WO2005059869A1

WO2005059869A1 - Adhesive label

Info

Publication number: WO2005059869A1
Application number: PCT/JP2004/018563
Authority: WO
Inventors: Masahiko Kawashima; Yutaka Matsuki
Original assignee: Asahi Kasei Life & Living Corporation
Priority date: 2003-12-18
Filing date: 2004-12-13
Publication date: 2005-06-30
Also published as: JPWO2005059869A1; TW200530093A

Abstract

An adhesive label capable of solving problems in a conventional gas filling/packaging/sealing method wherein a gas barrier heat-shrinkable film is used and, when the film is heated by a microwave oven, the film covering a packaged body is ruptured with explosive sound due to a rise in pressure in the packaged body, contents in the packaged body are spattered in the microwave oven or the packaged body is crushed by a heat shrinkage stress of the covering heat-shrinkable film. The adhesive label comprises a base material layer and an adhesive agent layer, and at least one of layers forming the adhesive label is formed in a heat-shrinkable layer. Accordingly, the adhesive label can be prevented from being automatically re-adhered to a container after heating is completed by the deformation of the adhesive label. As a result, the container can be prevented from being recessed or crushed by the volumetric change of the container or a bag in cooling.

Description

Specification

Bonding Rabenore technical field

[0001] The present invention relates to an adhesive label, a packaging method, a container or bag equipped with the adhesive label, and an envelope.

Background art

Recently, in addition to the conventional form of purchasing food in supermarkets and cooking and eating the purchased food in each home, cooking is performed in a backyard such as a supermarket or in a central kitchen etc. Purchased ready-to-eat foods etc. and the form to eat at home is increasing. This reflects the desire to do housework simply because they do not have time for cooking because they want to work together, and want to take more time for their own hobbies.

[0003] On the other hand, with regard to ready-made foods in supermarkets and convenience stores, products have been actively developed to suit the taste, amount, etc. of individual foods, in addition to the convenience of ready-made foods. Food is put into the market. In addition, even with the same type of products, supermarkets and convenience stores are changing the shape and design of packaging containers to maximize the display effect and to pursue the taste of food. As a result, containers of various sizes and shapes are on the market.

Particularly in the field of sugar beet, in the same large-scale sales of conventional products, it is desirable to eat a small amount (such as small people or an amount suitable for single use) and seasoning (with Kyoto flavor). Etc) can be selected. In addition, the color of the container may be changed for each food item to maximize the display effect by design. As a result, the market is full of containers of various sizes, shapes and colors. As a result, for small and large-sized food containers such as supermarkets and convenience stores, it is necessary to change the equipment for packaging food in small quantities and in multiple varieties, and the production efficiency is reduced due to the complexity. The problem is that the management of parts of packaging machines is complicated.

[0005] Food sellers such as supermarkets and convenience stores that solve this problem extend the product life of sugar beets etc., reduce the number of expired items (so-called loss), and cut off the production brand. We are seeking to improve productivity by reducing replacement.

[0006] As a method of storing goods for a long time, so-called gas-filled packaging in which food is stored under a suitable gas atmosphere has been known and studied. As the shelf life of products is extended by using food as gas-packed packaging, it is expected that production efficiency will be improved, such as long-term product distribution and reduction of shelf-life products.

[0007] Such gas-filled packaging methods have been variously studied conventionally. For example, Patent Document 1 is characterized by comprising a tray portion for accumulating contents and a lid portion covering the tray, a gas injection port is provided on the top surface of the lid, and a gas exhaust port is provided around the lid. A gas-filled packaging method is disclosed in which a gas-filled packaging tray is used, and the entire periphery is covered and sealed with a heat-shrinkable film having gas barrier properties. In this gas-filled packaging method, the gas injection port provided on the top surface of the lid and the exhaust port provided around the lid are covered with a gas barrier heat-shrinkable film, so that the gas filled can be reliably sealed. It is good at being able to

[0008] While force is applied, the method represented by Patent Document 1 uses a heat-shrinkable film having a gas-barrier property and a gas outlet located on the top surface of the lid and a gas outlet around the lid. Since the whole circumference is covered, by heating the package in a microwave oven etc., the water contained in the food in the packaging container, the gas filled, etc. are thermally expanded and the internal pressure in the package is raised. As a result, the heat-shrink film which has been generated and wrapped breaks with the noise, and there is a problem that the contents in the package are scattered in the microwave oven. Further, even if the packaged heat shrinkable film does not rupture, a part of the heat seal portion of the heat shrinkable film is opened when the internal pressure rises, and water vapor is released into the container through the gap. As a result, since the inside of the container is depressurized at the time of cooling, the container itself is dented at atmospheric pressure, leaving the problem that the container is crushed.

Furthermore, when heated by a microwave oven or the like, the heat-shrink film which has been enclosed starts to shrink further due to the heat, and the heat-shrink stress of the heat-shrink film squeezes the package, container and lid and gas barrier properties As the heat-shrinkable film is double-wrapped and the packaging material used for packaging is increased, the problem of increased burden on businesses under the Container Recycling Act remains.

Patent Document 1: Japanese Patent Application Laid-Open No. 9-29567. Disclosure of the invention

Problem that invention tries to solve

An object of the present invention is to provide an adhesive label, a packaging method, a container or a bag equipped with the adhesive label, and a package, which solve such problems.

Means to solve the problem

[0011] The present inventors, as a result of intensive studies to solve the above problems, have found that the above problems can be achieved by the following adhesive label, packaging method and package. The present invention is completed by this discovery.

That is, the present invention provides the following.

(1) An adhesive label having a substrate layer and an adhesive layer, wherein at least one of the layers constituting the adhesive label is a heat shrinkable layer.

(2) An item in which the layer constituting the adhesive label includes a functional part and a protective layer, the functional part is provided on the adhesive layer of the adhesive label, and the protective layer is provided to cover the functional part Adhesive label as described in (1).

(3) The adhesive label of item (2), wherein at least a part of the protective layer is in contact with the adhesive layer.

(4) In the item (2), wherein the functional part includes at least one selected from an oxygen concentration detecting agent, an oxygen absorbing agent, a humidity control agent, a fugitive transpiration agent, a carbon dioxide gas generating agent, a freshness maintaining agent and a temperature detecting agent. Adhesive label as described.

(5) The adhesive label as described in the item (2) in which the functional part contains an enzyme.

(6) The adhesive label as described in the item (1) which has a layer which consists of gas barrier materials.

(7) The adhesive label as described in item (2), wherein the protective layer is a heat shrinkable layer.

(8) The adhesive label according to item (1), wherein the adhesive layer contains any adhesive selected from acrylic, rubber and silicon adhesives.

(9) A package container or bag having at least one air passage is sealed at a location other than the air passage, and gas in the container or bag is degassed or replaced with another gas via the air passage, Then, the packaging method which block | closes this air path with the adhesive label as described in an item (1).

(10) A packaging container or bag having the adhesive label described in item (1).

(11) A package having the adhesive label according to item (1). Effect of the invention

With the adhesive label of the present invention, it is possible to degas the package or fill the package with gas S, so that the deterioration of the contents such as oxidation can be prevented, and the preservability of the food is dramatically improved. S ability. In addition, when the package is heated by a microwave oven or the like, the package can be heated without damaging the appearance of the package, and the gas inside the package whose internal pressure has risen can be discharged safely. By automatically preventing adhesion by deformation of the adhesive label, it is possible to prevent container dents and collapses due to volume change of the container or bag during cooling. Furthermore, by providing the adhesive label with the functional part, it is possible to easily obtain an adhesive label having a specific function.

Brief description of the drawings

FIG. 1 is a plan view showing an example of the shape of the adhesive label of the present invention and the shape of an air passage.

FIG. 2 is a perspective view and a cross-sectional view of an example of the adhesive label of the present invention.

FIG. 3 is a perspective view and a cross-sectional view of an example of the adhesive label of the present invention.

FIG. 4 is a side view and a top view of a container (main body) used in an example of the present invention.

FIG. 5 is a side view and a top view of a lid used in an example of the present invention.

FIG. 6 is a side view and a partially enlarged cross-sectional view when the container (main body) and the lid used in the example of the present invention are stacked.

FIG. 7 is a perspective view showing an example of a package using the adhesive label of the present invention, where A is a lid top surface and B is a diagram showing a case where the adhesive label is adhered to the lid side surface.

FIG. 8 is a perspective view showing an example of a package using the adhesive label of the present invention, showing the case where the adhesive label is adhered to the side of the bag.

BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, the present invention will be described in detail, focusing on particularly preferred embodiments thereof.

In the prior art gas-filled packaging sealing method, a heat shrinkable film having gas barrier properties is used, and when heated by a microwave oven or the like, the heat shrinkable film ruptures with loud noise due to the rise in internal pressure in the package, and the package is packaged. There was a problem that the contents inside the body were scattered in a microwave oven, and the heat shrink stress of the wrapped heat shrink film caused the package to be crushed. On the other hand, in the present invention, an adhesive label having gas-nore uniformity is used. Thus, when the package is heated by a microwave oven or the like, the package can be heated without impairing the appearance of the package, and the gas inside the package whose internal pressure has risen can be safely discharged, and automatically after heating is completed. By preventing the adhesive label from re-adhering to the container by deformation of the adhesive label, it is possible to prevent container dent or collapse due to volume change of the container or bag during cooling.

