required cross-sectional shape such as a substantially circular shape, a substantially quadrangular shape, a substantially hexagonal shape, or a substantially elliptical shape in a horizontal section view, and is three-dimensionally a straight body shape. The straight body shape is a shape in which the circumferential length does not differ between the upper and lower sides. The trunk portion in the illustrated example is substantially cylindrical. The cap portion 912 has a truncated cone shape (a shape whose circumferential length increases as it goes downward), and is externally fitted to the threaded cylinder portion and screwed. Accordingly, the threaded tube portion is covered with the cap portion 912 and is not exposed, and the lower edge of the cap portion 912 is located immediately above the trunk portion. Moreover, the lower end of the cap part 912 and the upper end of a trunk | drum are substantially the same perimeter.

The heat-shrinkable adhesive label 1 of the label continuum is peeled from the release paper A. The heat-shrinkable pressure-sensitive adhesive label 1 is arranged so that the horizontal perforation line 25 of the heat-shrinkable pressure-sensitive adhesive label 1 coincides with the boundary portion between the container main body 911 and the cap portion 912 of the first container 91 or the upper vicinity portion or the lower vicinity portion thereof. While aligning, the left end portion of the heat-shrinkable pressure-sensitive adhesive label 1 is affixed to the container body 911 via an adhesive portion (pressure-sensitive adhesive layer 3) provided on the back surface of the left-side end portion of the heat-shrinkable pressure-sensitive adhesive label 1. . Then, the heat shrinkable pressure-sensitive adhesive label 1 is wound around the container 91 with the horizontal direction of the heat-shrinkable pressure-sensitive adhesive label 1 as a circumferential direction, and an adhesive portion (sticky) provided on the back surface of the right end portion of the heat-shrinkable pressure-sensitive adhesive label The right end portion of the heat-shrinkable pressure-sensitive adhesive label 1 is stuck on the surface of the left end portion and pasted through the agent layer 3).
Finally, by heating the entire heat-shrinkable pressure-sensitive adhesive label 1 to a predetermined temperature (for example, 80 ° C. to 180 ° C.), the heat-shrinkable pressure-sensitive adhesive label 1 is shrunk in the circumferential direction and the container body 911 and the cap portion 912 Thus, the labeled container 10 as shown in FIGS. 7 to 10 is obtained.

In the obtained labeled container 10, the heat-shrinkable pressure-sensitive adhesive label 1 wound around the container is in close contact with the entire outer periphery of the container main body 911 and the cap portion 912, and the upper portion 1 a of the heat-shrinkable pressure-sensitive adhesive label 1. (The upper portion 1a includes a knob 29) is bent to the top surface side of the cap portion 912 and locked to the peripheral end portion of the top surface, and the lower portion 1b of the heat-shrinkable adhesive label 1 However, it bends to the bottom surface side of the container main body 911 and is locked to the peripheral end portion of the bottom surface. Moreover, since the adhesive layer 3 is provided in the entire lower region of the heat-shrinkable pressure-sensitive adhesive label 1, the heat-shrinkable pressure-sensitive adhesive label 1 is adhered to the entire straight body of the container body 911 with almost no gap. .
In particular, the heat-shrinkable pressure-sensitive adhesive label 1 is wound around the heat-shrinkable pressure-sensitive adhesive label 1 by aligning it so that the horizontal perforation line 25 coincides with the boundary portion between the container body 911 and the cap portion 912 or the upper vicinity thereof. Since the region is bonded to the entire outer surface of the body portion of the container main body 911 via the pressure-sensitive adhesive layer 3 (adhesion portion), the water vapor barrier property of the container main body 911 in which the contents are stored can be secured satisfactorily. Moreover, since the pressure-sensitive adhesive is used as the pressure-sensitive adhesive layer 3, the pressure-sensitive pressure-sensitive adhesive adheres to the container main body 911 with a predetermined adhesive force at room temperature, so that the above effect is not impaired.

When opening such a container 10 with a label, the knob 29 is picked with a finger, the heat-shrinkable adhesive label 1 is cut using the oblique perforation line 26, and further along the horizontal perforation line 25 in the circumferential direction. By cutting off, the upper region of the heat-shrinkable pressure-sensitive adhesive label 1 can be removed.
Since the rigidity of the heat-shrinkable substrate 2 of the present invention is moderate, even after the heat-shrinkable pressure-sensitive adhesive label 1 is heat-shrinked, the knob 29 is not so hard and can be picked without feeling pain in the fingertips. Can do.

  In the heat-shrinkable base material 2 of the heat-shrinkable pressure-sensitive adhesive label 1 of the present invention, the front surface layer 5 and the back surface layer 6 are composed of a cyclic olefin layer, and the intermediate layer 7 has an elastomer layer. Since the cyclic olefin layer is excellent in rigidity, the heat-shrinkable base material 2 having it on the front and back surfaces is reasonably strong, and therefore, the mounting operation of the heat-shrinkable pressure-sensitive adhesive label 1 on the container should be performed without hindrance. Can do. Furthermore, since the heat-shrinkable base material 2 is reasonably strong, for example, when the heat-shrinkable pressure-sensitive adhesive label 1 is manufactured by the above-described manufacturing method, a cut line D is formed in the base material C. In addition, the unnecessary region C1 of the base material C can be easily removed. In addition, in the heat-shrinkable pressure-sensitive adhesive label 1 that is temporarily attached to the release paper A and supplied, the heat-shrinkable pressure-sensitive adhesive label 1 can be easily peeled from the release paper A.

  Moreover, the heat-shrinkable base material which has a cyclic olefin layer and an elastomer layer is excellent in water vapor | steam barrier property and heat-shrinkability. For this reason, by attaching the heat-shrinkable pressure-sensitive adhesive label 1 of the present invention to a container, it is possible to prevent moisture from entering the contents or releasing moisture from the contents. Furthermore, since it is excellent in heat-shrinkability, when the heat-shrinkable pressure-sensitive adhesive label 1 is attached to a container, the heat-shrinkable pressure-sensitive adhesive label 1 comes into close contact with the outer surface of the container. If the heat-shrinkable pressure-sensitive adhesive label 1 of the present invention is used, for example, as described above, the upper part and the lower part of the heat-shrinkable pressure-sensitive adhesive label 1 are sufficiently bent to the top and bottom surfaces of the container, and the heat-shrinkable pressure-sensitive adhesive label. It is also possible to obtain a labeled container 10 in which the upper and lower ends of 1 are in close contact with the top and bottom surfaces of the container. In addition, by providing the intermediate layer 7 with an elastomer layer, the heat-shrinkable substrate 2 that can be easily cut along the perforation line can be configured.

In the above, the case where the heat-shrinkable pressure-sensitive adhesive label is attached to a container having a straight barrel-shaped container body is illustrated, but the heat-shrinkable pressure-sensitive adhesive label may be attached to a container having an irregularly shaped container body. Good.
For example, the case where the heat-shrinkable pressure-sensitive adhesive label 1 is attached to an eye drop container having an irregularly shaped container body will be described.

In FIG. 11, the second container 92 includes a container main body 921 for containing contents and a cap portion 922 that closes the spout of the container main body 921. The cap portion 922 is attached to the container main body 921 by a screw action, for example, similarly to the first container.
The container main body 921 has a barrel portion that stores the contents, and a threaded cylinder portion (not shown) formed above the barrel portion. The outer shape of the body portion is a required cross-sectional shape such as a substantially circular shape, a substantially quadrangular shape, a substantially hexagonal shape, or a substantially elliptical shape in a horizontal section view, and is not a three-dimensional shape in three dimensions. That is, the trunk portion includes a large diameter portion 921a and a small diameter portion 921b having a smaller peripheral length than the large diameter portion 921a. In the example shown in the drawing, the body portion is continuous between the two large diameter portions 921a and 921a, the small diameter portion 921b formed between the two large diameter portions, and the large diameter portion 921a and the small diameter portion 921b. A diameter changing portion 921c that is formed and has a circumferential length that changes.
The cap portion 922 has, for example, a required cross-sectional shape (for example, a substantially circular horizontal cross section) and a three-dimensionally straight body. The circumferential length of the cap portion 922 is smaller than the circumferential length of the upper end of the barrel portion of the container main body 921, and therefore, the gap between the cap portion 922 and the trunk portion of the container main body 921 is caused by the difference in circumferential length. A stepped portion 923 exists.