Also, after degassing or gas filling through the air vent, the air vent is sealed with an adhesive label, so that the effect of gas filling is maintained by its gas porosity, and the oxygen outside the container is maintained. Can prevent the influx of As a result, deterioration such as oxidation of the contents can be prevented, and the storage stability of food can be dramatically improved.

Furthermore, by providing the adhesive label with the functional part, it can be easily made an adhesive label having a specific function.

For example, when the oxygen absorbing portion is provided as a functional portion on the adhesive label, the oxygen absorbing function is attached to absorb the oxygen which is greatly involved in the deterioration of the contents in the container or the bag, and to suppress the discoloration and decay of the contents. You can get a label. In addition, when the oxygen concentration detection unit is provided on the adhesive label as a functional unit, an adhesive label with an oxygen detection function can be obtained, which can visually confirm the presence or absence of oxygen in the container or the bag at a glance. Furthermore, when an adhesive label has both an oxygen absorbing part and an oxygen detecting part, one adhesive label can be provided with a plurality of functions, and it is possible to obtain an adhesive label capable of preventing quality deterioration and confirming quality at a glance. it can.

The adhesive label referred to in the present invention is a flat shape having an adhesive on the surface contacting the lid of the package, and sealing the air passage provided by the lid without a gap through the adhesive. (Sealing) The force S can be used, and it may be in any shape as long as it can be sealed so as not to dissipate the gas present in the packaging container. As an example of the planar shape of the adhesive label, a square (A in FIG. 1), a rectangle (B in FIG. 1), a quadrangle (C in FIG. 1) having corner portions R, a polygon (D in FIG. 1) ), Circle (E in Fig. 1), semicircle (F in Fig. 1), ellipse (G in Fig. 1), semi-ellipse (H in Fig. 1), star (1 in Fig. 1), irregular shape (Fig. 1) J), circle + knob (K in Fig. 1), rectangle + knob (L in Fig. 1), ellipse + knob (M in Fig. 1), square + knob (N in Fig. 1), etc.

Examples of the configuration of the adhesive label include a single layer or multilayer structure and the like made of paper, metal thin film, resin and the like. The adhesive label is made of the same material as the container from the viewpoint of separate collection. More preferably, it consists of fat. In addition, the adhesive label may be made of a resin (hereinafter referred to as "gas barrier resin") having gas barrier properties from the viewpoint of preventing sparks due to electron collision during microwave heating and from the viewpoint of preventing gas dissipation. More preferable. Further, in the present invention, the adhesive label preferably has a certain degree of strength from the viewpoint of preventing breakage due to external piercing. In the measurement based on Article 10 of the Agricultural and Forest Standard, the puncture strength is preferably 2. ON or more, more preferably 2.5 N or more, and still more preferably 3. ON or more.

The adhesive label of the present invention has two layers of a base material layer and an adhesive layer. The material of the base material layer used in the adhesive label of the present invention may be any material as long as it has a certain degree of rigidity, for example, plastic, metal, wood, paper, other single layer or laminated layers of the above materials. Body etc. can be mentioned.

The adhesive label of the present invention is preferably made of a thermoplastic resin or thermosetting resin generally used for a container or a lid, from the viewpoint of processability and the viewpoint of sorting and discarding.

For example, as a thermoplastic resin, polyethylene resin, polypropylene resin, polystyrene resin, methacrylic resin, polyvinyl chloride resin, polyamide resin, polycarbonate resin, polyethylene terephthalate resin, polybutylene terephthalate resin, cellulose acetate resin, ethylene one-bullet Alcohol-based copolymer resins (EVOH etc.) and the like can be mentioned, and as thermosetting resins, urea resin, melanin resin, xylene resin, phenol resin, unsaturated polyester resin and the like can be mentioned. These resins may be single resins or copolymer resins.

Further, a thermoplastic resin is preferably used from the viewpoint of easiness of label processing. Examples of thermoplastic resins include polyolefin resins including polyethylene resin (HDPE, LLDPE, etc.), polypropylene resin (PP), polybutene-11 resin (PB), and poly-4-methylpentene resin. Resin (PO), or ethylene / acetic acid / bule copolymer resin (EVA), ethylene / monomethyl methacrylate copolymer resin (EMA etc.), ethylene / vinyl alcohol copolymer resin (EVOH etc), etc. Aromatic polyester resins such as modified polyolefin resins (PO modified products), polyethylene terephthalate resins (modified resins) (PET etc.), polybutylene telephthalate resins (modified resins) (PBT etc), or Aliphatic polyester resin including polylactic acid resin, polyglycolic acid resin, chlorinated vinyl resin including polyvinylidene chloride resin (PVDC), polyvinyl chloride resin (PVC) Copolymer resin (containing same hydrogenated resin), << Olefin (ethylene, etc.)-styrene copolymer resin (containing same hydrogenated resin), ethylene monocyclic hydrocarbon compound copolymer resin (containing same hydrogenated resin) And polyamide-based resins (Ny); In addition, a single layer or a multilayer of these resin compositions selected mainly from at least one selected from the above resins, or a laminate of different resins with these layers, or a stretched or not formed of these resins Stretched labels can be used. Among them, polyethylene resins (especially HDPE), polypropylene resins (PP), ethylene-vinyl alcohol copolymer resins (EVOH etc.), polyamide resins (Ny), polyethylene terephthalate from the viewpoint of heat resistance and gas barrier properties. Partially contains an aromatic component such as a (modified) resin (PET), a polybutylene terephthalate (modified) resin (PBT), or a polylactic acid resin or a polyglycolic acid resin An aliphatic component polyester-based resin (PET) or the like is preferably used.

[0023] The adhesive label of the present invention is a film or sheet of a single layer or multilayer constitution made of these resins. In the case of a multi-layered structure, co-extrusion methods, various laminate methods and the like may be appropriately selected as a method of forming multi-layered structures. For the film and sheet used in the adhesive label of the present invention, a material having a gas barrier property is more preferable from the viewpoint of maintaining the gas filling.

The adhesive label of the present invention preferably has gas barrier properties. As a method of imparting gas barrier property to the adhesive label, a base material layer made of a resin having gas barrier property may be used, or a resin layer provided with an inorganic substance in a layer may be provided. . For example, gas barrier properties may be imparted to the resin layer by depositing an inorganic substance of silica and Z or alumina on a low density polyethylene resin layer having poor gas barrier properties. In addition, a composite barrier substance of organic type and inorganic type may be used.

[0025] As the gas barrier properties of the adhesive label, carbon dioxide gas permeation amount is 143935 ml Z (m 2 'day'MPa), oxygen gas permeation amount is 1-3948 ml / (m ² 'day'MPa), nitrogen gas Permeation power S 1 1481 ml / (m ² · day · MPa) is preferred, and carbon dioxide gas is more preferred. Permeation amount of nitrogen is 1: 1-4500ml / (m ² · day · MPa), oxygen permeation amount of 1 – 2500ml / (m ² · day'MPa), nitrogen gas permeation is 1- 1300ml / (m ² 'day' More preferably, carbon dioxide gas transmission rate is 1-4000 ml / (m ² · day · MPa), oxygen gas transmission rate is 1- 1300 ml / (m ² · day MPa), nitrogen gas transmission rate Is one thousand 1000 ml / (m ² · day · MPa). Even more preferably, the carbon dioxide gas transmission rate is 1 to 1000 ml Z (m ² 'day' MPa), the oxygen gas transmission rate is 1 to 300 ml Z (m ² 'da MPa), and the nitrogen gas transmission rate is 1 to 250 ml / (m ² (day. MPa).

The thickness of the gas barrier base layer (hereinafter referred to as “gas barrier base layer”) used in the present invention varies depending on the oxygen gas transmission rate of the resin used, and the above-mentioned oxygen gas permeation It is preferred to ensure a thickness that is 1 1 1974 ml / (m ² 'day'MPa). For example, in the case of ethylene-bule alcohol-based copolymer resin (EVOH) having a low oxygen gas transmission rate, it is possible to achieve the desired oxygen gas transmission rate at about several μm from the viewpoint of the oxygen gas transmission rate. is there. However, due to poor rigidity as an adhesive label, the working efficiency at the time of affixing with a label application machine is poor. From the viewpoint of handling of the label, resins having other stiffness, such as polypropylene resin (PP), polyester It is necessary to laminate a layer made of resin (PET) and a layer made of EVOH. In the case of a gas barrier substrate layer in which a layer composed of PP and a layer composed of EVOH are laminated, the gas barrier substrate layer preferably has an oxygen gas transmission rate of 1 1974 ml / (m ² · day · M Pa) The thickness of the adhesive label from the waist point of 20 150 / im force S preferred. More preferably, it is 30 to 120 / im, more preferably 35 to 115 μm.

In addition, known additives, for example, an antioxidant, a light stabilizer, an antistatic agent, an antifogging agent, a coloring agent, a lubricant and the like are mixed in the base layer within a range not impairing the effects of the present invention. You may In addition, the substrate layer may be coated with known surface treatment, for example, vinylidene chloride or the like such as corona discharge treatment, flame treatment, irradiation treatment including electron and plasma, ion etching treatment, and the like.

In the present invention, the adhesive layer of the adhesive label will be described. First, the term “adhesion” as used in the present invention means bonding an adhesive label to a bag, a container or a lid. The adhesive strength can be selected by selecting the type of adhesive, the amount applied, etc. according to the desired adhesive strength, which is acceptable if selected. Even if the adhesive has weak adhesive strength, it is sufficient if the adhesive label and the bag, container or lid can be attached and sealed. Typical types of adhesives include solvent type, hot melt type, reactive type and the like, but any adhesive having adhesive properties will eliminate the trouble, for example, rubber adhesive, acrylic adhesive, vinyl ether adhesive And silicone adhesives and resin compositions mainly comprising at least one selected from these.

From the viewpoint of easily setting a desired adhesive strength, rubber-based adhesives, acrylic-based adhesives, and bule ether-based adhesives are preferable. More preferred are rubber adhesives and acrylic adhesives. Furthermore, since the amount of the solvent extract is small and the amount of impurities is small, acrylic adhesive power S is further more preferable. In addition, these adhesives contain known additives such as an antioxidant, a light stabilizer, an antistatic agent, an antifogging agent, a coloring agent and the like within the range not impairing the effects of the present invention. It is also good. In addition, silicon or the like having a peeling effect is printed on the gas barrier substrate layer in advance so that partial peeling is intentionally generated between the gas layer-one substrate layer and the adhesive layer of the adhesive label of the present invention. The agent layer peels off from the gas barrier substrate layer and is the adherend. Container · lid · left in the bag, even if it is equipped with tamper proof printing.

[0030] Examples of the rubber-based adhesive include natural rubber containing cis 1, 4 polyisoprene as a main component, synthetic rubber containing styrene 'butadiene rubber (SBR), polyisobutylene, butyl rubber or the like as a main component, or Styrene 'Butadiene' Styrene copolymer rubber (SBS), Styrene 'isoprene. Styrene copolymer rubber (SIS), etc. At least one adhesive elastomer selected from block rubbers and the like as a main component, liquid at room temperature or Rosin-based resins, terpene-based resins, petroleum resins, chroman 'indene resins, etc. that are thermoplastic resins of solid amorphous, amorphous oligomers (medium-molecular-weight polymers of dimers or higher) with molecular weights of several hundred to about 10,000. Those obtained by blending an adhesion-imparting agent and a softener such as mineral oil, liquid polybutene, liquid polyisopylene, liquid polyacrylate and the like can be mentioned.

As the acrylic adhesive, for example, a main monomer which imparts adhesiveness represented by a low Tg, homopolymer represented by acrylic acid alkyl ester, acrylic acid ester of lower alkyl, methacrylic acid alkyl ester, etc. Comonomers that give cohesion such as acetic acid, styrene, acrylonitrile, etc. that can be copolymerized with the main monomer and give a high Tg, carboxyl group-containing monomers such as acrylic acid and methacrylic acid (such as atalylate), hydroxyl groups, An adhesive reaction product of a functional group-containing monomer which gives an adhesive property such as a xy group or an amino group to be a crosslinking point may optionally be blended with the above-mentioned adhesion imparting agent, softener and the like.

As the Bielether-based adhesive, for example, homopolymers such as Biel methyl ether, vinyl ether, vinyl isobutyl ether, or copolymers with atarilate (adhesive elastomer 1), in some cases, the above-mentioned adhesion promoters, Those containing a soft glaze and the like can be mentioned.

As a silicone adhesive, for example, a polymer having a residual silanol group (Si OH) at the end of a polymer chain represented by high molecular weight polydimethylsiloxane or polydimethyl diphenyl siloxane (or adhesive elastomer 1) And the above-mentioned adhesion imparting agents, softeners and the like.

The adhesive strength can be widely set in view of gas barrier properties, particularly gas-filled packaging, and from the viewpoint of food hygiene, acrylic, rubber and silicon adhesives are preferable.

The adhesive strength in the present invention is 0 · 1-10 N / cm in the measurement method by the 180 degree peeling method of JIS-Z-0237 from the viewpoint of adhesive strength at bonding and peel strength at peeling. Preferred,. More preferably, it is 0.2 to 9.5 N / cm, still more preferably 0.3 to 7.5 N / cm.

The thickness of the adhesive layer used in the present invention varies depending on the adhesive used, but the adhesive strength which is good when the adhesive strength is 0.1 to 10 N / cm depends on the thickness of the adhesive layer. It is not a thing. For example, in the case of an acrylic adhesive, the thickness of the adhesive layer is preferably 3 to 50 / im force S from the viewpoint of adhesive strength. Moreover, More preferably, it is 5-40 / im, More preferably, it is 8-35 / im.

The gas barrier adhesive label of the present invention may be provided with a knob to impart easy openability.

For example, from the viewpoint of preventing the package from bursting when heated, the gas barrier adhesive label is provided with a semicircular knob, and the easy openability such as easy opening by opening the knob from the lid is given. Is more preferred. In addition, an acrylic emulsion may be used as an adhesive of the label. In this case, when the package is heated, water vapor from the contents weakens the adhesive strength of the adhesive, and the internal pressure in the package automatically opens a part of the label to prevent rupture. In the present invention, the heat shrinkable layer is a function to prevent the adhesive label from completely blocking the air passage again by its own weight after heat treatment in a microwave oven or the like due to the deformation of the heat shrinkable layer after heating. On the adhesive label. That is, the adhesive label of the present invention comprises a heat shrinkable layer at least in part. Therefore, when heat treatment is performed in a microwave oven etc., the water contained in the contents in the container or bag is discharged as steam to the outside of the container or bag as an open port, and the heat of the water vapor is the heat shrinkable layer of the adhesive label. The adhesive label is deformed by being given to. The deformation prevents the adhesive label from completely blocking the air passage again by its own weight after the heat treatment. As a result, it is possible to prevent the container or the bag from being dented or crushed at atmospheric pressure due to the pressure reduction in the container or the bag.

In the present invention, the heat-shrinkable layer may be disposed anywhere on the adhesive label, but the heat-shrinkable layer may be disposed in a portion close to the surface layer of the adhesive label from the viewpoint of the ease of heat contraction and its effect. Preferably, it is disposed on the outermost surface of the adhesive label, more preferably on the layer adjacent to the adhesive surface of the adhesive layer.

The heat shrinking function of the heat shrinkable layer of the present invention is exhibited using water vapor generated at the time of heating of a microwave oven or the like. Therefore, the heat shrinkage start temperature is preferably 50 ° C. or more and 150 ° C. or less, more preferably 80 ° C. or more and 150 ° C. or less, and still more preferably 90 ° C. or more and 150 ° C. or less. Such heat-shrinkability is usually imparted by stretching. The heat shrinkage start temperature can be controlled by setting the temperature at the time of stretching of the resin, the stretching method, the stretching ratio and the type of polymer. Even if all of the adhesive labels that have been interfered with using any known method such as tenter type or bubble type are drawn, the drawn film is attached to at least a part of the adhesive label. There is no problem even if it matches. The bonding method is a known method such as dry lamination, sand lamination, melt lamination, adhesion processing with an adhesive, etc. There is no problem even if a method of deviation is used.

The shrinkage ratio differs depending on where the heat-shrinkable layer is provided on the adhesive label, but the shrinkage ratio can be such that the entire surface of the adhesive label does not adhere to the container again after microwave heating is completed. Is preferred. For example, FIG. 2 is shown as an example of a preferred embodiment of the present invention. In the adhesive label shown in FIG. 2, an acrylic adhesive of 25 g / m ² is used as the adhesive layer on polyethylene terephthalate (75 μm in thickness) which does not shrink as the base material layer. And a stretched polystyrene film (25 μm) as a heat-shrinkable layer on the adhesive layer. In this embodiment, the heat-shrinkable layer is shrunk by the water vapor jetted from the stretched polystyrene pore force container, and the contraction causes the polyethylene terephthalate substrate to bend toward the heat-shrinkable layer side, and the curve adheres to the container. You can prevent that force S. However, if this degree of bending is excessive, it may be difficult to re-seal the vent after cooling. When it is desired to re-seal after cooling, it is important to control this bending by controlling the shrinkage rate of the heat-shrinkable layer.

In the embodiment illustrated in FIG. 2, the shrinkage factor at 90 ° C. of the stretched polystyrene film is MD direction / TD direction = 3% Z3%. The MD direction indicates a direction (Machinery Direction) parallel to the drawing direction, and the TD direction indicates a direction (Transverse Direction) perpendicular to the drawing direction. In addition, the contraction rate needs to be the same contraction rate in both the MD direction and the TD direction. It is preferable to have anisotropy from the viewpoint of the deformed shape at the time of contraction. The ratio of shrinkage ratio is preferably a shrinkage ratio in the MD direction / a shrinkage ratio in the TD direction (or a shrinkage ratio in the TD direction / a shrinkage ratio in the MD direction) of 1.1 or more, more preferably 1.3 or more. Furthermore, even if the heat-shrinkable film is attached by bonding through an adhesive of an adhesive label, there is no problem if the adhesive label is deformed by water vapor generated by heat treatment in a microwave oven or the like.