Similarly, after the heat-shrinkable pressure-sensitive adhesive label 1 is wound around the second container 92, the heat-shrinkable pressure-sensitive adhesive label 1 is circumferentially heated by heating the whole heat-shrinkable pressure-sensitive adhesive label 1 to a predetermined temperature. The container 10 is contracted to adhere to the outer surfaces of the container main body 921 and the cap portion 922, and the labeled container 10 as shown in FIG. 12 is obtained.
In the obtained labeled container 10, the heat-shrinkable pressure-sensitive adhesive label 1 is in close contact with the entire outer periphery of the container main body 921 and the cap portion 922. In particular, the heat-shrinkable pressure-sensitive adhesive label 1 is beautifully deformed along the small-diameter portion 921b and the stepped portion 923 of the trunk due to heat shrinkage, and is attached to the container main body 921 with almost no gap through the pressure-sensitive adhesive layer 3. .
As described above, when the heat-shrinkable pressure-sensitive adhesive label 1 of the present invention is used, the heat-shrinkable pressure-sensitive adhesive label 1 is in close contact with the reduced diameter portion 921b and the stepped portion 923. A labeled container 10 having no air layer between the labels 1 can be obtained, and the labeled container 10 has excellent water vapor barrier properties.

[Second Embodiment]
The second embodiment relates to a heat-shrinkable pressure-sensitive adhesive label that is preferably attached to a prefilled syringe, for example.
Hereinafter, the second embodiment will be described. In the description, the configuration and effects different from those of the first embodiment will be mainly described, and the same configuration and the like as those of the first embodiment will be described. In some cases, the terms or symbols are used as they are, and the description of the configuration is omitted.
In FIG. 13, the heat-shrinkable pressure-sensitive adhesive label 1 according to the present embodiment includes a heat-shrinkable base material 2 and a pressure-sensitive adhesive layer 3 provided on the back side of the heat-shrinkable base material 2 as in the first embodiment. And having. The pressure-sensitive adhesive layer 3 is provided on the entire back surface of the heat-shrinkable substrate 2. The heat-shrinkable pressure-sensitive adhesive label 1 of this embodiment is not formed with an opening auxiliary line such as a perforation line. But you may form the auxiliary line for opening as needed.

An example of a prefilled syringe to which the heat-shrinkable adhesive label 1 is attached is shown in FIG.
In FIG. 14, a third container 93 (prefilled syringe) includes a synthetic resin container main body 931 in which an injection needle mounting portion 935 serving as a drug injection port is formed on the front closing surface 934 of the cylindrical body, and an injection needle. The cap part 932 attached to the mounting part 935, the plunger stopper part 933 inserted in the back opening part of the container main body 931, and the chemical | medical agent (not shown) enclosed in the container main body 931 are included.

Specifically, the container main body 931 is formed on the body portion having a substantially cylindrical outer shape, the front closing surface 934 closing the front opening portion of the body portion, and the front closing surface 934, and the body portion. It has an injection needle mounting portion 935 made of a small-diameter cylindrical portion communicating with the inside, and a latching portion 936 that protrudes outward from the periphery of the rear opening of the trunk portion.
The container body 931 is formed of a known synthetic resin molded product such as polyethylene, polypropylene, cyclic polyolefin, and polyethylene terephthalate.
A rubber plunger stopper 933 is inserted into the container main body 931.
A cap portion 932 made of a molded product such as rubber or synthetic resin such as butyl rubber is detachably attached to the injection needle mounting portion 935 of the container main body 931. For example, the cap portion 932 is formed in a columnar shape having a smaller diameter than the body portion of the container main body 931, and is fitted to the middle portion of the injection needle mounting portion 935. In the container main body 931, the medicine is filled and sealed from the plunger plug portion 933 to the cap portion 932.