Furthermore, even if the adhesive label of the present invention has a member having a further specific function, there is no problem if the adhesive label is deformed by the contraction of the heat-shrinkable layer. In this case, an example of a preferred embodiment is illustrated in FIG. In FIG. 3, a member (functional portion) having a function is adhered to the adhesive layer of the adhesive label, and a heat shrinkable film which is a heat shrinkable layer is used as a protective layer to cover the functional portion. It is a bonded functional adhesive label.

As described above, the heat-shrinkable layer may be used as a protective layer of the functional part. The functional part may be a liquid having a specific function (functional liquid), but it is preferable from the viewpoint of directional handling in which the functional liquid is in a solid state. Therefore, it is preferable that the functional fluid be carried on the support. Examples of the support include metals, plastics, crystalline cellulose, gels (including sol-like mucilage), filter paper, porous structures and the like. Specifically, tablets obtained by tableting using the trade name Avicel (Asahi Kasei Co., Ltd.), etc., those covered with a gel such as gelatin or agar, or impregnated with a water-absorbent filter paper, etc. But the functional fluid Any structure may be used as long as it can be handled as a feature. The adhesive label of the present invention may be subjected to visual effects such as printing to distinguish it from other products, but when a functional part is used, at least the adhesive label is used to confirm the expression of the function. It is preferable to have a transparent part in part. Specifically, in order to confirm the functional part of the adhesive label, only the functional part of the protective layer should not be printed, or the protective layer should be printed so as to have a haze value sufficient to confirm discoloration. Is preferred. As such a haze value, 10% or less is preferable. More preferably, it is at most 8%, more preferably at most 6%.

The functional units of the present invention will be specifically described. The functional unit of the present invention visually detects and instructs an environmental condition such as a gas environment, temperature and humidity inside a container or a bag. For example, when detecting and instructing the oxygen concentration in a container or a bag, a support such as filter paper may be impregnated with a redox indicator such as methylene blue as a functional liquid or an enzyme detection liquid using an enzyme and an enzyme and a substrate. , Can be an oxygen detection agent.

The redox indicator in the present invention changes the light absorption wavelength by oxidation or reduction of a substance, and the presence or absence of oxygen can be determined by detecting the changed light absorption wavelength. It is The available wavelength range of the light absorption wavelength can be any wavelength as long as the changed wavelength can be measured or detected.

[0046] For example, if there is a change range in the UV region, it is better if it is detected using a UV measuring device. In addition, it is preferable that the light absorption wavelength change region (wavelength change region) is a visible light region (400 nm to 600 nm), since the change in wavelength can be visually confirmed without using a machine for measuring the wavelength. The light absorption wavelength change reaction of the redox indicator means that the light absorption wavelength is changed due to the structural change of the redox indicator itself or the reaction with another compound that the redox indicator contains in the oxygen detection agent part. Say.

[0047] The light absorption wavelength change reaction of this redox indicator may be either a reversible reaction or an irreversible reaction without any problem. A reversible reaction is preferred because it can be used over and over again. In addition, by selecting various redox indicators used in the present invention, it is possible to detect the presence or absence of oxygen with a desired color and a desired oxygen concentration, and further to set the oxygen concentration to be detected, the color change rate, etc. It can be set as desired. Furthermore, the oxidation of the present invention If the color change caused by the former indicator is an irreversible reaction, the degree of exposure of the contents in the package to oxygen can be determined by the color difference (color shading, color change, etc.), so the degree of exposure of the contents in the package to oxygen is Accumulated display is possible.

[0048] If the wavelength change range of the redox indicator is in the visible light range (400 nm 600 nm), it is preferable because visual confirmation can be performed at a glance using a machine for measuring the wavelength. Furthermore, if several kinds of redox indicators can be mixed stably and can react independently, it is possible to detect environmental changes inside the container or bag stepwise. is there. For example, if several kinds of redox indicators with completely different oxygen concentration, reaction rate and color at the time of reaction are used for the reaction of the redox indicator, the certain oxygen concentration will be orange, and further the oxygen concentration It is possible to change the color stepwise depending on the oxygen concentration, such as blue, when Y is high. In addition, it is possible to change the color stepwise depending on the oxygen exposure time, such as brown when the oxygen exposure time is short and red when the oxygen concentration exposure time is long.

[0049] Examples of the redox indicator referred to in the present invention include methylene blue, gallocyanine, methyl red, methyl bio red, thymol blue, anthocyanin, methyl yellow, pheno nore red, thymolo levtalein, azaline yellow, anthraquinone, safranin, β -Mochiguchi There may be mentioned tin, lycopene, resorufin, thionine, cresyl blue, toluidine blue, methylologen, litmus, bromthymol blue, carmine, phenolphthalene and the like. Among them, methylene blue, methinole red, methyl bio red, thymol blue, anthocyanin, methyl yellow, phenol red, anthraquinone, safranine, beta-heavy tin, resorufin, thionine, cresyl blue, methyl orange, litmus, bromochi mo reno no 1, phenol pro Ren is preferred, more preferably methylene blue, methyl red, thymol blue, anthocyanin, phenol red, anthraquinone, / 3-carotin, cresyl blue, methyl orange, litmus, bromthymol blue, phenolphthalene, still more preferably methylene blue, Methylored red, anthocyanin, anthraquinone, / 3-carotene, methyl orange, litmus, bromthymol blue, pheno It is Nolephtalen.

Further, the redox indicator that can be used in the present invention is a redox for oxygen Discolor by the function. On the other hand, this function may also function by carbon dioxide, and a redox indicator may be used as a carbon dioxide detection agent as well as an oxygen detection agent. In addition, an enzyme detection solution using an enzyme, an enzyme and a substrate will be described. In the present invention, the enzyme is a polymer that acts as a catalyst for various in vivo chemical reactions, and an enzyme (oxidase) that catalyzes a redox reaction depending on the type of reaction catalyzed. Enzyme that catalyzes transfer of functional group (transferase), Enzyme that catalyzes hydrolysis reaction (hydrolase), Enzyme that catalyzes elimination reaction and addition reaction (lyase), Enzyme that catalyzes isomerization reaction (isomerase), ATP Etc. It is classified into an enzyme (ligase) that catalyzes a synthesis reaction that couples two molecules in conjunction with hydrolysis.

Essentially, enzymes are responsible for catalyzing these in vivo reactions in order to maintain the organism. The enzyme used in the present invention can detect the presence or absence of oxygen by detecting the changed light absorption wavelength which is good if the light absorption wavelength of the enzyme or the substrate changes due to the presence or absence of oxygen among these enzyme reactions. It can be judged.

The available wavelength range of the light absorption wavelength can be any wavelength as long as the changed wavelength can be measured or detected. For example, if there is a change range in the UV region, it may be detected using a UV measuring device. It is preferable that the change range is a visible light range (400 nm to 600 nm), as it can be confirmed visually without using a machine for measuring the wavelength. In addition, even if carbon dioxide and alcohol are present in the package, the oxygen detection agent using the light absorption wavelength reaction of the enzyme does not affect the enzyme reaction for determining the presence or absence of oxygen, so it is stable and accurate. It is possible to confirm the presence or absence of oxygen (by color if it is in the visible light range) by changing the light absorption wavelength.

The change in the light absorption wavelength may be caused either by the structural change of the enzyme itself or by the structural change of the substrate by the enzyme reaction. An example is given in which the structure of the enzyme itself changes. In the case of metal-containing enzymes (copper enzymes), the metal (copper) is present in the system in an ionic state by elimination of some of the metals (copper) that constitute the enzyme, and the metal ions are present. It has a distinctive color (blue). Also, an example is given in which the structure of the substrate is changed by the enzyme reaction. The substrate takes on hydrogen from the hydroxyl group and amino group constituting the substrate to form a double bond or to exhibit a color by association of substrate molecules. [0054] When the light absorption wavelength is changed due to the structural change of the substrate due to the catalytic action of the enzyme, the presence or absence of oxygen can be detected with a desired color by variously selecting the enzyme and the substrate, and further detecting oxygen It is possible to set the concentration and change the color change rate as desired. Furthermore, if the substrate change due to the enzyme reaction is irreversible, it can be integrated and displayed how much the contents in the package have been exposed to oxygen. For example, when the light absorption wavelength of the substrate itself is changed due to the structural change of the substrate due to the enzyme reaction, this change is irreversible, and if the change range of the wavelength is the visible light region, the acid of the contents in the package is Since the degree of exposure to the element can be determined visually by color difference (color shade, color change, etc.), how much oxygen the contents in the package have been exposed to can be integrated.

[0055] Furthermore, since the enzyme reaction independently reacts with various substrates between the enzyme and the substrate, several kinds of enzymes and substrates can be used in a mixed state. For example, when one kind of enzyme is used as a mixture of several kinds of substrates having completely different oxygen concentration, reaction rate and color at the time of reaction, it is yellow at one oxygen concentration and blue at high oxygen concentration. It is possible to change the color stepwise by oxygen concentration etc. In addition, it is possible to change the color stepwise depending on the oxygen exposure time, such as brown when the oxygen exposure time is short and red when the oxygen exposure time is long.

Such enzymes that change the light absorption wavelength include oxidase, catalase and benreoxidase, flavin monooxygenase, same hydromonooxygenase, iron monooxygenase, ribulose 2 Phosphate oxygenases, dioxygenases and the like can be mentioned. Specifically, catecholoxidases (EC 1. 10. 3. 1), laccases (EC 1. 10. 3. 2), pilyl oxidases (EC 1. 3. 3. 5), ascorbine The acid oxidase (EC 1.10.3.3), 3-hydroxyanthranilic acid oxidase (EC 1.10.3.5), etc. may be mentioned. When the reaction is carried out by adding a substrate, all enzymes which significantly accelerate the light absorption wavelength change reaction are included in the presence of oxygen. These may be used alone or in combination.

Further, as the substrate, any substrate may be used as long as the structure is changed by the above-described enzyme and the light absorption wavelength is changed.

As examples of substrates, relatively high activity of hydroxyl group, amino group, cyano group, carbonyl group etc. Examples thereof include benzine diols, hydroquinones, polyphenols, phenylendiamines, ascorbic acid, cyanine dyes, L-ascorbetes, and aminophenols, and the like, which are compounds having a functional group. For example, as a substrate, phenyl-phenyl derivatives such as phenylphenyl derivatives, aniline derivatives, toluidine derivatives, benzoic acid derivatives and the like can be mentioned by using a redox reagent, and specific examples thereof include N, N dimethylanilin, N, N getilanilin, 2, 4 dichlorophenyl, N-acetyl-Nole (N- (2-hydroxy-3-sulfopropyl) -3, 5-dimethoxyanilin (DAOS), N-acetyl _ N_ sulfopropyl-3, 5 dimethyl alcohol Niline (MAPS), N-Ethyl _ N_ (2-hydroxy-3 _ sulfopropyl) _3, 5_ dimethylamine (MA MA S), N- ethynole N_ (2-hydroxy 3_ sulfopropyl)-m- Toluidine (TOS), N-Ethyl_N-Sulphopropyl-m_Anicidin (ADPS), N-Ethinore-N-Sulphopropylanilin (ALPS), N-Ethyl_N_Sulphopropyl-3, 5-Dimethoxya Nirin (DAPS), N_sulfo RO PILL _3, 5-Dimethoxyanilin (HDAPS), N-Ethino-R-N-Sulphopropyl-I m_-Tonoridine (TOPS), N-ETH-N- (2-Hydroxy- 3 sulfo-propyl) m-Anicidin (AD S) ), N-acetyl-N- (2-hydroxy-3-sulfopropyl) anilin (ALOS), N_3- (2-hydroxy-3 sulfopropyl) _3, 5-dimethoxyanilin (HDAOS), N-sulfopropylanilin (HALPS), o-dianisidine, o-tolidine, 3,3-diaminobenzidine, 3,3,5,5-tetramethylbenzidine, N- (carboxymethylaminocarboyl) -4, 4-bis (dimethylamino) ) Biphenylamine (DA64), 10-(Carboxymethylamino power norebonyl) _3, 7_ bis (dimethylamino) phenothiazine (DA 67), 3, 5-dinitroresornic acid, 5-aminosalicylic acid, 3-hydro Cyanthranilic acid, 3, 5-diaminobenzoic acid, etc., and 4-aminoantipyrine, 0-pheniradidiamine, 1-amino-1 2-naphthol- 1 4-sulfonic acid, 1-phenileu 3-methyl-5- Pyrazolone, 2-amino-1-naphtho-l-6-sulfonic acid, 3-methyl_2-benzothiazolinone hydrazone, 2-amino-1-phenol-1-sulfonic acid, 2,6-dibromo-4-aminophenyl, 2, 2'-Azinol- (3-Ethylbenzothiazoline 6-sulphonic acid) dianmonium salt, 2, 2, _ azinobis (3 ethylbenzothiazoline _ 6_sulphonic acid) Ammonium salt (ABTS), force tec -Also, tannin, epicatequin, epigalocatechin etc. may be mentioned.

In addition, when it is intended to observe fluorescently further, a compound that emits fluorescence by oxidation, eg, For example, homovanillic acid, 4-hydroxyphenylacetic acid, tyramine, paracresol, diacetinole fluorescin derivatives and the like, and as a chemiluminescent compound, pyrogau-nore etc. may also be mentioned. The substances shown here are only an example, and all substances that significantly accelerate the light absorption wavelength change reaction when the enzyme is added and reacted with oxygen are included in this.

In addition, another compound may be coupled to the substrate to adjust the light absorption wavelength. In addition to substrates such as 4-amino-phenol (4AP), 2,6-dibromo-l-aminophenol, ABTS, etc., when phenol, 4-hydroxybenzoic acid, etc. are allowed to co-exist and act on enzymes, light is absorbed in the visible light range A wavelength reaction occurs, and the color tone differs depending on the type of substrate, and the color tone can be selected. Furthermore, when it is desired to change the light absorption wavelength change reaction by enzymes more drasticly than a certain threshold of oxygen concentration, or when the light absorption wavelength change reaction is caused in the presence of oxygen, the sensitivity as an oxygen detection agent is too high. The coexistence of an antagonist such as an inhibitor, a substrate analog or a reducing agent can slow the reaction of changing the light absorption wavelength or reduce the sensitivity. Inhibitors include azide, cetyldithiocarbamic acid, thiosulfate, fluoride, cyanide, PCMB, EDTA, divalent and trivalent metals, etc., and substrate analogs such as D_amino acids, 3,5— Examples include dinitrobenzoic acid and thiosalicylic acid. Examples of the reducing agent include dithiothreitol, cysteine, glutathione, mercaptoethanol, potassium ferricyanide, hydrogen iodide, sodium thiosulfate, aldehydes, sugars, formic acid, oxalic acid and the like. What is shown here is just an example, and antagonists of different types and concentrations may be used in combination as appropriate.

Furthermore, since the above-described redox indicator, enzyme, enzyme detection solution using an enzyme and a substrate consumes oxygen in a reaction system, it can be used as an oxygen absorber in the functional part.

Thus, by impregnating the functional part of the present invention with a functional liquid having a specific function, it is possible to easily introduce functions such as a humidity control agent, an ethanol evaporation agent, a carbon dioxide gas generating agent, etc. to the adhesive label It is. The functional part of the present invention mainly indicates a site containing a functional liquid, but may contain other substances (eg, acid 'alkali regulator, stabilizer, other coloring agents (eg, coloring), etc.) in the support, There should be no functional problem.

[0061] The protective layer in the present invention plays a role as a heat shrinkable layer, as well as the environment in the container or the bag. It is preferable to have the function of transmitting to the functional unit. In addition, when the contents are food, it is preferable to provide a protective function to ensure safety by isolating functional liquid from coming into direct contact with the contents. For example, when the functional part contains an oxygen detection agent and an oxygen absorbent, the protective layer may be a film which can separate the contents from the functional liquid, such as metal, paper, etc., in addition to the commonly used resin film. Good. Among them, it is preferable to use, as the protective layer, a resin film in which the oxygen permeability can be easily set for a while from the viewpoint of oxygen detection concentration, oxygen detection rate, oxygen absorption amount, oxygen absorption rate and the like. Then, the oxygen permeability and the water vapor permeability of the resin film may be selected as necessary. For example, when it is desired to confirm the presence or absence of oxygen instantaneously with low oxygen, it is preferable to use a resin film having high oxygen permeability and as thin as possible.

The resin film that can be used in the present invention has no problem in single layer or multiple layers, and the resin used may be selected according to the desired oxygen detection concentration. Examples of the resin film include polyolefin resins (polyethylene resin (HDPE, LLDPE, etc.), polypropylene resin (PP), polybutene-11 resin (PB), poly-4-methylpentene resin, etc. Polyolefin resins such as PO) or ethylene monovinyl acetate copolymer resin (EVA), ethylene monomethyl methacrylate copolymer resin (EMA etc), ethylene vinyl alcohol copolymer resin (EVOH etc) Aromatic polyester resin such as modified product (PO modified product), polyethylene terephthalate (modified) resin (PET etc.), polybutylene terephthalate (modified) resin (PBT etc), or polylactic acid resin And aliphatic polyester resins including polydarhydric acid resins, polysalt biphenylidene resins (PVD C), polysalt vinyl resins (PVC) Chlorinated resin, α-olefin or carbon monoxide copolymer resin (including hydrogenated resin), ethylene (others such as ethylene, etc.) styrene copolymer resin (containing hydrogenated resin), ethylene-cyclic carbonization A resin composition selected mainly from at least one of a hydrogen compound copolymer resin (containing a hydrogenated resin), a polyamide resin (Ny), a strong pro-rataton resin, etc. as a single layer, or a multilayer of these, or this layer A film obtained by laminating different resins, or a stretched (including a film having a shrinkability) or an unstretched resin film made of these resins may be mentioned.

Further, the moisture permeability of the protective layer of the present invention is, from the viewpoint of the oxygen absorption function, 0.11 to 300 gZ (m ² More preferably, it is 0 · 1−280 g / (m ² ′ 24 hr), more preferably 0.3 3 − 260 g / (m ² ′ 24 hr). Furthermore, the thickness of the protective layer of the present invention is preferably 3 to 100 μm ΐ, more preferably 10 to 80 μm, and more preferably 15 from the viewpoint of mechanical stiffness and handling when produced by a machine. It is 70 μm.