As shown in FIG. 15A, one side end portion (for example, the left end portion) of the heat-shrinkable pressure-sensitive adhesive label 1 is attached to the body portion of the container body 931, and the heat-shrinkable pressure-sensitive adhesive label 1 is attached. By rotating the container body 931 while applying tension, the heat-shrinkable pressure-sensitive adhesive label 1 is wound around the trunk. Then, the heat-shrinkable pressure-sensitive adhesive label 1 is wound around the container body 931 in a cylindrical shape by superimposing the back surface of the right-side end portion on the surface of the right-side end portion and adhering it through the adhesive portion (adhesive layer 3). It can be attached (see FIG. 5B).
Finally, the heat-shrinkable pressure-sensitive adhesive label 1 is thermally contracted in the circumferential direction of the container body 931 by passing it through a shrink tunnel or the like and heating it to a predetermined temperature (for example, about 80 to 120 ° C.), as shown in FIG. Such a labeled container 10 can be obtained.

In the labeled container 10, the heat-shrinkable pressure-sensitive adhesive label 1 is attached to the container main body 931 through the adhesive layer 3 with almost no gap from the trunk of the container main body 931 to the front closing surface 934 of the container main body 931. In addition, the front end portion of the heat-shrinkable pressure-sensitive adhesive label 1 is attached to a part of the injection needle mounting portion 935 and the cap portion 932 via the pressure-sensitive adhesive layer 3.
The labeled container 10 of this embodiment is also excellent in water vapor barrier properties.

  16 illustrates the labeled container 10 in which the heat-shrinkable pressure-sensitive adhesive label 1 is adhered to a part of the cap portion 932. However, the present invention is not limited to this. For example, as illustrated in FIG. The container 10 with a label to which the heat-shrinkable adhesive label 1 is attached may be used from the body portion of the container body 931 to the entire peripheral surface 932a of the cap portion 932. In the illustrated example, the heat-shrinkable adhesive label 1 is attached only to the edge of the front surface 932b of the cap portion 932, and the front surface 932b of the cap portion 932 is exposed, but the heat-shrinkable property of the present invention. Since the base material has a large thermal shrinkage rate, the exposed area of the front surface 932b can be made as small as possible.

DESCRIPTION OF SYMBOLS 1 Heat-shrinkable adhesive label 2 Heat-shrinkable base material 3 Adhesive layer 5 Front surface layer 6 Back surface layer 7,71,72,73,74,75 Intermediate | middle layer 91,92,93 Container 911,921,931 Container main body 912 922,932 Cap part 10 Container with label

Claims (3)

A heat-shrinkable substrate having a surface layer, a back surface layer, and an intermediate layer between the surface layer and the back surface layer, wherein the surface layer and the back surface layer contain a cyclic olefin polymer as a main component resin. A heat-shrinkable base material comprising a resin layer, and the intermediate layer has a resin layer containing an olefin elastomer as a main component resin;
An adhesive layer provided on the back side of the heat-shrinkable substrate;
A heat-shrinkable pressure-sensitive adhesive label. The heat-shrinkable adhesive label according to claim 1 and a long strip-shaped release paper,
A plurality of the heat-shrinkable pressure-sensitive adhesive labels are temporarily attached to the release surface of the release paper via the pressure-sensitive adhesive layer so that the heat-shrink direction of the pressure-sensitive adhesive label is the longitudinal direction of the release paper. , Label continuum. A heat-shrinkable adhesive label according to claim 1 and a container having a container body,
A labeled container in which the heat-shrinkable pressure-sensitive adhesive label is wound around the container main body and attached to the container main body via an adhesive layer, and is heat-shrinked and adhered.

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