The container referred to in the present invention is a container which has a form consisting of a receiving container and a lid and is for containing contents. The material of the container may be any as long as it can contain the contents, and plastic, metal, wood, paper, other single substance or lamination of the aforementioned materials, etc. may be mentioned. Also, the lid mentioned here covers the upper part of the receiving container, and any material can be used as long as it can cover the receiving container containing the contents. Plastic, metal, wood, paper, etc. Or a laminate of the above materials. From the viewpoint of checking the contents visually, it is preferable that the lid covering the upper part is a transparent plastic with excellent gloss.

[0065] In the present invention, the term "bag" refers to a container into which things are put and the mouth is closed. The material of the bag may be any plastic, metal, paper, other single substance or a laminate of the aforementioned materials, as long as the bag can be formed. Here, plastic refers to thermoplastic resin and thermosetting resin, but any resin generally used for containers or bags may be used. For example, as thermoplastic resins, polyethylene resin, polypropylene resin, polystyrene resin, methacrylic resin, polychlorinated burle resin, polyamide resin, polycarbonate resin, polyethylene terephthalate resin, polybutylene terephthalate resin, cellulose acetate resin, ethylene-bule alcohol system Copolymer resins (EVOH etc.) and the like are mentioned, and as thermosetting resins, urea resin, melanin resin, xylene resin, phenol resin, unsaturated polyester resin etc. are mentioned, and these single resins or copolymer resins etc. It can be mentioned.

[0066] For forming the container or the bag, films and sheets such as single layer or multilayer structure composed of these resins can be used. In addition, the container or the bag is preferably made of a plastic having gas-nore uniformity from the viewpoint of sealing property. In the case of packaging by a container, it is preferable that the container or the lid have gas barrier properties. However, containers and lids that do not have gas barrier properties can be treated with a gas barrier film using Packaging and covering so as to cover the outer part · Even if the container and lid having gas barrier properties are covered with a film having no gas barrier property so as to cover parts other than the air passage · Sealed Also, if the entire container is then sealed by sealing the air passage with an adhesive label, there is no problem.

[0067] In the case of the container, the shape of the edge of the opening surface of the receiving container and the lid may be linear or curved. In addition, the shape of the container opening surface may be circular, triangular, rectangular (rectangular, square), other polygonal, or rhombus, elliptical, or amorphous formed of a curve. For example, a so-called food pack, in which one side of a receptacle and a lid is joined via a hinge part. In addition, the bag and the receiving container and the lid are made of films and sheets such as single layer or multilayer structure composed of these resins. Further, in the case of a multilayer structure, there are coextrusion methods, various laminating methods and the like as a method of forming a multilayer, but it may be appropriately selected. In the sheet used in the present invention, a material having a gas barrier property may be used as needed. In order to form a container from this thermoplastic resin sheet, it is preferable to form it by a heat forming method such as pressure forming, vacuum forming, vacuum pressure forming and the like. Also, the air passage may be cut out by, for example, cutting off a cutting blade called a punching die at an arbitrary position of the molded container.

In addition, the openings of the receiving container and the lid may have flanges of various shapes. The flange means a hook-like connecting portion which overlaps when the container and the lid overlap, and may have a fitting structure. The fitting structure means that the opening of the receiving container and the lid has a groove for fitting between the container and the lid. The fitting portion can be roughly divided into three types: outer fitting, inner fitting, and inner and outer fitting. The outer fitting is a shape that is inexpensive and easy to create, as it does not require much mold precision when molding the container.

On the other hand, inner fitting requires mold accuracy when molding the container as compared with outer fitting, and it is expensive in cost, but if the contents are sugary vegetables etc containing juice, the juice content will be high. It can prevent the outflow from the container. Further, the inside and outside fitting requires the accuracy of the mold when molding the container, and the cost becomes quite expensive, but the container and the lid come off even if a slight impact is applied which increases the fitting strength of the fitting portion. It is the most expensive fitting shape without it.

The packaging method in the present invention will be described. In the packaging method of the present invention, the contents are put in a container or a bag, and degassing or degassing through an air passage with the seal other than the air passage closed. Then, the air passage is sealed and sealed by closing the air passage with an adhesive label. In particular, when using a container, put the contents in the container and seal the polymerizing flange portion of the container and the lid, then degas the air in the container from the air passage provided in the lid or replace it with the desired gas, Seal the vent in the lid with the label. In the case of a sealed container, the lid covers the upper part of the receiving container, and the material is resin, and so long as it can cover the receiving container containing the contents. Further, from the viewpoint of visually confirming the contents, it is preferable that the lid covering the upper part is transparent, and that it is a resin that is more transparent and superior in gloss than the viewpoint of cosmetic properties. Furthermore, it is preferable that the height of the receiving container is lower than the height of the lid covering the upper part, from the viewpoint of exerting the sense of volume of the contents by the display effect of the container. The shape of the container in the present invention may be rectangular, cylindrical, conical, polygonal, polyhedral, cylindrical or the like, or any combination thereof. Further, the sealing of the air passage by the adhesive label means that the air passage (hole) provided in the lid is straddled and glued in a bent state.

The air passage of the present invention will be described. The air passage of the present invention is a passage through which gas can move in and out of the container or bag. Also, the size, shape, number, etc. of the gas should be able to move in and out of the packaging container. Among them, it is more preferable that the air passage be provided on the lid, from the viewpoint of the ease of closing the hole after gas replacement and the prevention of the outflow of the contents, on the top face of the preferable lid.

[0072] The pore size, relative to the internal volume 1000 cm ³ of the packaging container, it is preferable aperture area of the holes is 0. 3- 3c m ^2. Within this range, particularly in the case of a container, the resistance of passage during gas degassing and gas filling is small, and deformation of the container during gas replacement is small, and the mechanical strength of the adhesive label may be relatively small. Have an effect. The opening area of the preferred vent path 0. A 3- 3 cm ^2, more preferably 0. 4-2. 8 cm ^2, more preferably from 0. 6- 2. 5 cm ^2.

[0073] The opening shape of the air passage of the present invention only needs to be able to ventilate the inside and the outside of the packaging container. As an example, the opening shape of the air passage is a square (A in FIG. 1), a rectangle (B in FIG. 1), a quadrangle (C in FIG. 1) having corner portions R, a polygon (D in FIG. 1). ), Circles (E in Fig. 1), semicircles (F in Fig. 1), ellipses (G in Fig. 1), semi-elliptics (H in Fig. 1), stars (1 in Fig. 1), amorphous (Fig. 1) In addition to fully cut-out cutouts such as J), U-shaped Examples include 切) in Fig. 1, V (P in Fig. 1), U (Q in Fig. 1), C (R in Fig. 1), and irregular cuts (S in Fig. 1). These cut shapes are more preferred because there are no chips when drilling the lid.

[0074] When the opening shape of the air passage is such a slit shape, the area of the air passage is represented by the maximum area which is opened when the cut tongue portion is folded back and the hole is expanded.

Furthermore, in order to reduce the complexity when closing the air passage and to improve the appearance of the packaging container, the number of air passages is preferably as small as possible. In addition, even if the air passage is a large number of holes, it is possible to reduce the mechanical strength of the adhesive label by concentrating the small holes in one location and closing them with one adhesive label. Is also preferable because it can be used.

[0075] By sealing the opening of the container or bag of the present invention, it becomes possible to control the composition of the gas inside the packaging container or bag through the air passage, which differs from the oxygen concentration in the air. Environment can be realized. Examples of environments different from oxygen concentration in air include vacuum packaging in which the inside of a container or bag is deaerated and sealed in a vacuum and sealed, and gas substitution in a container or bag in which gas substitution is performed in a desired gas atmosphere. Packaging etc. are mentioned.

The gas replacement in the present invention will be described. In the present invention, gas replacement means replacing air in a sealed container with a desired gas. The gas replacement has effects such as the improvement of the storage stability of the contents and the appearance of the color of the product. For example, by holding food or the like in an inert gas, (1) oxidation of fat and oil components can be prevented, (2) preservation of active ingredients such as vitamin, (3) rot due to mold, fungus and yeast reproduction. The effects such as prevention, (4) discoloration of pigment, prevention of discoloration, and (5) prevention of scattering of aroma are obtained. Furthermore, the storage stability of the contents can be further improved by substituting it with a gas having a bacteriostatic action such as carbon dioxide gas.

[0077] The gas may be any of the generally known gases. For example, nitrogen, carbon dioxide (carbon dioxide gas), oxygen, argon and the like can be mentioned, and these can be used alone or in combination.

Also, ozone having a bactericidal effect against fungi and fungi and yeast, and natural and synthetic antibacterial substances (eg, hinokitiol etc.) may be used. The gas replacement method may be any method as long as gas replacement can be performed. The gas replacement method generally includes a gas flash method, a nozzle method, and a chamber-one method. The gas flush method is a method of replacing the air in the container or bag with the gas by gas flushing the desired gas in the container or bag. In addition, the Noznore method is a method mainly used for gas replacement of bags. A nozzle is inserted into a force bag, the air in the bag is degassed from the nozzle, and then the desired gas is removed from the Noznore. It is a method of introducing and replacing in a bag. Furthermore, in the one-chamber type, a container or bag containing contents is placed in a certain space (chamber one), the inside of the chamber is once evacuated, and then the desired gas is introduced into the chamber to carry the container or bag. Gas exchange inside the These methods may be freely selected according to speed, cost, substitution rate and the like.

[0079] Also in degassing packaging for sucking and degassing the gas in the container or bag, the gas in the container or bag is replaced with the desired gas in order to control the composition of the gas remaining in the container or bag. After that, it is preferable to perform suction and degassing.

As the gas composition in the container or the bag, when the content is a food, it is preferable to use carbon dioxide having a bacteriostatic action as one of the composition components in order to prevent the rot of the food. The content of carbon dioxide may be 100%, which is preferably 3% or more of the whole due to the bacteriostatic effect. Also, in order to prevent food spoilage, it is good to use alcohol with germicidal action as one of the gas components. The alcohol content may be up to a saturated vapor amount which is preferably at least 0.5% of the whole, from the effect of the bactericidal action. The term "alcohols" as used herein refers to a compound in a form in which a hydrogen atom of a hydrocarbon is substituted by a hydroxyl group, and examples thereof include methanol, ethanol, propanol, isopropanol, butanol and the like. From the viewpoint of food safety, the alcohols of the present invention are preferably ethanol, propanol and isopropanol, more preferably ethanol and propanol, and still more preferably ethanol.

When the container of the present invention (FIG. 7A: when the adhesive label is provided on the lid top surface, FIG. 7B: when the adhesive label is provided on the lid side surface) or a bag (FIG. 8) is used as a package The contents mainly include food. Foods include fresh fish called fresh fish, fresh meat, fresh vegetables, as well as fresh vegetables sold at supermarkets, convenience stores, etc. Food, steamed food, fried food), lunch box, etc. Furthermore, in addition to the food packaging described above, it may be used in any application where it is necessary to confirm the presence or absence of oxygen in the sealed space. For example, in addition to packaging of metal parts such as precision machine parts and screws, and packaging of electric parts such as electronic boards, there are applications to medicines, cosmetics and the like.

[Example]

Hereinafter, embodiments of the present invention will be described in detail based on examples, but the present invention is not limited to these examples.

<1. Creation of adhesive label>

1-1. Adhesive label

An adhesive label was prepared using the multilayer sheet and adhesive layer having the layer constitution and thickness shown in Table 13 as the base material layer of the adhesive label. The shrinkage start temperature of the produced adhesive label and the peeling state by the package test are shown in Table 13. (Base material layer: diameter 35 mm φ, adhesive layer: 25 g / m 2)

1-2. Preparation of adhesive label with oxygen detection function

100 mM of the enzyme (ascorbine acid oxidase) and the substrate (2, 2, 1-azino-bis (3-ethylbenzylazothiazoline- 1-sulfonic acid) diammoium salt (ABTS)) as a solvent (oxygen concentration Oppm) as a solvent The enzyme solution was dissolved at a concentration of 80 U / ml of the enzyme solution and 4 mg / ml of the substrate solution, respectively, in acetic acid-sodium acetate buffer (adjusted to · = 4 · 0) to prepare a pre-prepared enzyme solution and a pre-prepared substrate solution. The prepared enzyme and substrate solutions were mixed in an oxygen-free atmosphere in a glove box to prepare a functional fluid. As shown in Fig. 3, a 340 μm thick filter paper with a diameter of 5 mm is bonded to the center of the adhesive label (material: ΡΕΤ 75 μ 直径, diameter 35 mm 、, acrylic (AC) adhesive 25 g / m ² ) The filter paper was coated with 5 μl of the functional fluid, the centers were aligned, and the heat-shrinkable and protective layer (material: OPS 25 μm, diameter 22 mm φ) was used to cover the filter paper to form an adhesive label. This adhesive label was attached to a separator (PET / ALZPET 3 layer) coated with aluminum foil (AL) with PET. Storage was carried out by sticking 1000 sheets of adhesive labels in a state of being attached to a separator, sealing the nitrogen with an oxygen scavenger together with a barrier film in a roll state, and storing under refrigeration (5 ° C.) in a light shielding state.

<2. Create container (body, lid, adhesive tape)> 2-1. Main body

A dry film of LL / NY / EVOH / NY co-pressed film (50 μ ΐ に) was formed on a filled polypropylene resin sheet (PP) and molded (Fig. 4). The above "LL" means linear low density polyethylene.

2-2. Lid

An OPS sheet (250 μm) formed by dry laminating a LLZNY / EV〇H / NY co-pushed film (50 μm) was used. After molding, an opening with a diameter of 20 mm was punched out round on the upper surface of the lid using an intermediate pump of a molding machine, and then the periphery of the molded lid was punched out to make the lid (FIG. 5).

2-3. Adhesive tape

An acrylic adhesive was applied at 25 g / m ² to unstretched nylon (30 zm), and it was slit to a width of 10 mm and wound on a paper tube.

<3. Package test 1>

An adhesive label and an oxygen absorbent adhesive label were prepared by coating an aluminum foil with a PET-coated separator (PET / AL / PET trilayer) according to the above procedure. A container with a 20 mmφ holed lid on the top surface and a container containing the contents was sealed with adhesive tape, and the container was placed in a glove box adjusted to the mixed gas composition shown in Table 11. The adhesive label peeled off from the separator was adhered from the outside of the lid to the open top surface of the hole to obtain a sealed container (FIG. 6). After that, the color development time and the oxygen concentration were measured for a while (storage temperature: 20 ° C., container volume: 500 cc, contents: chopsticks (100 g of rice + 100 g of ingredients)).

<4. Evaluation of each physical property>

4-1. Moisture permeability

It carried out based on JIS-Z-0208. (40 ° C-90% RH)

4-2. Oxygen permeability

It went according to ASTM-D-3985. (20 ° C_60% RH)

4-3. Haze measurement

It carried out based on ASTM-D-1003.

4-4. Creation of oyakodon The omelet bowl of the present invention was prepared using chicken meat, chicken eggs, soup stock and the like according to the usual preparation method. Moreover, the rice used what was cooked with the rice cooker using standard rice.

4-5. Measurement of oxygen and carbon dioxide composition ratio in packaging container space

The oxygen concentration and the carbon dioxide concentration in the space inside the sealed packaging container at 20 ° C. were measured using PBI Dansensor Corporation Checkpoint (trade name). The nitrogen concentration is 100

Calculated by subtracting oxygen concentration and carbon dioxide concentration from%.

4-6. Storage temperature measurement

The temperature was measured using a button-type cool memory (trade name) manufactured by Sanyo Electric Co., Ltd. (Adhesive label storage temperature 5 ° C, evaluation storage temperature 20 ° C)

4-7. Bonding strength

It measured by the 180-degree peeling method of JIS_Z_0237. The outline of the measurement method is shown below. A 25 mm wide label was attached to the stainless steel plate, and the force required to peel one end of the label from the stainless steel plate in the 180 ° direction at a peeling speed of 300 m / min toward the other end was used.

4-8. Stab strength

Fix the label sheet before labeling in accordance with Agricultural and Forestry Standard Article 10 in a 125 mm square frame and pierce the needle with a diameter of 1.0 mm and a tip shape of 0.5 mm R at a speed of 50 mm / min. The maximum load until the needle penetrated was measured, and the value was taken as the strength.

4-9. Measurement of thermal contraction rate and thermal contraction start temperature

Immerse a sample piece (50 mm square in MD and TD directions) in silicone oil set to a prescribed temperature for 3 minutes, then measure the length of each side of the heat shrunk sample piece and shrink at that temperature The rate was calculated. In addition, a temperature at which the shrinkage rate is 3% or more was taken as the shrinkage start temperature.

4-10. Warpage measurement of adhesive label

The adhesive label after the experiment obtained by each example was placed on a flat place, and the maximum height in the vertical direction was measured.

<5. Package Test 2>

A composite filler-filled polypropylene resin sheet and a composite polystyrene sheet were formed into the shapes shown in FIG. 4 (main body) and FIG. 5 (lid), and the respective flanges were sealed with adhesive tape ( Figure 6). The inside of the container was replaced with a gas having the gas composition shown in Table 13 via an air passage, and the air passage of the container was sealed using the adhesive label shown in Table 13. Thereafter, the measurement of the oxygen composition ratio in the container, the observation of the ability of the oxygen detecting agent provided in the adhesive label, and the observation of the heat treatment with an electron range (1600 W) were performed.

Evaluation

AA: capable of oxygen detection. After heating starts with the microwave, the internal pressure rises with the temperature rise of the contents, the adhesive label peels off, the internal pressure is released safely, the package bursts in the microwave and the contents scatter Can be prevented. After microwave treatment, the package was taken out and it was observed whether the adhesive label closed the air passage by the adhesive label's own weight. As a result, the adhesive label was attached to the adhesive side due to the shrinkage of the heat shrink layer (protective layer). It warps into an arc and does not completely block the air passage. In addition, when the package was cooled to a certain extent, an attempt was made to reseal the arc-shaped adhesive label with a finger, and it is possible to re-seal by the adhesive force of the adhesive layer of the adhesive label.

A: After the start of heating by the microwave, the internal pressure rises with the temperature rise of the contents, the adhesive label peels off, the internal pressure is released safely, and the package ruptures in the microwave. It is possible to prevent the contents from scattering. After microwave treatment, the package was taken out, and it was observed whether the adhesive label closed the air passage by the adhesive label's own weight. The adhesive label formed the adhesive side by shrinkage of the heat-shrinkable layer (protective layer). It warps into a circular arc and does not completely block the air passage. In addition, when the package was cooled to a certain extent, an attempt was made to reseal the arc-shaped adhesive label with a finger, and it is possible to re-seal by the adhesive force of the adhesive layer of the adhesive label.

B: After heating is started by the microwave, the internal pressure rises with the temperature rise of the contents, the adhesive label peels off, the internal pressure is released safely, and the package bursts in the microwave. It is possible to prevent the contents from scattering. After microwave treatment, the package was taken out, and it was observed whether the adhesive label closed the air passage by the adhesive label's own weight. The adhesive label formed the adhesive side by shrinkage of the heat-shrinkable layer (protective layer). It warps into a circular arc and does not completely block the air passage. However, when the package was cooled to a certain extent, an attempt was made to re-seal the arc-shaped adhesive label with a finger, but due to the adhesive force of the adhesive layer of the adhesive label, re-sealing was attempted. Impossible to seal.

C: After heating is started by the microwave, the internal pressure rises with the temperature rise of the contents, the adhesive label does not peel off, the internal pressure is safely released, and the package is ruptured in the microwave It can not prevent the contents from being scattered. Alternatively, after microwave treatment, it was observed whether the package was taken out and the adhesive label closed the air passage by its own weight, and the adhesive label completely closed the air passage after the internal pressure was released. After that, the whole container is crushed by atmospheric pressure.

[Example 1 1 7]

Based on Tables 1 and 2, adhesive labels of Example 1-17 were prepared. The package test was performed using those adhesive labels. The results are shown in Tables 1 and 2.

In Example 17 of the present invention, in heating treatment with a microwave oven, it is possible to safely discharge the gas in the package which has risen in internal pressure, and to automatically re-adhere the adhesive label to the container after heating is completed. It could be prevented by the deformation of the adhesive label. Therefore, it was possible to prevent the container from being dented or crushed due to the volume change of the container or the bag at the time of cooling. In addition, since the container having a gas barrier, the lid, the adhesive tape and the adhesive label are used in this embodiment, the gas barrier function is exhibited to prevent the inflow of oxygen from the outside of the container and to prevent deterioration of contents such as oxidation. Was able to dramatically improve the preservation of food. Furthermore, in Example 7 of the present invention (adhesive label with oxygen detection function: FIG. 3 equivalent), the functional part in the adhesive label is white in low oxygen condition (only color of filter paper) and blue-green in high oxygen condition. And exhibited an oxygen detection function.

[Comparative Examples 1 and 2]

Based on Table 3, adhesive labels of Comparative Examples 1 and 2 were prepared. A package test was performed using the adhesive labels. The results are shown in Table 3.

The adhesive labels of Comparative Examples 1 and 2 were able to safely release the internal pressure of the package when heated by the microwave oven. However, after the internal pressure was released, the adhesive label closed the air passage by the own weight of the adhesive label, and after cooling, the package was crushed by atmospheric pressure.

In Tables 13 and 13 below, PET is polyethylene terephthalate (PET-based label obtained by SATO Ichikeni) and PE is polyethylene (Kojin Co., Ltd. Kojin Polyset-UM Particularly, PE-based shrink film, NY: nylon (emblic film manufactured by Unichika Co., Ltd.), PP: polypropylene (Kojin Co., Ltd. cordin polyset PP shrink film), PS: polystyrene (Asahi Kasei Co., Ltd.) Indicates film (trade name), OPS (registered trademark). Also, the symbol "*" indicates that stretching was performed.

[table 1]

Example 1 Example 2 Example 3 Example 4 Layer Configuration of Adhesive Label

Base layer Base layer Base layer

[S009 base layer

Heat shrink layer Heat shrink layer Heat shrink layer Heat shrink layer

Adhesive layer Adhesive layer Adhesive layer Adhesive layer

PET (50 pm)

Material exhibition PET (75 pm) PP (25 μηπ) PET (75 μπι) PET (75 μπι) Adhesive by dry lamination

Resin heat shrinkage S * PS (25 μππ) * PS (25) * PE (25 μητι) * PP (25

(Thickness) Adhesive layer AC system (25 g / m ² ) Rubber system (25 g / m ² ) AC system (25 g / m ² ) Silicon system (25 g / m ² ) Function

Number of layers

Sticking strength (N) 3.1 3.5 3.1 3 1 Adhesive label oxygen permeability

150 100 150 150 (ml / (m ² -day-MPa))

Adhesive strength

6.2 2.5 8.4

(N / 10 mm width)

Warpage amount of adhesive label

3.5 3.3

(mm)

Package test results A to B

Initial gas composition

Oxygen 0.1 0.1 0.1 0.2 Silicon dioxide 70.2 50.3 69.6 30.5

29.7 49.6 30.3 69.3 Gas composition Nitrogen

Result after 10 days

Oxygen 0.3 0.4 0.3 0.5 carbon dioxide 62.2 30.2 40.1 17.2

37.5 69.4

Nitrogen 59.6 82.3

Example 5 Example 6 Example 7 Layer Configuration of Adhesive Label

Base layer Heat-shrink layer Base layer

Adhesive Ji Heat Shrink Layer Base Layer

Functional part [7 adhesive layer adhesive layer heat collecting box layer base layer PET (75 μπη) PET (75 μιτη) PET (75 μη)) heat collecting box) * ΝΥ (25 μμ)) * PS (25 μι)) * PS (25 μπτι resin of each layer 5

(Thickness) adhesive layer AC system (25 g / m ² rubber (25 g I m ^z) AC system (25 g / m '逋紙+ acid棄検known liquid functional layer

(Diameter 5 mm Thickness 340 μι) Number of layers 4 Sticking strength (Ν) 3.6 3.5 3.3 Adhesive label oxygen permeability

150 150 150

(ml / (m'-day MPa))

Adhesive strength

6.6 4.6

(N's 10 mm width)

Warpage of adhesive label j

4.1 4.4

(mm)

Packaging Test Results A A AA

Initial gas composition

Oxygen 0.2 0.3 0.2

L carbon monoxide 70.2 10.1 90.2

29.6 89.6 9.6 Gas composition Nitrogen

Result after 10 days

Oxygen 0.3 0.5 0.5: 1 »oxygen 60.4 4.2 71.3

Nitrogen 39.3 95.3 28.2

Although the present invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the present invention. is there.

This application is based on Japanese Patent Application (No. 2003-421244) filed on Dec. 18, 2003, the contents of which are incorporated herein by reference.

Industrial applicability

With the adhesive label of the present invention, the inside of the container can be degassed or filled with gas, and the deterioration of the contents such as oxidation can be prevented, and as a result, the storage stability of the food can be dramatically improved. Can. In addition, when the package is heated by a microwave oven or the like, the appearance of the package is not impaired. It can heat up. In addition, the gas in the package which has been raised in internal pressure at the time of heating can be discharged safely by the adhesive label of the present invention. In addition, by preventing the adhesive label from being re-adhered to the container automatically after the heating is completed, the container can be prevented from being dented or crushed due to the volume change of the container or the bag during cooling. Furthermore, by providing the adhesive label with the functional part, the adhesive label having the function can be easily made.

Claims

The scope of the claims

[I] An adhesive label comprising a substrate layer and an adhesive layer, wherein at least one of the layers constituting the adhesive label is a heat shrinkable layer.

[2] The layer constituting the adhesive label further includes a functional part and a protective layer, and the functional part is provided on the adhesive layer of the adhesive label, and the protective layer is provided to cover the functional part. The adhesive label according to claim 1.

[3] The adhesive label according to claim 2, wherein at least a part of the protective layer is in contact with the adhesive layer.

[4] The functional part according to claim 2, wherein the functional part contains at least one selected from an oxygen concentration detecting agent, an oxygen absorbing agent, a humidity control agent, an ethanol evaporation agent, a carbon dioxide gas generating agent, a freshness maintaining agent and a temperature detecting agent. Adhesive label as described.

[5] The adhesive label according to claim 2, wherein the functional part contains an enzyme.

[6] The adhesive label according to claim 1, further comprising a layer made of a gas barrier material.

[7] The adhesive label according to claim 2, wherein the protective layer is a heat shrinkable layer.

8. The adhesive label according to claim 1, wherein the adhesive layer comprises any adhesive selected from acrylic, rubber and silicon adhesives.

[9] A container or bag having at least one air passage is sealed at a location other than the air passage, and gas in the container or bag is degassed or replaced with another gas via the air passage, Then, the packaging method which block | blocks the said air path with the adhesive label of Claim 1.

[10] A packaging container or bag having the adhesive label according to claim 1.

[II] A package comprising the adhesive label according to claim 1.